JP5523816B2 - Modified resin composition, method for producing the same, and curable resin composition containing the same - Google Patents

Description

  The present invention relates to a modified resin composition obtained by reacting an epoxy resin and an alkoxysilane compound, a method for producing the same, a curable resin composition containing the composition, and a use thereof.

  Conventionally, an epoxy resin composition using an acid anhydride-based curing agent gives a transparent cured product and has high heat resistance and adhesiveness. Therefore, a light emitting diode (hereinafter abbreviated as a light emitting diode) and a photo It has been suitably used as a sealing resin for optical semiconductors such as diodes. However, in recent years, the performance of optical semiconductors has been improved, and as a resin for sealing light emitting diodes, in addition to the conventionally required good transparency, high heat resistance and adhesiveness, heat yellowing resistance, cold heat resistance during thermal cycling A cured product having excellent impact properties and having no surface tack is desired, and bisphenol A-based epoxy resins, bisphenol F-based epoxy resins, alicyclic epoxy resins, and the like that have been conventionally used In fact, a composition made of a resin cannot obtain sufficient characteristics.

  As a resin for a light-emitting element sealing material, several studies have been made on silicone resins having a siloxane skeleton that is stable against heat or light as a repeating unit. However, although the silicone resin is excellent in light resistance and heat resistance, it has low adhesiveness and peeling from the base material. Further, in some cases, the cured product has low hardness, surface tackiness, etc. Actually, many improvements are required, not satisfactory performance.

  On the other hand, some studies have also been made on modified resin composition compounds having a siloxane skeleton as a repeating unit and having an epoxy group as an organic group. The modified resin composition has not only the excellent transparency and heat resistance of the epoxy resin and a cured product having no surface tackiness, but also the oxidation resistance, and further, the cured product possessed by the silicone. It is expected to have flexibility.

For example, Patent Document 1 contains a T structure as an essential repeating unit and contains an epoxy group-containing organic group in the range of 0.1 to 40 mol% with respect to all organic groups bonded to a silicon atom in one molecule. A modified resin composition has been proposed.
Patent Document 2 describes a composition containing a silicone compound having a molecular weight in a specific range and having at least two epoxy groups in one molecule and its use for an optical semiconductor sealing material.
Patent Documents 3 to 5 disclose resin compositions obtained by mixing an epoxy resin and a silicone resin condensed in advance.
Patent Documents 6 to 11 disclose resin compositions obtained by mixing an epoxy resin and alkoxysilanes or a partial condensate thereof and then subjecting to dealcoholization reaction.
Patent Document 12 discloses a resin composition consisting of a modified phenoxy resin and an epoxy resin containing an alkoxy group twice the number of Si atoms in the molecule.

Japanese Patent No. 3263177 JP 2005-171021 A JP 2006-225515 A JP 2006-241230 A JP 2008-120443 A JP 2001-059011 A JP 2001-059013 A JP 2002-179762 A JP 2002-249539 A JP 2003-246838 A JP 2005-179401 A JP 2007-321130 A

  However, the resin compositions described in Patent Documents 1 and 2 are not yet at a satisfactory level with respect to cold-heat shock resistance and adhesiveness. Furthermore, the above-mentioned modified resin composition has low storage stability in some cases, and the viscosity of the resin tends to increase remarkably during storage, so it cannot be said that it has sufficient practicality.

  Moreover, the composition obtained by mixing the silicone resin previously condensed in the absence of an epoxy resin with an epoxy resin described in Patent Documents 3 to 5 has low storage stability, and the composition of the resin during storage is low. Viscosity tends to increase significantly. Furthermore, in some cases, it cannot be said that the epoxy resin and the silicone resin are sufficiently practical, for example, the epoxy resin and the silicone resin cannot be uniformly mixed.

Furthermore, when silicone is produced by dealcoholization reaction, alkoxy groups tend to remain in the silicone, and a resin composition containing an alkoxysilane residue as described in Patent Documents 6 to 12 is cured. The cured product obtained in this manner tended to decrease the thermal shock resistance during thermal cycling and the adhesiveness due to the generation of alcohol and vaporization by hydrolysis over time.
As described above, the materials disclosed in Patent Documents 1 to 12 still do not have sufficient performance, and further, in the Patent Document, there is a description or suggestion regarding a phenyl group having a fluorine atom as a substituent. Not seen at all.

  In view of the above circumstances, the present invention forms a cured product having good transparency, excellent heat-resistant yellowing, light resistance under heating conditions, and thermal shock resistance in a thermal cycle. An object of the present invention is to provide a modified resin composition that can be used and has good storage stability, and a curable resin composition, a light-emitting component, and a semiconductor device using the same.

  As a result of intensive investigations to solve the above problems, the present inventor is a modified resin composition obtained by reacting an epoxy resin and an alkoxysilane compound having a specific structure at a specific ratio, It has been found that the above problems can be solved by adjusting the amount of residual alkoxy groups in the composition to a specific range, and the present invention has been completed.

That is, the present invention is as follows.
[1] A modified resin composition obtained by reacting an alkoxysilane compound represented by the following general formula (1) in the presence of an epoxy resin (A),
_{^{(R 1) n -Si- (OR}} 2) 4-n ··· (1)
(Wherein n represents an integer of 0 or more and 3 or less. In addition, each R ¹ is independently a hydrogen atom or a) selected from an unsubstituted or substituted structure group consisting of a chain, a branch, and a ring. An organic group containing a cyclic ether group having an aliphatic hydrocarbon unit having one or more kinds of structures, 4 to 24 carbon atoms, and 1 to 5 oxygen atoms, b) unsubstituted Or a substituted aliphatic hydrocarbon unit having one or more structures selected from the group consisting of a chain, a branched chain and a ring, having 1 to 24 carbon atoms and 0 oxygen atoms A monovalent aliphatic organic group that is 5 or less, and c) an unsubstituted or substituted aromatic hydrocarbon unit that is unsubstituted or substituted as necessary, from a chain, branched, and cyclic An aliphatic hydrocarbon unit comprising at least one structure selected from the group consisting of And at least one organic group selected from the group consisting of monovalent aromatic organic groups having 6 to 24 carbon atoms and 0 to 5 oxygen atoms. On the other hand, each R ² independently has a hydrogen atom or d) an unsubstituted or substituted aliphatic hydrocarbon unit having one or more types of structures selected from a chain, branched, or cyclic structure group. And a monovalent organic group having 1 to 8 carbon atoms. )
The alkoxysilane compound is
(B) n = 1 or 2, and at least one alkoxysilane compound containing a group having at least one cyclic ether group as R ¹ ;
(C) an alkoxysilane compound containing n = 1 or 2 and a phenyl group having at least one fluorine atom as a substituent as R ¹ ;
Including
A modified resin composition represented by the following general formula (2), wherein a mixing index α of the alkoxysilane compound is 0.001 or more and 19 or less.
Mixing index α = (αc) / (αb) (2)
(In the formula (2), αb is represented by the general formula (1), the content (mol%) of the component (B) in the alkoxysilane compound, and αc is represented by the general formula (1). The content (mol%) of the component (C) in the alkoxysilane compound is shown.)

[2] The modified resin composition according to [1], wherein the amount of residual alkoxy groups in the modified resin composition is 5% or less.
[3] The modified resin composition according to the above [1] or [2], wherein the condensation rate of the alkoxysilane compound is 80% or more.
[4] The epoxy resin (A) is selected from the group consisting of an alicyclic epoxy resin, an aliphatic epoxy resin, a polyfunctional epoxy resin composed of a glycidyl etherified product of a polyphenol compound, and a nuclear hydride of an aromatic epoxy resin. The modified resin composition according to any one of [1] to [3] above, wherein the modified resin composition is one or more polyfunctional epoxy resins.
[5] The mixing index β of the alkoxysilane compound represented by the following general formula (3) is any one of the above [1] to [4], which is 0.01 or more and 1.4 or less. Modified resin composition of
Mixing index β = {(βn2) / (βn0 + βn1)} (3)
(In the formula (3), βn2 is the content (mol%) of the alkoxysilane compound in which n = 2 in the alkoxysilane compound represented by the general formula (1), and βn0 is the general formula (1). The content (mol%) of the alkoxysilane compound in which n = 0 in the alkoxysilane compound represented by the formula: βn1 is the alkoxysilane in which n = 1 in the alkoxysilane compound represented by the general formula (1) The content (mol%) of the compound is shown, and 0 ≦ {(βn0) / (βn0 + βn1 + βn2)} ≦ 0.1.

[6] Any one of [1] to [5] above, wherein a mixing index γ of the epoxy resin (A) represented by the following general formula (4) and the alkoxysilane compound is 0.02 to 15. The modified resin composition according to Item 1;
Mixing index γ = (γa) / (γs) (4)
(Here, in formula (4), γa is the mass (g) of the epoxy resin (A), and γs is an alkoxysilane compound in which n = 0 to 2 in the alkoxysilane compound represented by the general formula (1). The mass (g) of each is shown.)
[7] In the presence of the epoxy resin (A), the alkoxysilane compound represented by the following general formula (1) containing at least the following component (B) and component (C) is allowed to remain in the reaction system of water or a solvent. A step (a) of producing an intermediate by cohydrolysis by a refluxing step without taking out, and a step (b) of subjecting the intermediate produced by the step (a) to a dehydration condensation reaction,
And the modified index of the alkoxysilane compound represented by the following general formula (2) is 0.001 or more and 19 or less.
_{^{(R 1) n -Si- (OR}} 2) 4-n ··· (1)
(Wherein n represents an integer of 0 or more and 3 or less. In addition, each R ¹ is independently a hydrogen atom or a) selected from an unsubstituted or substituted structure group consisting of a chain, a branch, and a ring. An organic group containing a cyclic ether group having an aliphatic hydrocarbon unit having one or more kinds of structures, 4 to 24 carbon atoms, and 1 to 5 oxygen atoms, b) unsubstituted Or a substituted aliphatic hydrocarbon unit having one or more structures selected from the group consisting of a chain, a branched chain and a ring, having 1 to 24 carbon atoms and 0 oxygen atoms A monovalent aliphatic organic group that is 5 or less, and c) an unsubstituted or substituted aromatic hydrocarbon unit that is unsubstituted or substituted as necessary, from a chain, branched, and cyclic An aliphatic hydrocarbon unit comprising at least one structure selected from the group consisting of And at least one organic group selected from the group consisting of monovalent aromatic organic groups having 6 to 24 carbon atoms and 0 to 5 oxygen atoms. On the other hand, each R ² independently has a hydrogen atom or d) an unsubstituted or substituted aliphatic hydrocarbon unit having one or more types of structures selected from a chain, branched, or cyclic structure group. And a monovalent organic group having 1 to 8 carbon atoms. )
(B) n = 1 or 2, and at least one alkoxysilane compound containing a group having at least one cyclic ether group as R ¹ .
(C) An alkoxysilane compound containing n = 1 or 2 and a phenyl group having at least one fluorine atom as a substituent as R ¹ .
Mixing index α = (αc) / (αb) (2)
(Here, in the formula (2), αb represents the content (mol%) of the component (B), and αc represents the content (mol%) of the component (C).)

[8] The alkoxysilane compound represented by the following general formula (1) containing at least the following component (B) and component (C) is co-hydrolyzed by a refluxing step without distilling water or a solvent out of the reaction system. A step (c) of decomposing and producing an intermediate, and a step (d) in which a dehydration condensation reaction is performed in the presence of an epoxy resin (A) in the intermediate produced by the step (c),
And the modified index of the alkoxysilane compound represented by the following general formula (2) is 0.001 or more and 19 or less.
_{^{(R 1) n -Si- (OR}} 2) 4-n ··· (1)
(Wherein n represents an integer of 0 or more and 3 or less. In addition, each R ¹ is independently a hydrogen atom or a) selected from an unsubstituted or substituted structure group consisting of a chain, a branch, and a ring. An organic group containing a cyclic ether group having an aliphatic hydrocarbon unit having one or more kinds of structures, 4 to 24 carbon atoms, and 1 to 5 oxygen atoms, b) unsubstituted Or a substituted aliphatic hydrocarbon unit having one or more structures selected from the group consisting of a chain, a branched chain and a ring, having 1 to 24 carbon atoms and 0 oxygen atoms A monovalent aliphatic organic group that is 5 or less, and c) an unsubstituted or substituted aromatic hydrocarbon unit that is unsubstituted or substituted as necessary, from a chain, branched, and cyclic An aliphatic hydrocarbon unit comprising at least one structure selected from the group consisting of And at least one organic group selected from the group consisting of monovalent aromatic organic groups having 6 to 24 carbon atoms and 0 to 5 oxygen atoms. On the other hand, each R ² independently has a hydrogen atom or d) an unsubstituted or substituted aliphatic hydrocarbon unit having one or more types of structures selected from a chain, branched, or cyclic structure group. And a monovalent organic group having 1 to 8 carbon atoms. )
(B) n = 1 or 2, and at least one alkoxysilane compound containing a group having at least one cyclic ether group as R ¹ .
(C) An alkoxysilane compound containing n = 1 or 2 and a phenyl group having at least one fluorine atom as a substituent as R ¹ .
Mixing index α = (αc) / (αb) (2)
(Here, in the formula (2), αb represents the content (mol%) of the component (B), and αc represents the content (mol%) of the component (C).)

[9] The modified resin composition according to [7] or [8] above, wherein a mixing index β of the alkoxysilane compound represented by the following general formula (3) is 0.01 to 1.4. Production method;
Mixing index β = {(βn2) / (βn0 + βn1)} (3)
(In the formula (3), βn2 is the content (mol%) of the alkoxysilane compound in which n = 2 in the alkoxysilane compound represented by the general formula (1), and βn0 is the general formula (1). The content (mol%) of the alkoxysilane compound in which n = 0 in the alkoxysilane compound represented by the formula: βn1 is the alkoxysilane in which n = 1 in the alkoxysilane compound represented by the general formula (1) The content (mol%) of the compound is shown, and 0 ≦ {(βn0) / (βn0 + βn1 + βn2)} ≦ 0.1.
[10] Any one of the above [7] to [9], wherein a mixing index γ of the epoxy resin (A) represented by the following general formula (4) and the alkoxysilane compound is 0.02 to 15. A method for producing the modified resin composition according to Item;
Mixing index γ = (γa) / (γs) (4)
(In the formula (4), γa is the mass (g) of the epoxy resin (A), and γs is an alkoxysilane compound in which n = 0 to 2 in the alkoxysilane represented by the general formula (1). (The mass (g) is shown respectively.)

[11] The modified resin composition according to any one of the above [7] to [10], wherein the temperature in the refluxing step that does not involve distillation of water or solvent out of the reaction system is 50 to 100 ° C. Manufacturing method.
[12] Any of [7] to [11] above, wherein the condensation ratio of the intermediate obtained by cohydrolysis by a refluxing step without distilling water or solvent out of the reaction system is 70% or more. A method for producing the modified resin composition according to claim 1.
[13] The method for producing a modified resin composition according to any one of [7] to [12] above, wherein alkoxide-based organic tin is used as a catalyst in the co-hydrolysis.
[14] A curable resin composition obtained by further adding a curing agent to the modified resin composition according to the above [1].
[15] A curable resin composition obtained by further adding a curing accelerator to the curable resin composition according to the above [14].
[16] A light-emitting component produced using the curable resin composition according to [15] above.
[17] A semiconductor device including the light-emitting component according to [16].

  According to the present invention, it is possible to form a cured product having excellent heat-resistant yellowing, light resistance, and thermal shock resistance (cold thermal shock resistance in a thermal cycle), and a modified resin having good storage stability. It becomes possible to provide a composition.

  Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present invention”) will be described in detail. This invention is not limited to the form shown below.

The modified resin composition in the present invention is a modified resin composition obtained by reacting an alkoxysilane compound represented by the following general formula (1) in the presence of the epoxy resin (A),
_{^{(R 1) n -Si- (OR}} 2) 4-n ··· (1)
(Wherein n represents an integer of 0 or more and 3 or less. In addition, each R ¹ is independently a hydrogen atom or a) selected from an unsubstituted or substituted structure group consisting of a chain, a branch, and a ring. An organic group containing a cyclic ether group having an aliphatic hydrocarbon unit having one or more kinds of structures, 4 to 24 carbon atoms, and 1 to 5 oxygen atoms, b) unsubstituted Or a substituted aliphatic hydrocarbon unit having one or more structures selected from the group consisting of a chain, a branched chain and a ring, having 1 to 24 carbon atoms and 0 oxygen atoms A monovalent aliphatic organic group that is 5 or less, and c) an unsubstituted or substituted aromatic hydrocarbon unit that is unsubstituted or substituted as necessary, from a chain, branched, and cyclic An aliphatic hydrocarbon unit comprising at least one structure selected from the group consisting of And at least one organic group selected from the group consisting of monovalent aromatic organic groups having 6 to 24 carbon atoms and 0 to 5 oxygen atoms. On the other hand, each R ² independently has a hydrogen atom or d) an unsubstituted or substituted aliphatic hydrocarbon unit having one or more types of structures selected from a chain, branched, or cyclic structure group. And a monovalent organic group having 1 to 8 carbon atoms. )
The alkoxysilane compound is
(B) n = 1 or 2, and at least one alkoxysilane compound containing a group having at least one cyclic ether group as R ¹ ;
(C) an alkoxysilane compound containing n = 1 or 2 and a phenyl group having at least one fluorine atom as a substituent as R ¹ ;
Including
The mixing index α of the alkoxysilane compound represented by the following general formula (2) is 0.001 or more and 19 or less.
Mixing index α = (αc) / (αb) (2)
(In the formula (2), αb is the content (mol%) of the component (B) in the alkoxysilane compound represented by the general formula (1), and αc is represented by the general formula (1). (The content (mol%) of the component (C) in the alkoxysilane compound is shown.)

  The epoxy resin (A) used in the present invention is not particularly limited, and examples thereof include alicyclic epoxy resins, aliphatic epoxy resins, polyfunctional epoxy resins composed of glycidyl ethers of polyphenol compounds, and glycidyl ethers of novolak resins. Conventionally known epoxies such as polyfunctional epoxy resins, aromatic hydrides of aromatic epoxy resins, heterocyclic epoxy resins, glycidyl ester epoxy resins, glycidylamine epoxy resins, epoxy resins obtained by glycidylation of halogenated phenols, etc. Resin. These epoxy resins may be used alone or in combination.

  The alicyclic epoxy resin that can be used in the present invention is not particularly limited as long as it is an epoxy resin having an alicyclic epoxy group, and examples thereof include a cyclohexene oxide group, a tricyclodecene oxide group, and a cyclopentene oxide. An epoxy resin having a group or the like can be given. Specific examples of the alicyclic epoxy resin include 4-vinyl epoxycyclohexane, dioctyl epoxyhexahydrophthalate, and di-2-ethylhexyl epoxyhexahydrophthalate as monofunctional alicyclic epoxy compounds. Examples of the bifunctional alicyclic epoxy compound include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexyloctyl-3,4-epoxycyclohexanecarboxylate, 2- (3,4 -Epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexene dioxide, bis (3,4-epoxy-6-methyl) (Cyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3,4-epoxy-6-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethyl Glycol di (3,4-epoxycyclohexylmethyl) ether, ethylenebis (3,4-epoxycyclohexane carboxylate), 1,2,8,9- diepoxylimonene, and the like. Examples of the polyfunctional alicyclic epoxy compound include 1,2-epoxy-4- (2-oxiranyl) cyclohexene adduct of 2,2-bis (hydroxymethyl) -1-butanol. Furthermore, as what is marketed as a polyfunctional alicyclic epoxy compound, Epolide GT401, EHPE3150 (made by Daicel Chemical Industries Ltd.), etc. are mentioned.

The typical example of an alicyclic epoxy resin is shown below.

  The aliphatic epoxy resin that can be used in the present invention is not particularly limited, and specifically, 1,4-butanediol, 1,6-hexanediol, polyethylene glycol, polypropylene glycol, pentaerythritol. And glycidyl ethers of polyhydric alcohols such as xylylene glycol derivatives.

The following are typical examples of aliphatic epoxy resins.

  The polyfunctional epoxy resin comprising a glycidyl etherified product of a polyphenol compound that can be used in the present invention is not particularly limited, and specifically, bisphenol A, bisphenol F, bisphenol S, 4,4′-biphenol. Tetramethyl bisphenol A, dimethyl bisphenol A, tetramethyl bisphenol F, dimethyl bisphenol F, tetramethyl bisphenol S, dimethyl bisphenol S, tetramethyl-4,4'-biphenol, dimethyl-4,4'-biphenylphenol, 1- (4-hydroxyphenyl) -2- [4- (1,1-bis- (4-hydroxyphenyl) ethyl) phenyl] propane, 2,2′-methylene-bis (4-methyl-6-tert-butylphenol) , 4,4'- Chileden-bis (3-methyl-6-t-butylphenol), trishydroxyphenylmethane, resorcinol, hydroquinone, 2,6-di (t-butyl) hydroquinone, pyrogallol, phenols having a diisopropylidene skeleton, 1,1 Examples thereof include phenols having a fluorene skeleton such as di (4-hydroxyphenyl) fluorene, polyfunctional epoxy resins that are glycidyl etherified products of polyphenol compounds of phenolized polybutadiene, and the like.

A typical example of a polyfunctional epoxy resin which is a glycidyl etherified product of a phenol having a bisphenol skeleton is shown below.

  When a polyfunctional epoxy resin that is a glycidyl etherified product of a polyphenol compound is used, these repeating units (n in the chemical formula showing the above representative examples) are not particularly limited, but preferably 0 or more and 50 It is less than the range. If the number of repeating units is 50 or more, the fluidity is lowered, which may cause a practical problem. From the viewpoint of increasing the reactivity with the alkoxysilane compounds, and further from the viewpoint of increasing the fluidity of the resulting modified resin composition, the range of the repeating unit is preferably in the range of 0 to 10, more preferably 0.001 or more. The range is 2 or less.

  The polyfunctional epoxy resin that is a glycidyl etherified product of novolak resin is not particularly limited, and examples thereof include phenol, cresols, ethylphenols, butylphenols, octylphenols, bisphenol A, bisphenol F, bisphenol S, and naphthol. Glycidyl etherified products of various novolac resins such as novolak resins made from various phenols such as chlorophenols, phenol novolak resins containing xylylene skeleton, phenol novolac resins containing dicyclopentadiene skeleton, biphenyl skeleton containing phenol novolac resins, fluorene skeleton containing phenol novolac resins Etc.

Below, the typical example of the polyfunctional epoxy resin which is the glycidyl etherification product of a novolak resin is shown.

  The nuclear hydride of the aromatic epoxy resin that can be used in the present invention is not particularly limited. For example, a glycidyl etherified product of a phenol compound (bisphenol A, bisphenol F, bisphenol S, 4,4′-biphenol, etc.) or Nuclear hydrides of aromatic rings of various phenols (phenol, cresols, ethylphenols, butylphenols, octylphenols, bisphenol A, bisphenol F, bisphenol S, naphthols, etc.), nuclear hydrides of glycidyl ethers of novolac resins, etc. Is mentioned.

  There is no limitation in particular as a heterocyclic epoxy resin, For example, the heterocyclic epoxy resin etc. which have heterocyclic rings, such as an isocyanuric ring and a hydantoin ring, are mentioned.

  The glycidyl ester-based epoxy resin is not particularly limited, and examples thereof include epoxy resins composed of carboxylic acids such as hexahydrophthalic acid diglycidyl ester and tetrahydrophthalic acid diglycidyl ester.

  The glycidylamine epoxy resin is not particularly limited, and examples thereof include epoxy resins obtained by glycidylating amines such as aniline, toluidine, p-phenylenediamine, m-phenylenediamine, diaminodiphenylmethane derivatives, diaminomethylbenzene derivatives, and the like. It is done.

  Epoxy resins obtained by glycidylation of halogenated phenols are not particularly limited. For example, brominated bisphenol A, brominated bisphenol F, brominated bisphenol S, brominated phenol novolac, brominated cresol novolac, chlorinated bisphenol S, Examples thereof include epoxy resins obtained by glycidyl etherification of halogenated phenols such as chlorinated bisphenol A.

  Among the above, a cured product obtained by curing the target modified resin composition of the present invention is excellent in transparency, heat yellowing resistance, light resistance, and thermal shock resistance during thermal cycling. One or more kinds selected from the group consisting of alicyclic epoxy resins, aliphatic epoxy resins, polyfunctional epoxy resins composed of glycidyl ethers of polyphenol compounds, and nuclear hydrides of aromatic epoxy resins. It is preferably a polyfunctional epoxy resin, one or more polyfunctional epoxy selected from the group consisting of an alicyclic epoxy resin, a polyfunctional epoxy resin comprising a glycidyl etherified product of a polyphenol compound, and a nuclear hydride of an aromatic epoxy resin. More preferably, it is a resin.

  Although there is no restriction | limiting in particular about the viscosity in 25 degreeC of the epoxy resin (A) used by this invention, Since it tends to ensure the fluidity | liquidity as a liquid and to improve compatibility with an alkoxysilane compound, it is 1000 Pa. The liquid is preferably s or less, more preferably 500 Pa · s or less, still more preferably 300 Pa · s or less, and particularly preferably 100 Pa · s or less.

  The epoxy equivalent (WPE) of the epoxy resin (A) used in the present invention is not particularly limited, but is preferably 100 g / eq or more from the viewpoint of enhancing the storage stability of the modified resin composition of the present invention. From the viewpoint of increasing the thermal shock resistance of the cured product obtained by curing the modified resin composition of the invention, it is preferably 700 g / eq or less, more preferably in the range of 100 g / eq to 500 g / eq, and more preferably 100 g / eq. The range of eq or more and 300 g / eq or less is more preferable.

The alkoxysilane compound that can be used in the present invention indicates a silicon compound having 1 to 4 alkoxyl groups, and is represented by the following general formula (1).
_{^{(R 1) n -Si- (OR}} 2) 4-n ··· (1)
(Wherein n represents an integer of 0 or more and 3 or less. In addition, each R ¹ is independently a hydrogen atom or a) selected from an unsubstituted or substituted structure group consisting of a chain, a branch, and a ring. An organic group containing a cyclic ether group having an aliphatic hydrocarbon unit having one or more kinds of structures, 4 to 24 carbon atoms, and 1 to 5 oxygen atoms, b) unsubstituted Or a substituted aliphatic hydrocarbon unit having one or more structures selected from the group consisting of a chain, a branched chain and a ring, having 1 to 24 carbon atoms and 0 oxygen atoms A monovalent aliphatic organic group that is 5 or less, and c) an unsubstituted or substituted aromatic hydrocarbon unit that is unsubstituted or substituted as necessary, from a chain, branched, and cyclic An aliphatic hydrocarbon unit comprising at least one structure selected from the group consisting of And at least one organic group selected from the group consisting of monovalent aromatic organic groups having 6 to 24 carbon atoms and 0 to 5 oxygen atoms. On the other hand, each R ² independently has a hydrogen atom or d) an unsubstituted or substituted aliphatic hydrocarbon unit having one or more types of structures selected from a chain, branched, or cyclic structure group. And a monovalent organic group having 1 to 8 carbon atoms. )

  Here, the cyclic ether group in this invention is demonstrated. The cyclic ether group in the present invention refers to an organic group having an ether in which carbon of a cyclic hydrocarbon is substituted with oxygen, and usually means a cyclic ether group having a 3- to 6-membered ring structure. Among them, a 3-membered or 4-membered cyclic ether group having a large ring strain energy and high reactivity is preferable, and a 3-membered cyclic ether group is particularly preferable.

Next, R ¹ in the present invention will be described. In the present invention, each R ¹ independently represents a hydrogen atom, or [a] an aliphatic hydrocarbon having one or more structures selected from the group consisting of a chain, a branch, and a ring, which are unsubstituted or substituted. An organic group having a unit and containing a cyclic ether group having 4 to 24 carbon atoms and 1 to 5 oxygen atoms, [b] an unsubstituted or substituted chain, branched, and A monovalent aliphatic organic having an aliphatic hydrocarbon unit having one or more types of structures selected from a cyclic structural group, having 1 to 24 carbon atoms, and having 0 to 5 oxygen atoms A group, and [c] one or more aromatic hydrocarbon units that are unsubstituted or substituted, and are selected from the group consisting of a chain, branched, and cyclic structures that are unsubstituted or substituted as necessary. Having an aliphatic hydrocarbon unit consisting of a structure and having 6 to 24 carbon atoms And at least one organic group selected from the group consisting of monovalent aromatic organic groups having 0 and 5 or less oxygen.

  [A] having an aliphatic hydrocarbon unit composed of one or more structures selected from the group consisting of an unsubstituted or substituted chain, branched, and cyclic structure, and having 4 to 24 carbon atoms Examples of the organic group containing a cyclic ether group having 1 to 5 oxygen atoms include 4 carbon atoms such as β-glycidoxyethyl, γ-glycidoxypropyl, and γ-glycidoxybutyl. Glycidoxyalkyl group, glycidyl group, β- (3,4-epoxycyclohexyl) ethyl group, γ- (3,4-epoxycyclohexyl) propyl group, β- (3 , 4-epoxycycloheptyl) ethyl group, β- (3,4-epoxycyclohexyl) propyl group, β- (3,4-epoxycyclohexyl) butyl group, β- (3,4-epoxycyclo) Hexyl) such as an alkyl group substituted with a cycloalkyl group having a carbon number of 5-8 having an epoxy group and a pentyl group.

  [B] having an aliphatic hydrocarbon unit having at least one structure selected from the group consisting of an unsubstituted or substituted chain, branched and cyclic structure, and having 1 to 24 carbon atoms Examples of the monovalent aliphatic organic group having 0 to 5 oxygen atoms include [b-1] methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, and isobutyl group. T-butyl group, sec-butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, n-heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, Chain organic group consisting of aliphatic hydrocarbon such as tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, [b-2] cyclopentyl group, methylcyclopentyl group Organic groups consisting of hydrocarbons containing cyclic units such as cyclohexyl, methylcyclohexyl, norbornyl, [b-3] methoxyethyl, ethoxyethyl, propoxyethyl, methoxypropyl, ethoxypropyl, propoxypropyl, etc. Examples include an organic group containing an ether bond, [b-4] vinyl group, allyl group, isopropenyl group, butenyl group, isobutenyl group, pentenyl group, hexenyl group, and the like.

  [C] one or more structures selected from the group consisting of a chain, a branch and a ring, which are unsubstituted or substituted aromatic hydrocarbon units, and are optionally substituted or substituted. Examples of the monovalent aromatic organic group having an aliphatic hydrocarbon unit comprising 6 to 24 carbon atoms and 0 to 5 oxygen atoms include, for example, a phenyl group, a tolyl group, and a xylyl group. Group, benzyl group, α-methylstyryl group, 3-methylstyryl group, 4-methylstyryl group and the like, and phenyl groups having at least one fluorine atom as a substituent, such as 2-fluorophenyl Group, 3-fluorophenyl group, 4-fluorophenyl group, 2,3-difluorophenyl group, 2,4-difluorophenyl group, 2,5-difluorophenyl group, 2,6-difluorophene Group, 3,4-difluorophenyl group, 3,5-difluorophenyl group, 2,4,6-trifluorophenyl group, 2,3,4-trifluorophenyl group, 2,3,5-trifluorophenyl Group, 2,4,5-trifluorophenyl group, 2,3,6-trifluorophenyl group, 3,4,5-trifluorophenyl group, 2,3,4,6-tetrafluorophenyl group, 2, Examples include 3,4,5-tetrafluorophenyl group, 2,3,4,5,6-pentafluorophenyl group, and the like.

In the modified resin composition of the present invention, R ¹ may be one or a mixture of two or more of the above [a] to [c].

  Further, within the above range of carbon number and oxygen number, the organic group is a hydroxyl unit, alkoxy unit, acyl unit, carboxyl unit, alkenyloxy unit, acyloxy unit, ester bond, oxygen atom or silicon. Hetero atoms such as nitrogen, phosphorus and sulfur excluding atoms and halogen atoms may be contained. Moreover, said [a]-[c] may be the organic group in which 1 type or 2 types or more were mixed.

Since the light resistance of the modified resin composition of the present invention tends to be good and the heat-resistant yellowing tends to improve, the organic group R ¹ of the general formula (1) in the present invention includes the above [a], [ b-1], [b-2], and [c] are preferably selected from the group consisting of [beta] -glycidoxyethyl, [gamma] -glycidoxypropyl, and [gamma] -glycidoxybutyl. A glycidoxyalkyl group, a glycidyl group, a β- (3,4-epoxycyclohexyl) ethyl group, a γ- (3,4-epoxycyclohexyl) propyl group, a β- ( 3,4-epoxycycloheptyl) ethyl group, β- (3,4-epoxycyclohexyl) propyl group, β- (3,4-epoxycyclohexyl) butyl group, β- (3,4-epoxycyclohexyl) penti And an organic group selected from those having 1 to 8 carbon atoms in [b-1] and [b-2] and having 0 oxygen, and phenyl in [c] More preferably selected from the group consisting of a group, a phenyl group having at least one fluorine atom as a substituent, and a benzyl group, and [a] is β-glycidoxyethyl, γ-glycidoxypropyl, γ A glycidoxyalkyl group, a glycidyl group, a β- (3,4-epoxycyclohexyl) ethyl group to which an oxyglycidyl group having 4 or less carbon atoms such as glycidoxybutyl is bonded, [b-1] and [b-2 ] From an organic group selected from those having 1 to 3 carbon atoms and 0 oxygen number, and [c] a phenyl group having at least one fluorine atom as a substituent. Selected It is particularly preferred.

Next, R ² in the present invention will be described. In the present invention, each R ² is independently a hydrogen atom, or [d] an unsubstituted or substituted aliphatic hydrocarbon composed of one or more structures selected from a chain, branched, and cyclic structure group A monovalent organic group having a unit and having 1 to 8 carbon atoms. A monovalent organic having 1 or more and 8 or less carbon atoms, having an aliphatic hydrocarbon unit having one or more structures selected from an unsubstituted or substituted chain, branched, or cyclic structure group Examples of the group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, sec-butyl group, n-pentyl group, isopentyl group, neopentyl group, n Chains consisting of aliphatic hydrocarbons such as hexyl, n-heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl Cyclic groups such as organic groups, cyclopentyl group, methylcyclopentyl group, cyclohexyl group, methylcyclohexyl group, norbornyl group Organic group consisting of hydrocarbons.
The alkoxysilane compound may be a mixture of two or more different organic groups of the above [d]. These may be organic groups in which one kind or two or more kinds are mixed.
Among these organic groups, a methyl group, an ethyl group, an n-propyl group, and an isopropyl group are preferable, and a methyl group and an ethyl group are more preferable because the reactivity of the alkoxysilane compound tends to increase.

In the present invention, as the alkoxysilane compound, at least in the alkoxysilane compound represented by the general formula (1), (B) n = 1 or 2, and R ¹ is a group having at least one cyclic ether group. Containing at least one alkoxysilane compound, and (C) n = 1 or 2 and an alkoxysilane compound containing a phenyl group having at least one fluorine atom as a substituent as R ^1. is necessary.
In the case where (B) n = 1 or 2 and at least one alkoxysilane compound containing at least one cyclic ether group as R ¹ is not contained, the modified resin composition of the present invention is used. The cured product obtained by curing will have insufficient thermal shock resistance and adhesiveness. On the other hand, when (C) n = 1 or 2 and R ¹ does not contain an alkoxysilane compound containing a phenyl group having at least one fluorine atom as a substituent, the modified resin composition undergoes phase separation. In addition, reproducible cold-heat shock resistance and adhesiveness cannot be obtained, and heat-resistant yellowing of a cured product obtained by curing the modified resin composition of the present invention or light resistance under heating conditions decreases. There is a tendency.

  Specific examples of the component (B) used in the present invention include, for example, 3-glycidoxypropyl (methyl) dimethoxysilane, 3-glycidoxypropyl (methyl) diethoxysilane, 3-glycidoxypropyl (methyl) ) Dibutoxysilane, 2- (3,4-epoxycyclohexyl) ethyl (methyl) dimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl (phenyl) diethoxysilane, 2,3-epoxypropyl (methyl) dimethoxy Silane, 2,3-epoxypropyl (phenyl) dimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltributoxysilane, 2- (3,4 -Epoxycyclohexyl) ethyltrimethoxysilane, 2 (3,4-epoxycyclohexyl) ethyl triethoxysilane, 2,3-epoxypropyl trimethoxysilane, 2,3-epoxy propyl triethoxy silane, and the like. These can be used as one kind or a mixture of two or more kinds.

  The component (C) used in the present invention is an alkoxysilane compound containing a phenyl group having at least one fluorine atom as a substituent.

  In the modified resin composition obtained by reacting the alkoxysilane compound represented by the following general formula (1) in the presence of the epoxy resin (A), use an alkoxysilane containing a phenyl machine having a fluorine atom as a substituent. The reason why the cured product obtained by curing exhibits heat-resistant yellowing or light resistance under heating conditions is not clear, but is estimated as follows. That is, in a cured product obtained by curing a modified resin composition having a phenyl group as a substituent mainly used to develop compatibility with the epoxy resin (A), yellowing occurs during heating, or heating At least one of the causes of yellowing when irradiated with light under conditions is the above-mentioned phenyl group, and by introducing a fluorine atom as a substituent into the phenyl group, the chemical stability of the phenyl group itself Is estimated to be based on the improvement.

Specific examples of alkoxysilane compounds containing a phenyl group having at least one fluorine atom as a substituent as R ¹ in the present invention include, for example, dimethoxymethyl-2-fluorophenylsilane, dimethoxymethyl-3-fluorophenylsilane , Dimethoxymethyl-4-fluorophenylsilane, dimethoxymethyl-2,3-difluorophenylsilane, dimethoxymethyl-2,4-difluorophenylsilane, dimethoxymethyl-2,5-difluorophenylsilane, dimethoxymethyl-2,6- Difluorophenylsilane, dimethoxymethyl-3,4-difluorophenylsilane, dimethoxymethyl-3,5-difluorophenylsilane, dimethoxymethyl-2,4,6-trifluorophenylsilane, dimethoxymethyl-2 , 3,4-trifluorophenylsilane, dimethoxymethyl-2,3,5-trifluorophenylsilane, dimethoxymethyl-2,4,5-trifluorophenylsilane, dimethoxymethyl-2,3,6-trifluorophenyl Silane, dimethoxymethyl-3,4,5-trifluorophenylsilane, dimethoxymethyl-2,3,4,6-tetrafluorophenylsilane, dimethoxymethyl-2,3,4,5-tetrafluorophenylsilane, dimethoxymethyl 2,3,4,5,6-pentafluorophenylsilane, diethoxymethyl-2-fluorophenylsilane, diethoxymethyl-3-fluorophenylsilane, diethoxymethyl-4-fluorophenylsilane, diethoxymethyl- 2,3-difluorophenylsilane, diexime 2,4-difluorophenylsilane, diethoxymethyl-2,5-difluorophenylsilane, diethoxymethyl-2,6-difluorophenylsilane, diethoxymethyl-3,4-difluorophenylsilane, diethoxymethyl- 3,5-difluorophenylsilane, diethoxymethyl-2,4,6-trifluorophenylsilane, diethoxymethyl-2,3,4-trifluorophenylsilane, diethoxymethyl-2,3,5-trifluoro Phenylsilane, diethoxymethyl-2,4,5-trifluorophenylsilane, diethoxymethyl-2,3,6-trifluorophenylsilane, diethoxymethyl-3,4,5-trifluorophenylsilane, diethoxy Methyl-2,3,4,6-tetrafluorophenylsilane, diet Dialkoxysilanes such as dimethyl-2,3,4,5-tetrafluorophenylsilane, diethoxymethyl-2,3,4,5,6-pentafluorophenylsilane, trimethoxy-2-fluorophenylsilane, trimethoxy -3-fluorophenylsilane, trimethoxy-4-fluorophenylsilane, trimethoxy-2,3-difluorophenylsilane, tritoxyl-2,4-difluorophenylsilane, trimethoxy-2,5-difluorophenylsilane, trimethoxy-2,6 -Difluorophenylsilane, trimethoxy-3,4-difluorophenylsilane, trimethoxy-3,5-difluorophenylsilane, trimethoxy-2,4,6-trifluorophenylsilane, trimethoxy-2,3,4-trifluorophenylsila , Trimethoxy-2,3,5-trifluorophenylsilane, trimethoxy-2,4,5-trifluorophenylsilane, trimethoxy-2,3,6-trifluorophenylsilane, trimethoxy-3,4,5-triphenyl Fluorophenylsilane, trimethoxy-2,3,4,6-tetrafluorophenylsilane, trimethoxy-2,3,4,5-tetrafluorophenylsilane, trimethoxy-2,3,4,5,6-pentafluorophenylsilane , Triethoxy-2-fluorophenylsilane, triethoxy-3-fluorophenylsilane, triethoxy-4-fluorophenylsilane, triethoxy-2,3-difluorophenylsilane, triex-2,4-difluorophenylsilane, triethoxy-2,5 -Difluorophenyl , Triethoxy-2,6-difluorophenylsilane, triethoxy-3,4-difluorophenylsilane, triethoxy-3,5-difluorophenylsilane, triethoxy-2,4,6-trifluorophenylsilane, triethoxy-2,3 , 4-trifluorophenylsilane, triethoxy-2,3,5-trifluorophenylsilane, triethoxy-2,4,5-trifluorophenylsilane, triethoxy-2,3,6-trifluorophenylsilane, triethoxy-3 , 4,5-trifluorophenylsilane, triethoxy-2,3,4,6-tetrafluorophenylsilane, triethoxy-2,3,4,5-tetrafluorophenylsilane, triethoxy-2,3,4,5, Mono, such as 6-pentafluorophenylsilane Alkoxysilane compounds, and the like. These can be used as one kind or a mixture of two or more kinds.

  Among these, since the heat resistance yellowing of the cured product obtained by curing the modified resin composition of the present invention or the light resistance under heating conditions is further improved, the component (C) used in the present invention Dimethoxymethyl-2-fluorophenylsilane, dimethoxymethyl-4-fluorophenylsilane, dimethoxymethyl-2,4-difluorophenylsilane, dimethoxymethyl-2,6-difluorophenylsilane, dimethoxymethyl-2,4,6 -Trifluorophenylsilane, dimethoxymethyl-2,3,4,5,6-pentafluorophenylsilane, preferably selected from the group consisting of dimethoxymethyl-2-fluorophenylsilane, dimethoxymethyl-4-fluorophenylsilane Dimethoxymethyl-2,4-difluorophenylsilane Dimethoxy-2,6-difluorophenyl silane, dimethoxy methyl-2,4,6-trifluorophenyl silane, and more preferably selected from the group consisting of.

Moreover, the modified resin composition in the present invention includes n = 0 indicating the number of R ¹ in the general formula (1), specifically, in addition to the components (A) to (C) described above, specifically, , (OR ² ) and 4 bonded alkoxysilane compounds. Examples of such alkoxysilane compounds include tetramethoxysilane, tetraethoxysilane, and tetrapropoxysilane. These can be used as one kind or a mixture of two or more kinds.

Furthermore, the modified resin composition in the present invention includes n = 0 indicating the number of R ¹ in the general formula (1), specifically, in addition to the components (A) to (C) described above, specifically, , (OR ² ) can be used with an alkoxysilane compound having one bonded. Examples of such alkoxysilane compounds include methoxytrimethylsilane, methoxytriethylsilane, ethoxytrimethylsilane, ethoxytriethylsilane, and the like.

Here, the mixing index α used in the present invention will be described.
In the alkoxysilane used in the present invention, “(B) in formula (1), n = 1 or 2, and R ¹ includes at least one group having a cyclic ether group” Mixing ratio of “silane compound” and “(C) alkoxysilanes having a phenyl group having n = 1 or 2 and R ¹ having at least one fluorine atom as a substituent in general formula (1)” Is defined as a mixture index α calculated by the following equation (2).
Mixing index α = (αc) / (αb) (2)
(In the formula (2), αb is the content (mol%) of the component (B) in the alkoxysilane represented by the general formula (1), and αc is an alkoxysilane represented by the general formula (1). (Indicates the content (mol%) of the component (C).)

  In the present invention, the above-mentioned mixing index α is that the cured product obtained by curing the modified resin composition of the present invention has high heat-resistant yellowing resistance and light resistance under heating conditions, while maintaining the light resistance under the heating condition. In ensuring fluidity and storage stability, the range of 0.001 or more, on the other hand, a cured product obtained by curing the modified resin composition of the present invention is highly heat-resistant yellowing, and heating conditions In order to ensure the fluidity of the modified resin composition and the cold-heat shock resistance of the cured product while maintaining the light resistance underneath, it is necessary to make it 19 or less. The value of α is more preferably in the range of 0.2 to 5, more preferably 0.3 to 2.

  In the modified resin composition of the present invention, the amount of residual alkoxy groups in the composition is improved since the thermal shock resistance and adhesiveness during thermal cycling of the cured product obtained by curing the composition of the present invention are improved. Is preferably 5% or less, more preferably 3% or less, still more preferably 1% or less, still more preferably 0.5% or less, and particularly preferably not contained at all. The amount of residual alkoxy groups is quantified by calculating the area ratio between the internal standard peak obtained by H-NMR measurement using 1,1,2,2-tetrabromoethane as the internal standard substance and the peak derived from the residual alkoxy group. can do.

Specifically, it can be determined by the following method and analysis method.
<H-NMR measurement>
(1) 10 mg of the modified resin composition, 20 mg of an internal standard substance (1,1,2,2-tetrabromoethane; Tokyo Kasei Kogyo), and 970 mg of deuterated chloroform are uniformly mixed to obtain an H-NMR measurement solution. .
(2) The H-NMR spectrum of the solution of (1) above is measured under the following conditions.
Apparatus: “α-400” manufactured by JEOL Ltd.
Nuclide: H
Integration count: 600 times <Analysis of measurement results>
(3) The area value of the residual alkoxy group-derived peak in the H-NMR spectrum is calculated.
(4) The area value of the peak derived from the internal standard substance in the H-NMR spectrum is calculated.
(5) The respective area values obtained in the above (3) and (4) are substituted into the following formula, and the obtained result is defined as the residual alkoxy group amount (%).
Residual alkoxy group amount (%) = (Area value of peak derived from residual alkoxy group) / (Area value of peak derived from internal standard substance) × 100

  Although there is no restriction | limiting in particular about the viscosity in 25 degreeC of the modified resin composition of this invention, The fluidity | liquidity as a liquid can be ensured and it exists in the tendency for a handleability to increase, Moreover, with the additive added as needed Since mixing tends to be easy, the liquid is preferably 1,000 Pa · s or less, more preferably 500 Pa · s or less, still more preferably 300 Pa · s or less, and 100 Pa · s. It is particularly preferred that

  Although there is no restriction | limiting in particular about the epoxy equivalent (WPE) of the modified resin composition of this invention, From a viewpoint of improving the storage stability of a modified resin composition, it is preferable to select a functional group so that it may be 100 g / eq or more. Moreover, it is preferable to select a functional group so that it may become 700 g / eq or less from a viewpoint of improving the cold-heat shock resistance of the hardened | cured material obtained by hardening | curing a modified resin composition. A more preferable range is a range of 100 g / eq to 500 g / eq, and a further preferable range is a range of 100 g / eq to 400 g / eq.

Next, the mixing index β used in the present invention will be described.
In the alkoxysilane compound used in the present invention, the mixing ratio of “an alkoxysilane compound where n = 2”, “an alkoxysilane compound where n = 1” and “an alkoxysilane compound where n = 0” is as follows: It is defined as a mixture index β calculated by Expression (3).
Mixing index β = {(βn2) / (βn0 + βn1)} (3)
(In the formula (3), βn2 is the content (mol%) of the alkoxysilane compound in which n = 2 in the alkoxysilane compound represented by the general formula (1), and βn0 is the general formula (1). The content (mol%) of the alkoxysilane compound in which n = 0 in the alkoxysilane compound represented by the formula: βn1 is the alkoxysilane in which n = 1 in the alkoxysilane compound represented by the general formula (1) The content (mol%) of the compound is shown, and 0 ≦ {(βn0) / (βn0 + βn1 + βn2)} ≦ 0.1.

  In the present invention, the above mixing index β is 0.01 or more because the fluidity of the modified resin composition is enhanced and the handleability tends to be improved. On the other hand, curing obtained by curing the modified resin composition It is preferably 1.4 or less, more preferably 0.03 or more and 1.2 or less, and more preferably 0.05 or more and 1.0 or less because the thermal and thermal shock resistance of the product tends to be improved. More preferably, it is in the range.

Next, the mixing index γ used in the present invention will be described.
The mixing index γ calculated by the following formula (4) is the mixing ratio of the epoxy resin (A) used in the present invention and the “alkoxysilane compound where n = 0 to 2” in the alkoxysilane compound. It is defined as
Mixing index γ = (γa) / (γs) (4)
(In the formula (4), γa is the mass (g) of the epoxy resin (A), and γs is an alkoxysilane compound in which n = 0 to 2 in the alkoxysilane represented by the general formula (1). (The mass (g) is shown respectively.)

  In the present invention, the mixing index γ is 0.02 or more because the thermal shock resistance during the thermal cycle of the cured product obtained by curing the modified resin composition tends to be increased. The range of 15 or less is preferable, the range of 0.04 or more and 7 or less is more preferable, and the range of 0.08 or more and 5 or less is more preferable because the light resistance of the cured product obtained by curing tends to be improved.

  In the modified resin composition of the present invention, the condensation rate of the alkoxysilane compound is 80% or more from the viewpoint of the storage stability of the modified resin composition, that is, the viscosity of the resin during storage is suppressed and the handleability is improved. It is preferably 82% or more, more preferably 85% or more, and particularly preferably 88% or more.

The condensation rate of the alkoxysilane compound of the present invention is present in the modified resin composition with respect to the number of moles (U) of the (OR ² ) group contained in the alkoxysilane compound represented by the general formula (1). It is shown as a mole fraction represented by the following formula (5) using the number of moles (V) of (OR ² ) groups in the silicone component.
Condensation rate of alkoxysilane compound (%) = [(U−V) / U] × 100 (5)

Next, an example of a specific method for producing the modified resin composition of the present invention will be described.
The modified resin composition of the present invention includes at least (B) and (C) represented by the following general formula (1) in the presence of the epoxy resin (A), and is represented by the following general formula (2). An alkoxysilane compound having a mixture index α of the alkoxysilane compound of 0.001 or more and 19 or less can be produced by reacting with the following [Production Method 1] or [Production Method 2].
_{^{(R 1) n -Si- (OR}} 2) 4-n ··· (1)
(Wherein n represents an integer of 0 or more and 3 or less. In addition, each R ¹ is independently a hydrogen atom or a) selected from an unsubstituted or substituted structure group consisting of a chain, a branch, and a ring. An organic group containing a cyclic ether group having an aliphatic hydrocarbon unit having one or more kinds of structures, 4 to 24 carbon atoms, and 1 to 5 oxygen atoms, b) unsubstituted Or a substituted aliphatic hydrocarbon unit having one or more structures selected from the group consisting of a chain, a branched chain and a ring, having 1 to 24 carbon atoms and 0 oxygen atoms A monovalent aliphatic organic group that is 5 or less, and c) an unsubstituted or substituted aromatic hydrocarbon unit that is unsubstituted or substituted as necessary, from a chain, branched, and cyclic An aliphatic hydrocarbon unit comprising at least one structure selected from the group consisting of And at least one organic group selected from the group consisting of monovalent aromatic organic groups having 6 to 24 carbon atoms and 0 to 5 oxygen atoms. On the other hand, each R ² independently has a hydrogen atom or d) an unsubstituted or substituted aliphatic hydrocarbon unit having one or more types of structures selected from a chain, branched, or cyclic structure group. And a monovalent organic group having 1 to 8 carbon atoms. )
(B) n = 1 or 2, and at least one alkoxysilane compound containing a group having at least one cyclic ether group as R ¹ ,
(C) an alkoxysilane compound containing n = 1 or 2 and a phenyl group having at least one fluorine atom as a substituent as R ¹ ;
Mixing index α = (αc) / (αb) (2)
(Here, in the formula (2), αb represents the content (mol%) of the component (B), and αc represents the content (mol%) of the component (C).)

[Production Method 1] is a method for producing a modified resin composition, which includes the following two steps, step (a) and step (b).
Step (a): In the presence of the epoxy resin (A), the alkoxysilane compound containing at least the above (B) and (C) represented by the general formula (1) is distilled out of the reaction system of water or a solvent. A process for producing an intermediate by co-hydrolysis by a refluxing process that does not involve.
Step (b): A step of subjecting the intermediate produced in step (a) to a dehydration condensation reaction.

[Production Method 2] is a method for producing a modified resin composition, which includes the following two steps, step (c) and step (d).
Step (c): Co-hydrolyzing the alkoxysilane compound containing at least the above (B) and (C) represented by the general formula (1) by a reflux step without distilling water or a solvent out of the reaction system And manufacturing the intermediate.
Step (d): A step in which the epoxy resin (A) is allowed to coexist with the intermediate produced in the step (c) to perform a dehydration condensation reaction.

  Here, “a step of producing an intermediate by cohydrolysis by a refluxing step not involving distillation of water or a solvent out of the reaction system” and “a step of dehydrating condensation reaction” will be described.

  "The step of producing an intermediate by cohydrolysis by a refluxing step that does not involve distilling water or solvent out of the reaction system" refers to the water and solvent formulated for cohydrolysis and the reaction. This is a step of reacting the resulting alkoxysilane compound-derived water or solvent while returning it to the reaction solution. The reaction mode is not particularly limited, and can be carried out by one or a combination of two or more of various reaction modes such as batch, semi-batch, or continuous. As a specific example, for example, a cooling tube is attached to the upper part of the reaction vessel and the reaction is performed while refluxing the generated water or solvent, or the reaction solution is stirred and / or circulated in a sealed vessel. And the like.

  On the other hand, the “step of dehydrating condensation reaction” means that the added water and solvent and the water and solvent generated in the above “refluxing step not involving distillation of water or solvent out of the reaction system” are removed. This is a step of performing a condensation reaction. For example, rotary evaporators, vertical stirring tanks equipped with distillation tubes, surface renewal stirring tanks, thin film evaporators, surface renewal biaxial kneaders, biaxial horizontal stirrers, wet wall reactors, free fall types One type or two or more types of devices such as a perforated plate reactor, a reactor in which a volatile component is distilled off while dropping a compound along a support, and the like can be used.

  The modified resin composition of the present invention can be produced by any of the above [Production Method 1] and [Production Method 2]. There is no particular limitation on the reaction method of the alkoxysilane compound in producing the modified resin composition of the present invention, and it is possible to react by batch conversion in the initial stage, and also in a sequential or continuous reaction system. It is also possible to add and react.

  In addition, the epoxy resin (A) can be added at once or divided and sequentially added in any of [Production Method 1] and [Production Method 2].

  In the case of following [Production Method 1], the step (a) and the step (b) may be performed continuously, or after the reaction mixture obtained in the step (a) is separated or recovered, the step (b) Can also be done.

  On the other hand, in the case of [Production Method 2], the step (c) and the step (d) are performed continuously, or the step (d) is performed after the reaction mixture obtained in the step (c) is recovered. You can also.

  Here, examples of the epoxy resin (A) and the alkoxysilane compound used in [Production Method 1] and [Production Method 2] include the same epoxy resins (A) and alkoxysilane compounds listed above. .

  Moreover, the suitable range of the mixing index α to γ of the alkoxysilane compound in [Production Method 1] and [Production Method 2] is the same as described above.

  In the [Production Method 1] or [Production Method 2] of the present invention, the intermediate at the time of completion of the step of producing the intermediate by co-hydrolysis by a reflux step without distilling water or solvent out of the reaction system. The condensation rate is not particularly limited, but even after the subsequent dehydration condensation step, many silicone-derived OH groups remain in the produced resin composition, and the residual OH groups are condensed during storage. It is preferably 70% or more, more preferably 78% or more, and even more preferably 80% or more, because it may cause remarkable thickening or gelation of the resin composition and may deteriorate storage stability. 83% or more is particularly preferable.

Incidentally, the degree of condensation of the intermediates in the process end to produce a co-hydrolyzed to intermediates in the present invention include alkoxysilane compounds represented by the general formula ⁽¹⁾ (OR 2) the number of moles of group It is shown as a mole fraction represented by the following formula (6) using the number of moles (S) of the (OR ² ) group in the silicone component present in the modified resin composition with respect to (R).
Intermediate condensation rate (%) = [(R−S) / R] × 100 (6)

  In the method for producing the modified resin composition of the present invention, the condensation rate of the alkoxysilane compound is 80% from the viewpoint of improving the storage stability of the modified resin composition, that is, suppressing the viscosity of the resin during storage and improving the handleability. Preferably, it is 82% or more, more preferably 85% or more, and particularly preferably 88% or more.

The condensation rate of the alkoxysilane compound of the present invention is present in the modified resin composition with respect to the number of moles (U) of the (OR ² ) group contained in the alkoxysilane compound represented by the general formula (1). It is shown as a mole fraction represented by the following formula (5) using the number of moles (V) of (OR ² ) groups in the silicone component.
Condensation rate of alkoxysilane compound (%) = [(U−V) / U] × 100 (5)

  In the method for producing the modified resin composition of the present invention, the amount of residual alkoxy groups in the resulting modified resin composition is 5% or less. When the amount of residual alkoxy groups exceeds 5%, the thermal shock resistance during the thermal cycle and the adhesiveness of the cured product obtained by curing the composition may be insufficient. The amount of residual alkoxy groups in the resulting modified resin composition is preferably 3% or less, more preferably 1% or less, still more preferably 0.5% or less, and particularly preferably not contained at all.

  In the step (a) or the step (c) of the present invention, water is allowed to coexist in the reaction system in order to hydrolyze the alkoxysilane compound. The main purpose of adding water is to hydrolyze the alkoxysilane compound. The timing of adding water is not particularly limited, and it may be added until the end of the step of producing an intermediate by co-hydrolysis, a method of batch addition at the initial stage of the reaction, a method of successive points during the reaction Alternatively, any method of adding continuously during the reaction may be used. Among these, the method of adding all at the beginning of the reaction is preferably used.

Here, the amount of water to be added will be described. The ratio of the amount of water to be added (number of moles) and the amount (number of moles) of (OR ² ) in the above formula (1) is defined as a mixing index ε represented by the following formula (7).
Mixing index ε = (εw) / (εs) (7)
(Here, in formula (7), εw represents the amount of water added (mol number), while εs represents the amount (mol number) of (OR ² ) in general formula (1)).

  In the present invention, the mixing index ε is preferably in the range of 0.1 to 5, more preferably in the range of 0.2 to 3, and still more preferably in the range of 0.3 to 1.5. If the mixing index ε is less than 0.1, the hydrolysis reaction may not proceed. If it exceeds 5, the storage stability of the modified resin composition may be reduced.

  Step (a) or step (c) described above can be carried out without a solvent or in a solvent. In the case of using a solvent, a known one can be used as long as it is an organic solvent that can dissolve the epoxy resin and the alkoxysilane compound and is inactive to them.

  Examples of the solvent used include dimethyl ether, diethyl ether, diisopropyl ether, 1,4-dioxane, 1,3-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, and anisole. Ether solvents; Ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone; Aliphatic hydrocarbon solvents such as hexane, cyclohexane, heptane, octane, isooctane; toluene, o-xylene, m-xylene, p-xylene, ethylbenzene Aromatic solvent such as ethyl acetate, ester solvent such as butyl acetate, etc .; methanol, ethanol, butanol, isopropano Le, n- butanol, butyl cellosolve, alcohol-based solvents such as butyl carbitol. These solvents can be used as one kind or a mixture of two or more kinds. Among these, from the viewpoint of suppressing ring opening of the epoxy group during the reaction, an ether solvent, a ketone solvent, an aliphatic hydrocarbon solvent, and an aromatic hydrocarbon solvent are preferable, and the ether solvent is 50% by mass or more. More preferable is a solvent containing, at least one or two or more mixed solvents selected from the group consisting of 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether and propylene glycol dimethyl ether are more preferable, and 1,4-dioxane and tetrahydrofuran are particularly preferable. preferable.

  In the case of step (a), the amount of the solvent added is added by the end of the step of producing the intermediate by cohydrolysis by the reflux step without distilling water or solvent out of the reaction system. On the other hand, in the case of the step (c), the intermediate is obtained by cohydrolyzing by a reflux step without distilling water or a solvent out of the reaction system. 0.01-20 times amount is preferable with respect to the total mass of the alkoxysilane compound added by the completion | finish time of the process to manufacture, 0.02-15 times amount is more preferable, 0.03-10 times amount is Further preferred. Since the molecular weight of the resin composition of the present invention can be controlled by the addition amount of the solvent, by setting the addition amount of the solvent within the above range, there is a tendency that a resin composition having an appropriate molecular weight and, therefore, an appropriate viscosity is obtained.

  The reaction temperature in the step (a) or the step (c) is usually in the range of 0 ° C. or higher and 200 ° C. or lower. If it is lower than 0 ° C., water may solidify. On the other hand, if it exceeds 200 ° C., the resin composition may be colored. From the viewpoint of increasing the reaction rate and suppressing the modification of the resin such as ring opening of the epoxy group, the reaction temperature is preferably in the range of 20 ° C. or higher and 150 ° C. or lower, more preferably in the range of 40 ° C. or higher and 120 ° C. or lower, and 50 ° C. The range of 100 ° C. or lower is more preferable. The reaction temperature need not be constant as long as it is within the above range, and may be changed during the reaction.

No particular limitation on the reaction time of step (a) or step (c), improves the reaction rate of (OR ²⁾ in the formula (1), from the viewpoint of suppressing denaturation of the resin, 0.1 A range of not less than 100 hours is preferable, a range of not less than 1 hour and less than 80 hours is more preferable, a range of not less than 3 hours and less than 60 hours is further preferable, and a range of not less than 5 hours and less than 50 hours is particularly preferable.

  On the other hand, the reaction temperature in the step (b) or the step (d) is usually in the range of 0 ° C. or higher and 200 ° C. or lower. When the temperature is less than 0 ° C, the reaction rate may decrease and the reaction time may be long. When the temperature exceeds 200 ° C, the resin composition may be colored. From the viewpoint of increasing the reaction rate and suppressing the modification of the resin such as ring opening of the epoxy group, the reaction temperature is preferably in the range of 20 ° C. or higher and 150 ° C. or lower, more preferably in the range of 40 ° C. or higher and 120 ° C. or lower, and 50 ° C. The range of 100 ° C. or lower is more preferable. The reaction temperature does not need to be constant as long as it is within the above range, and may be changed at the initial stage of the reaction or during the reaction.

  The reaction time of the step (b) or the step (d) is not particularly limited, but from the viewpoint of improving the reaction rate and suppressing the denaturation of the resin, a range of 0.1 hour or more and less than 100 hours is preferable. More preferably, the range is 5 hours or more and less than 80 hours, more preferably 1 hour or more and less than 50 hours, and particularly preferably 3 hours or more and less than 50 hours.

  The modified resin composition of the present invention can be produced in an inert gas such as nitrogen, helium, neon, argon, krypton, xenon, carbon dioxide or lower saturated hydrocarbon, or in the air. Among these gases, from the viewpoint of suppressing the modification of the resin, an inert gas such as nitrogen, helium, neon, argon, krypton, xenon, carbon dioxide or lower saturated hydrocarbon is preferable, and nitrogen, helium, neon, argon, Krypton, xenon and carbon dioxide are more preferred, nitrogen and helium are more preferred, and nitrogen is particularly preferred.

  The steps (a) to (d) for producing the modified resin composition of the present invention can be performed under the above-mentioned gas atmosphere, under the above-mentioned gas flow, under reduced pressure, under pressure, or a combination thereof. The pressure need not be constant and may be changed during the reaction.

  Among these, the step (a) and the step (c) are industrially easy reaction solutions of water and solvents blended for cohydrolysis and water and solvents derived from alkoxysilane compounds generated during the reaction. Therefore, the reaction is preferably performed under an atmospheric pressure atmosphere and / or under pressure.

  On the other hand, the step (b) and the step (d) include the water and the solvent added in the step (a) or the step (c), and the above-mentioned “refluxing step without distilling the water or the solvent out of the reaction system”. Since it is necessary to carry out the condensation reaction while removing the water and solvent produced in step 1, it is preferably carried out under an inert gas flow and / or under reduced pressure.

  In this invention, you may carry out by adding a hydrolysis-condensation catalyst in the case of the cohydrolysis of the above-mentioned (A) epoxy resin and alkoxysilane compound.

  The hydrolysis condensation catalyst is not particularly limited as long as it promotes a conventionally known hydrolysis condensation reaction. For example, a metal (lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, barium, Strontium, zinc, aluminum, titanium, cobalt, germanium, tin, lead, antimony, arsenic, cerium, boron, cadmium, manganese, bismuth, etc., organic metals (lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, barium) Strontium, zinc, aluminum, titanium, cobalt, germanium, tin, lead, antimony, arsenic, cerium, boron, cadmium, manganese, bismuth and other organic oxides, organic acid salts, organic halides, alkoxides, etc.), inorganic bases Magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, etc.), organic base (Ammonia, tetramethylammonium hydroxide, etc.).

  Among the above organic metals, organic tin is preferable. The organic tin refers to one in which at least one organic group is bonded to a tin atom, and examples of the structure include monoorganotin, diorganotin, triorganotin, and tetraorganotin. Examples of the organic tin include tin tetrachloride, monobutyltin trichloride, monobutyltin oxide, monooctyltin trichloride, tetra n-octyltin, tetra n-butyltin, dibutyltin oxide, dibutyltin diacetate, dibutyltin dioctate, dibutyl Tin diversate, dibutyltin dilaurate, dibutyltin oxylaurate, dibutyltin stearate, dibutyltin dioleate, dibutyltin / silicon ethyl reactant, dibutyltin salt and silicate compound, dioctyltin salt and silicate compound, dibutyltin bis ( Acetylacetonate), dibutyltin bis (ethyl malate), dibutyltin bis (butylmalate), dibutyltin bis (2-ethylhexylmalate), dibutyltin bis (benzylmalate), dibutyltin bis Allyl malate), dibutyltin bis (oleylmalate), dibutyltin malate, dibutyltin bis (O-phenylphenoxide), dibutyltin bis (2-ethylhexylmercaptoacetate), dibutyltin bis (2-ethylhexylmercaptopropionate) Dibutyltin bis (isononyl 3-mercaptopropionate), dibutyltin bis (isooctylthioglycolate), dibutyltin bis (3-mercaptopropionate), dioctyltin oxide, dioctyltin dilaurate, dioctyltin diacetate, Dioctyltin dioctate, dioctyltin didodecyl mercapto, dioctyltin versatate, dioctyltin distearate, dioctyltin bis (ethyl malate), dioctyltin bis (octylmalate), dioctyl Rutin malate, dioctyltin bis (isooctylthioglycolate), dioctyltin bis (2-ethylhexyl mercaptoacetate), dibutyltin dimethoxide, dibutyltin diethoxide, dibutyltin dibutoxide, dioctyltin dimethoxide, dioctyltin diethoxide, dioctyltin dibutoxide, Examples include tin octylate and tin stearate.

  Among the above organic metals, an alkali organic metal that exhibits alkalinity when a ligand is liberated is preferable. By using an alkali organic metal as the hydrolysis condensation catalyst, the storage stability of the modified resin composition of the present invention tends to be good. In addition, since the condensation reaction tends to progress rapidly by using an alkali organic metal, it is very useful for obtaining a resin composition having an intermediate condensation ratio of 60% or more.

  Among the alkali organic metals, alkali organic tin is preferable, and alkoxide organic tin is particularly preferable. Examples of the alkoxide-based organic tin include dibutyltin dimethoxide, dibutyltin diethyloxide, dibutyltin dibutoxide, dioctyltin dimethoxide, dioctyltin diethyloxide, dioctyltin dibutoxide, and the like.

  On the other hand, when an acid-based organic metal that shows acidity when the ligand is liberated is used as a hydrolysis-condensation catalyst, the hydrolysis reaction is carried out quickly, but the condensation reaction tends to be difficult to proceed. It is not preferable.

  The hydrolytic condensation catalysts described above may be used alone or in combination of two or more. For example, organic acid tin and alkaline organic tin may be used in combination, or may be treated with an inorganic base after reacting with an organic acid salt such as tin. In this case, the inorganic base is preferably a hydroxide of a polyvalent cation such as magnesium hydroxide, calcium hydroxide, strontium hydroxide or barium hydroxide.

  Although the addition amount of the hydrolysis condensation catalyst described above is not particularly limited, a preferable addition amount is 0. 0 of the total weight of the epoxy resin and the alkoxysilane compound used for producing the modified resin composition of the present invention. The range of 0001 mass% or more and 10 mass% or less is preferable, and the range of 0.01 mass% or more and 5 mass% or less is more preferable. When the addition amount of the catalyst to be used is less than 0.0001% by mass, it may be difficult to obtain the effect of promoting hydrolysis condensation depending on the composition of the modified resin composition. On the other hand, when it exceeds 10% by mass, the ring opening of the cyclic ether group may be promoted or the storage stability may be deteriorated.

  The modified resin composition of the present invention has a good storage stability and is capable of forming a cured product having excellent transparency, heat yellowing resistance, light resistance, and thermal shock resistance in thermal cycle. Since it is a composition and a cured product is formed by heat or energy rays, it is suitable as a raw material resin composition such as a light emitting device sealing material, an optical lens, a photosensitive resin, a fluorescent resin, a conductive resin, and an insulating resin. Can be used.

  The modified resin composition of the present invention includes an oxetane compound, a phosphor, a conductive metal powder, an insulating powder, a curing agent, a curing accelerator, a photoacid generator, and a cationic polymerization catalyst as necessary. It is also possible to mix a modifier, a vinyl ether compound, an organic resin other than the epoxy resin (A), and a silane coupling agent.

  A resin composition obtained by further adding an oxetane compound to the modified resin composition of the present invention will be described.

  The oxetane compound is not particularly limited as long as it is a compound containing an oxetane ring. For example, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, bis (3- Ethyl-3-oxetanylmethyl) ether, 3-ethyl-3- (phenoxymethyl) oxetane, 3-ethyl-3- (2,3-epoxypropoxymethyl) oxetane and the like. By blending these oxetane compounds, the polymerization rate tends to increase, and the viscosity of the composition tends to decrease.

Typical examples of oxetane compounds are shown below.

  The compounding quantity of the said oxetane compound is not specifically limited, Preferably it mix | blends by the mass ratio of modified resin composition: oxetane compound = 20: 80-95: 5 (100 in total). More preferably, it is 40: 60-80: 20. When the blending ratio of the resin composition is less than 20, the curing reaction may not proceed normally, and when it exceeds 95, the cured product may have poor adhesion.

  Further, in order to improve the compatibility between the resin composition and the oxetane compound, for example, an appropriate combination of an oxetane compound having an aromatic ring is combined with a resin composition using an epoxy resin having a bisphenol skeleton as a raw material. Choosing a combination is a common practice.

  A fluorescent resin composition obtained by further adding a phosphor to the modified resin composition of the present invention will be described.

  The phosphor in the present invention is a substance that emits fluorescence, that is, absorbs energy such as an electron beam, X-rays, ultraviolet rays, and an electric field, and emits a part of the absorbed energy as visible light (emission). It is not particularly limited as long as it is a substance to be used, and it can be employed regardless of whether it is inorganic or organic. Of these, inorganic phosphors that generally exhibit excellent light-emitting properties are preferred.

  The size of the inorganic phosphor that can be used in the present invention is not particularly limited, but usually a powder having a particle size of 1 to several tens of μm is used. In order to express the performance of the inorganic phosphor, a compound A called an activator (emission center) introduced into a compound A called a matrix is generally used. : Activator B ”.

  In particular, when the fluorescent resin composition is used as a sealing material for a light emitting diode, it is preferable to use a cerium-activated yttrium aluminate phosphor (YAG: Ce phosphor) for the reasons described later. When using as, it is preferable to use a phosphorescent phosphor. These may be used alone or in combination of two or more.

  The blending amount of the phosphor is preferably, as a mass ratio, resin composition: phosphor = 30: 70 to 95: 5, more preferably 50:50 to 80:20 (100 in total). When the blending amount of the phosphor is larger than the resin composition: phosphor = 30: 70, the fluidity as the phosphor resin composition may be deteriorated. When the blending amount is less than 95: 5, the phosphor as the phosphor The function may be insufficient.

  The matrix A and the activator B are not particularly limited, and examples of the matrix A include oxide phosphors and nitride phosphors. Examples of the activator B include rare earth elements such as europium (Eu) and cerium (Ce).

  As the above-mentioned oxide phosphor, for example, “YAG: Ce phosphor” in which the base A is yttrium aluminate (Y3Al5O12: hereinafter referred to as YAG) and the activator B is cerium (Ce) is well known. . When this is irradiated with blue light (around 460 nm), yellow light emission occurs efficiently. In this phosphor, the emission peak position is obtained by changing the structure of the matrix A by substituting a part of Y of “Y3Al5O12” with another Gd, Tb, or the like, or substituting a part of Al with Ga or the like. Can be shifted to the long wavelength side or the short wavelength side, which is very useful.

  In other words, the “YAG: Ce phosphor” means that the base A is YAG, or a part of Y is replaced with other Gd, Tb or the like, or a part of Al is replaced with Ga or the like. There is no particular limitation as long as the structure of A is changed and the activator B is a phosphor of Ce. Specific examples thereof include “Y3Al5O12: Ce3 +” and “(Y3, Gd0.9) Al5O12: Ce3 +”.

  In addition, as an example of the oxide phosphor, the base A is strontium barium silicate (Sr, Ba) 2 SiO 4 and europium (Eu) is introduced as the activator B, “(Sr, Ba) 2 SiO 4: Eu fluorescence. "Body" is known. In this system, the emission color can be adjusted from green to orange by changing the composition ratio of Sr and Ba.

  Examples of the nitride phosphor described above include the following.

  α-Sialon phosphor: Base A is a crystal in which a metal ion such as Ca, aluminum and oxygen are dissolved in α-type silicon nitride crystal, and “(Mp (Si, Al) 12 (O, N) 16 Here, M represents a metal ion, and p represents a solid solution amount. Specifically, “Cap (Si, Al) 12 (O, N) 16: Eu” and the like can be mentioned.

  β-sialon phosphor: the matrix A is represented by a composition of “Si6-qALqOqN8-q” in which aluminum and oxygen are dissolved in a β-type silicon nitride crystal. Here, q represents the amount of solid solution. Specific examples include “Si6-qALqOqN8-q: Eu”.

  CaAlSiN3 phosphor: The base A is a nitride crystal obtained by reacting calcium nitride, aluminum nitride, and silicon nitride at a high temperature of 1800 ° C., and specifically includes “CaAlSiN3: Eu” and the like.

  Specific examples of the inorganic phosphor include, for example, “6MgO.As2O5: Mn4 +, Y (PV) O4: Eu”, “CaLa0.1Eu0.9Ga3O7”, “BaY0. 9Sm0.1Ga3O7 "," Ca (Y0.5Eu0.5) (Ga0.5In0.5) 3O7 "," Y3O3: Eu, YVO4: Eu "," Y2O2: Eu "," 3.5MgO.0.5MgF2GeO2: Mn4 + " And “(Y · Cd) BO2: Eu”.

  Examples of blue light-emitting colors include “(Ba, Ca, Mg) 5 (PO 4) 3 Cl: Eu 2+”, “(Ba, Mg) 2 Al 16 O 27: Eu 2+”, “Ba 3 MgSi 2 O 8: Eu 2+”, “BaMg 2 Al 16 O 27: "Eu2 +", "(Sr, Ca) 10 (PO4) 6Cl2: Eu2 +", "(Sr, Ca) 10 (PO4) 6Cl2 / nB2O3: Eu2 +", "Sr10 (PO4) 6Cl2: Eu2 +", "(Sr, Ba , Ca) 5 (PO4) 3Cl: Eu2 + ”,“ Sr2P2O7: Eu ”,“ Sr5 (PO4) 3Cl: Eu ”,“ (Sr, Ca, Ba) 3 (PO4) 6Cl: Eu ”,“ SrO · P2O5 · B2O5: Eu "," (BaCa) 5 (PO4) 3Cl: Eu "," SrLa0.95Tm0.05Ga3O7 ", “ZnS: Ag”, “GaWO4”, “Y2SiO6: Ce”, “ZnS: Ag, Ga, Cl”, “Ca2B4OCl: Eu2 +”, “BaMgAl4O3: Eu2 +”, “(M1, Eu) 10 (PO4) 6Cl2 (M1 Is at least one element selected from the group consisting of Mg, Ca, Sr, and Ba).

  Examples of green light emitting colors include “Y3Al5O12: Ce3 + (YAG)”, “Y2SiO5: Ce3 +, Tb3 +”, “Sr2Si3O8 · 2SrCl2: Eu”, “BaMg2Al16O27: Eu2 +, Mn2 +”, “ZnSiO4: Mn”. "," Zn2SiO4: Mn "," LaPO4: Tb "," SrAl2O4: Eu "," SrLa0.2Tb0.8Ga3O7 "," CaY0.9Pr0.1Ga3O7 "," ZnGd0.8Ho0.2Ga3O7 "," SrLa0.6Tb0.4Al3O7 " , ZnS: Cu, Al ”,“ (Zn, Cd) S: Cu, Al ”,“ ZnS: Cu, Au, Al ”,“ Zn2SiO4: Mn ”,“ ZnSiO4: Mn ”,“ ZnS: Ag, Cu ” , “(Zn · Cd) S: Cu”, “ZnS “Cu”, “GdOS: Tb”, “LaOS: Tb”, “YSiO4: Ce · Tb”, “ZnGeO4: Mn”, “GeMgAlO: Tb”, “SrGaS: Eu2 +”, “ZnS: Cu · Co”, “ MgO.nB2O3: Ge, Tb "," LaOBr: Tb, Tm "," La2O2S: Tb "and the like.

  Further, “YVO4: Dy” having a white emission color, “CaLu0.5Dy0.5Ga3O7” having a yellow emission color, and the like are also included.

  Specific examples of the organic phosphor include, for example, 1,4-bis (2-methylstyryl) benzene (Bis-MSB), trans-4,4′-diphenylstilbene (DPS) having a blue emission color. ) And stilbene dyes such as 7-hydroxy-4-methylcoumarin (coumarin 4).

  Examples of commercially available products having yellow to green fluorescent colors include Brilliantsulfoflavine FF, Basic yellow HG, SINLOIHI COLOR FZ-5005 (manufactured by SINLOIHI), and the like.

  As what has a yellowish-red fluorescent color, Eosine, Rhodamine 6G, Rhodamine B etc. are mentioned as a commercial item, for example.

  In general phosphors, when light, an electron beam or the like, which is an irradiation excitation source, is cut off, light emission is immediately attenuated and disappears. However, as an exception, there is a phosphor that exhibits afterglow for several seconds to several tens of hours after the excitation source is cut off, and this is called a phosphorescent phosphor. The type is not particularly limited as long as it exhibits this property. Specifically, for example, “CaS: Eu, Tm”, “CaS: Bi”, “CaAl 2 O 4: Eu, Nd”, “CaSrS: Bi”, “Sr2MgSi2O7: Eu, Dy”, “Sr4Al14O25: Eu, Dy”, “SrAl2O4: Eu, Dy”, “SrAl2O4: Eu”, “ZnS: Cu”, “ZnS: Cu, Co”, “Y2O2S: Eu, Mg, Ti”, “CaS: Eu, Tm”, and the like are mentioned. Among them, “Sr2MgSi2O7: Eu, Dy”, “Sr4Al14O25: Eu, Dy”, “SrAl2O4: Eu” exhibiting long afterglow. , Dy "and" SrAl2O4: Eu "are preferable.

  The method for producing the fluorescent resin composition of the present invention is not particularly limited. For example, while the modified resin composition and the phosphor are simultaneously or separately heated as necessary, they are stirred in a mixing device described later. Examples thereof include a method of mixing and dispersing, a method of performing defoaming treatment under reduced pressure, if necessary, following the above method. Moreover, you may add suitably the below-mentioned hardening | curing agent, hardening accelerator, a polymerization initiator, an additive, etc. in one of said processes.

  Although the said mixing apparatus is not specifically limited, For example, a raikai machine, a 3 roll mill, a ball mill, a planetary mixer, a line mixer, a homogenizer, a homodisper etc. are mentioned.

  The conductive resin composition obtained by further adding conductive metal powder to the modified resin composition of the present invention will be described.

  The conductive metal powder that can be used in the present invention is not particularly limited as long as it is a metal powder containing silver, and may be not only silver powder but also metal powder having silver adhered or coated on the surface. Examples of the metal powder herein include metal elements such as aluminum, silicon, boron, carbon, magnesium, nickel, copper, graphite, gold, and palladium, and powders of metal oxides and metal nitrides thereof. Among these, aluminum, nickel, gold, and palladium are preferable from the viewpoint of conductivity.

  Specific examples of the metal oxide and the metal nitride include alumina, magnesium oxide, aluminum nitride, boron nitride, silicon nitride, fused silica, crystalline silica, magnesium silicate, aluminum and silicon composite metal oxide, aluminum and Examples include magnesium composite metal oxides.

  The conductive metal powder may be a surface-coated polymer such as polyethyleneimine, polyvinylpyrrolidone, polyacrylic acid, carboxymethylcellulose, polyvinyl alcohol, or a copolymer having a polyethyleneimine moiety and a polyethylene oxide moiety. By coating with these polymers, the dispersibility in the resin composition tends to be good.

  Since silver is an element having a low volume resistivity and the conductivity of the metal powder depends more on the surface state than the core carrier, the entire conductive metal powder particles are not silver. Both can also be used with metal powder having silver deposited or coated on its surface.

  The shape of the silver powder is not particularly limited, and examples thereof include scaly, spherical, and dendritic shapes.

  The scaly silver powder has many silver powder contacts and is excellent in conductivity, and when it is made into a conductive resin composition due to its orientation, it tends to be excellent in workability because it exhibits thixotropy. On the other hand, when used for a precise member, there may be a problem of poor electrical connection due to the orientation. The size is not particularly limited, but is preferably 50 μm or less, more preferably 1 to 20 μm, as an average particle size determined by a laser diffraction particle size distribution analyzer. Such an average particle size is preferable because the possibility of poor electrical connection is reduced even when used for precision electronic components.

  Since the spherical silver powder has almost no orientation, it is less likely to cause a problem in electrical joining, but the particles tend to be in contact with each other because of the point contact. The size is not particularly limited, but the average particle size is preferably 20 μm or less, more preferably 5 μm or less. When the average particle diameter exceeds 20 μm, the conductivity tends to be low. Furthermore, when using together with scale-like silver powder and using also for the purpose of aiming at electroconductivity by filling the gap | interval, it is preferable to select a thing of 5 micrometers or less.

  Although dendritic silver powder has a large specific surface area and excellent conductivity, the quality may become unstable due to its specific shape. The size is not particularly limited, but the average particle size is preferably 30 μm or less, more preferably 5 μm or less. This average particle size is preferable because it tends to be excellent in handling.

  In the present invention, it is preferable to use silver powders having different shapes in combination in view of these properties depending on the purpose and application.

  Moreover, the preferable compounding quantity with respect to the resin composition of electroconductive metal powder is 60-85 mass%, More preferably, it is 70-80 mass%. When the blending amount is 60% by mass or more, the conductivity tends to be further improved, and when it is 85% by mass or less, the bleed phenomenon tends to be prevented.

  An insulating resin composition obtained by further adding an insulating powder to the modified resin composition of the present invention will be described.

  Specific examples of the insulating powder that can be used in the present invention include non-oxide ceramic powders such as carbon, boron carbide, boron nitride, aluminum nitride, and titanium nitride; oxide powders such as beryllium, magnesium, aluminum, and titanium. Silicon oxide, silicon nitride, fused silica, crystalline silica, other fillers containing silicon; magnesium silicate, aluminum and silicon composite metal oxide, aluminum and magnesium composite metal oxide; muscovite, phlogopite, mica Powders such as knight, steatite, alumina, soda glass, borosilicate glass, quartz glass, and wood; resin powders such as silicon rubber and Teflon (registered trademark), etc., may be used alone or in combination. be able to. Among these, silicon oxide, silicon nitride, fused silica, crystalline silica, and other fillers containing silicon are preferred from the viewpoints of insulation and availability.

  The insulating powder may be surface-coated with a polymer such as a silane compound, polyethyleneimine, polyvinylpyrrolidone, polyacrylic acid, carboxymethylcellulose, polyvinyl alcohol, or a copolymer having a polyethyleneimine moiety and a polyethyleneoxide moiety. By coating with these polymers, the dispersibility in the resin composition tends to be good.

  Moreover, the preferable compounding quantity with respect to the resin composition of insulating powder is 5-50 mass%, More preferably, it is 10-30 mass%. When the blending amount is 5% by mass or more, the insulating property tends to be further improved, and when it is 50% by mass or less, the reliability of the semiconductor device tends to be improved due to the stress relaxation effect.

  In addition to the epoxy resin (A), an organic resin such as a silicone resin, an acrylic resin, a urea resin, and an imide resin can be added to the modified resin composition of the present invention.

  The modified resin composition of the present invention can be made into a curable resin composition by further adding a curing agent and / or a curing accelerator.

  A hardening | curing agent is a substance used in order to harden a resin composition, and is not specifically limited. As the curing agent, for example, acid anhydride compounds, amine compounds, amide compounds, phenol compounds and the like can be used, and in particular, aromatic acid anhydrides, cyclic aliphatic acid anhydrides, aliphatic acid anhydrides, and the like. An acid anhydride compound is preferred, and a carboxylic acid anhydride is more preferred.

  The acid anhydride compounds include alicyclic acid anhydrides, and alicyclic carboxylic acid anhydrides are preferred among carboxylic acid anhydrides. These hardened | cured materials may be used individually or may be used in combination of 2 or more type.

  Specific examples of the curing agent include phthalic anhydride, succinic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride. , Methylhexahydrophthalic anhydride, norbornane-2,3-dicarboxylic anhydride, methylnorbornane-2,3-dicarboxylic anhydride, diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, tetra Polyamide resins, bisphenols, phenols (phenols, alkyl-substituted phenols) synthesized from ethylenepentamine, dimethylbenzylamine, ketimine compounds, dimer of linolenic acid and ethylenediamine Naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and polycondensates of various aldehydes, polymers of phenols and various diene compounds, polycondensates of phenols and aromatic dimethylol, or bis Examples include condensates of methoxymethyl biphenyl with naphthols or phenols, biphenols and modified products thereof, imidazole, boron trifluoride-amine complexes, guanidine derivatives, and the like.

  Specific examples of the alicyclic carboxylic acid anhydride include 1,2,3,6-tetrahydrophthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, hexahydrophthalic anhydride, “4-methylhexahydro Phthalic anhydride / hexahydrophthalic anhydride = 70/30 ”, 4-methylhexahydrophthalic anhydride,“ methylbicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride / bicyclo [2.2. 1] heptane-2,3-dicarboxylic anhydride "and the like.

  Among these curing agents, since the light resistance of the cured product obtained by curing the modified resin composition of the present invention tends to increase, alicyclic acid anhydrides, two or more acid anhydrides per molecule More preferred are silicones having a product-containing functional group as a substituent, such as methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, norbornane-2,3-dicarboxylic anhydride, methylnorbornane-2,3-dicarboxylic anhydride. Further preferred. These curing agents can be used as one kind or a mixture of two or more kinds.

  The amount of the curing agent used is preferably 1 part by mass or more and 200 parts by mass or less, and more preferably 2 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the modified resin composition obtained by the present invention. When the amount of the curing agent used is less than 1 part by mass with respect to 100 parts by mass of the modified resin composition, the curing rate may decrease. On the other hand, when it exceeds 200 parts by mass, the moisture resistance of the cured product is deteriorated. There is.

  Examples of the curing accelerator used include imidazole compounds, quaternary ammonium salts, phosphonium salts, amine compounds, aluminum chelate compounds, organic phosphine compounds, metal carboxylates and acetylacetone chelate compounds. These curing accelerators can be used as one kind or a mixture of two or more kinds.

  Specific examples of these compounds include 2-methylimidazole, 2-ethyl-4-methylimidazole, 1,8-diaza-bicyclo (5,4,0) undecene-7, trimethylamine, benzyldimethylamine, triethylamine, dimethyl Amine compounds such as benzylamine, 2,4,6-trisdimethylaminomethylphenol and salts thereof, quaternary ammonium salts such as tetramethylammonium chloride, benzyltrimethylammonium bromide, tetrabutylammonium bromide, aluminum chelate, tetra-n- Organic phosphine compounds such as butylphosphonium benzotriazolate, tetra-n-butylphosphonium-0,0-diethyl phosphorodithioate, chromium (III) tricarboxylate, tin octylate, chromium Metal carboxylates and acetylacetone chelate compounds such acetylacetonate can be exemplified. Moreover, as a commercial item, U-CAT SA1, U-CAT 2026, U-CAT 18X etc. can be illustrated from a San Apro company. Among these, an imidazole compound, a quaternary ammonium salt, a phosphonium salt, an organic phosphine compound, and the like are preferably used because they give a cured product with less coloring.

  The blending amount of these curing accelerators is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, in order to increase the curing rate with respect to 100 parts by mass of the modified resin composition. It is especially preferable that it is 0.1 mass part or more. On the other hand, from the viewpoint of moisture resistance, it is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, still more preferably 3 parts by mass or less, and particularly preferably 1 part by mass or less.

  Moreover, the modified resin composition obtained by this invention can also be made into a curable composition by mix | blending a conventionally well-known cationic polymerization catalyst.

Examples of cationic polymerization catalysts that can be used include Lewis acid catalysts typified by BF ₃ / amine complexes, PF ₅ , BF ₃ , AsF ₅ , SbF ₅ , phosphonium salts, quaternary ammonium salts, sulfonium salts, benzylammonium. Salt, benzylpyridinium salt, benzylsulfonium salt, hydrazinium salt, carboxylic acid ester, sulfonic acid ester, thermosetting cationic polymerization catalyst represented by amine imide, diaryliodonium hexafluorophosphate, bis (dodecylphenyl) iodonium hexafluoroantimonate And UV curable cationic polymerization catalysts represented by the above.

  Among these, a thermosetting cationic polymerization catalyst is preferably used because a transparent cured product having a high glass transition temperature and excellent solder heat resistance and adhesion and less coloring can be obtained. As such a thermosetting cationic polymerization catalyst, for example, SI-100L, SI-60L (manufactured by Sanshin Chemical Co., Ltd.), CP-66, CP-77 (and above) which are sulfonium salt-based cationic polymerization initiators. Asahi Denka Kogyo).

  The blending amount of these cationic polymerization catalysts is usually preferably 0.001 part by mass or more and more preferably 0.005 part by mass or more for increasing the curing rate with respect to 100 parts by mass of the modified resin composition. Preferably, it is 0.01 mass part or more. On the other hand, from the viewpoint of moisture resistance, the range is preferably 10 parts by mass or less, more preferably 1 part by mass or less, still more preferably 0.5 parts by mass or less, and 0.2 parts by mass or less. It is particularly preferred.

A photoacid generator can be further added to the modified resin composition of the present invention to form a photosensitive resin composition. The photoacid generator that can be used in the present invention is not particularly limited as long as it is a compound that releases an acid when irradiated with light and initiates polymerization, and among them, an onium salt is preferable. Specific examples include diazonium salts, iodonium salts, sulfonium salts, and the like. These are each cationic moiety aromatic diazonium, aromatic iodonium, aromatic sulfonium, anionic portion is BF4 ^{-, PF6} -, SbF6 ^- , [BX4] ^- (wherein X is a phenyl group substituted with at least two fluorine or trifluoromethyl groups) and the like. Typical examples of the photoacid generator are shown below.

  More specific examples include boron difluoride aryldiazonium salts, phosphorus hexafluoride triarylsulfonium salts, phosphorus hexafluoride diaryliodonium salts, antimony hexafluoride triarylphosphonium salts, antimony hexafluoride. Diaryl iodonium salt, tri-4-methylphenylsulfonium salt of arsenic hexafluoride, tri-4-methylphenylsulfonium salt of antimony tetrafluoride, triarylsulfonium salt of tetrakis (pentafluorophenyl) borate, tetrakis (pentafluoro) Phenyl) borate diaryl iodonium salt, acetylacetone aluminum salt and orthonitrobenzylsilyl ether mixture, phenylthiopyridinium salt, phosphorus hexafluoride allene-iron complex and the like. Commercially available products include CD-1012 (manufactured by SARTOMER), PCI-019, PCI-021 (manufactured by Nippon Kayaku Co., Ltd.), Optmer SP-150, Optomer SP-170 (manufactured by ADEKA Corporation), UVI-6990. , UVI-6974 (manufactured by Dow Chemical Co., Ltd.), CPI-100P, CPI-100A, CPI-100L (manufactured by Sun Apro Co., Ltd.), TEPBI-S (manufactured by Nippon Shokubai Co., Ltd.), Rhodorsil 2074 (manufactured by Rhodia), and the like. . These can be used alone or in combination of two or more. Among these, sulfonium salts and iodonium salts are preferable from the viewpoint that the cured product is less colored, and sulfonium salts are particularly preferable in view of curability.

  Furthermore, it is also possible to mix | blend vinyl ether compounds with the said photosensitive resin composition as needed. Examples of these compounds include vinyl ether compounds that do not contain a hydroxyl group. Specifically, for example, ethylene glycol divinyl ether, butanediol divinyl ether, cyclohexane dimethanol divinyl ether, cyclohexane diol divinyl ether, trimethylolpropane trivinyl ether, pentaerythritol tetravinyl ether, glycerol trivinyl ether, triethylene glycol divinyl ether, diethylene glycol A divinyl ether etc. can be mentioned.

Moreover, a conventionally well-known cationic polymerization catalyst can also be mix | blended with the modified resin composition of this invention. Examples of cationic polymerization catalysts that can be used include Lewis acid catalysts such as BF ₃ / amine complexes, PF ₅ , BF ₃ , AsF ₅ , SbF ₅ , phosphonium salts, quaternary ammonium salts, sulfonium salts, benzyl ammonium Salt, benzylpyridinium salt, benzylsulfonium salt, hydrazinium salt, carboxylic acid ester, sulfonic acid ester, thermosetting cationic polymerization catalyst represented by amine imide, diaryliodonium hexafluorophosphate, bis (dodecylphenyl) iodonium hexafluoroantimonate And UV curable cationic polymerization catalysts represented by the above. Among them, a thermosetting cationic polymerization catalyst is preferably used because it tends to provide a transparent cured product having a high glass transition temperature and excellent solder heat resistance and adhesion and less coloring. Commercially available products of such thermosetting cationic polymerization catalysts include, for example, SI-100L, SI-60L (manufactured by Sanshin Chemical Co., Ltd.), CP-66, CP-, which are sulfonium salt cationic polymerization initiators. 77 (above, manufactured by Asahi Denka Kogyo Co., Ltd.).

  The modified resin composition obtained according to the present invention may contain a modifier as necessary from the viewpoint of imparting flexibility to the cured product and improving the peel adhesion. Examples of the modifier used include polyols containing two or more hydroxyl groups in one molecule, such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, 1,2-propanediol, 1,3- Propanediol, dipropylene glycol, tripropylene glycol, polypropylene glycol, 1,2-butanediol, 1,4-butanediol, neopentyl glycol, glycerin, erythritol, trimethylolpropane, 1,2,4-butanetriol, etc. Aliphatic polyols, polycarbonate diols, and silicones having a silanol group at the terminal are preferably used. These modifiers can be used as one kind or a mixture of two or more kinds.

  In the modified resin composition of the present invention, various silane coupling agents can be used for the purpose of improving physical properties such as adhesion. In this case, the residual alkoxy group in the modified resin composition needs to be 5% or less. If the residual alkoxy group exceeds 5%, the thermal shock resistance and the adhesiveness during thermal cycling of the cured product obtained by curing the composition will be insufficient.

  Suitable silane coupling agents for the modified resin composition of the present invention include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidyl. Sidoxypropylmethyldiethoxysilane, 3-glycidoxypropyldimethylmethoxysilane, 3-glycidoxypropyldimethylethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4- Epoxycyclohexyl) ethyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyldimethylethoxysilane, N- (2-aminoethyl) aminomethylto Methoxysilane, N- (2-aminoethyl) (3-aminopropyl) trimethoxysilane, N- (2-aminoethyl) (3-aminopropyl) triethoxysilane, N- (2-aminoethyl) (3- Aminopropyl) methyldimethoxysilane, N- [N ′-(2-aminoethyl) (2-aminoethyl)] (3-aminopropyl) trimethoxysilane, 2- (2-aminoethyl) thioethyltriethoxysilane, 2- (2-aminoethyl) thioethylmethyldiethoxysilane, 3- (N-phenylamino) propyltrimethoxysilane, 3- (N-cyclohexylamino) propyltrimethoxysilane, (N-phenylaminomethyl) trimethoxy Silane, (N-phenylaminomethyl) methyldimethoxysilane, (N-cyclohexylamino) Methyl) triethoxysilane, (N-cyclohexylaminomethyl) methyldiethoxysilane, piperazinomethyltrimethoxysilane, piperazinomethyltriethoxysilane, 3-piperazinopropyltrimethoxysilane, 3-piperazinopropyl Methyldimethoxysilane, 3-ureidopropyltriethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, mercaptomethylmethyldimethoxysilane, mercaptomethylmethyldiethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltri Ethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, 3- (trimethoxysilyl) propylsuccinic anhydride, 3 -(Triethoxysilyl) propyl succinic anhydride, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, Vinyltrimethoxysilane, vinyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methyl Vinyldimethoxysilane, methylvinyldiethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane , Methylcyclohexyldimethoxysilane, methylcyclohexyldiethoxysilane, methylcyclopentyldimethoxysilane, methylcyclopentyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxy Silane, 3-methacryloxypropyl triethoxysilane, etc. are mentioned. Moreover, the partial condensate of these silane coupling agents can also be used.

  Furthermore, the modified resin composition of the present invention includes inorganic fillers, colorants, leveling agents, lubricants, surfactants, antioxidants, light, other than those described above, as long as their functions are not impaired. Stabilizers can be added as appropriate. In addition, plasticizers, flame retardants, stabilizers, antistatic agents, impact strengthening agents, foaming agents, antibacterial / antifungal agents, conductive fillers, antifogging agents, and crosslinks that are generally used as additives for resins An agent or the like can be blended.

  Examples of the inorganic filler include silicas (melted crushed silica, crystal crushed silica, spherical silica, fumed silica, colloidal silica, precipitated silica, etc.), silicon carbide, silicon nitride, boron nitride, calcium carbonate, magnesium carbonate, Barium sulfate, calcium sulfate, mica, talc, clay, aluminum oxide, magnesium oxide, zirconium oxide, aluminum hydroxide, magnesium hydroxide, calcium silicate, aluminum silicate, lithium aluminum silicate, zirconium silicate, barium titanate, glass fiber, carbon Examples thereof include fibers and molybdenum disulfide. In particular, silicas, calcium carbonate, aluminum oxide, aluminum hydroxide, calcium silicate and the like are preferable, and silicas are more preferable in consideration of physical properties of the cured product. These inorganic fillers may be used alone or in combination of two or more.

  The colorant is not particularly limited as long as it is a substance used for the purpose of coloring. For example, phthalocyanine, azo, disazo, quinacridone, anthraquinone, flavantron, perinone, perylene, dioxazine, condensed azo, azomethine series Inorganic pigments such as titanium oxide, lead sulfate, chromium yellow, zinc yellow, chromium vermillion, valve shell, cobalt purple, bitumen, ultramarine, carbon black, chromium green, chromium oxide, cobalt green, and the like. These colorants may be used alone or in combination of two or more.

  The leveling agent is not particularly limited, and examples thereof include oligomers having a molecular weight of 4000 to 12000 made of acrylates such as ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, epoxidized soybean fatty acid, epoxidized abiethyl alcohol, Examples include hydrogenated castor oil and titanium-based coupling agents. These leveling agents may be used alone or in combination of two or more.

The lubricant is not particularly limited. For example, hydrocarbon lubricants such as paraffin wax, microwax and polyethylene wax; higher fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid and behenic acid. Higher fatty acid amide type lubricants such as stearylamide, palmitylamide, oleylamide, methylenebisstearamide, ethylenebisstearamide; hydrogenated castor oil, butyl stearate, ethylene glycol monostearate, pentaerythritol (mono- , Di-, tri-, or tetra-) stearate and other higher fatty acid ester lubricants; cetyl alcohol, stearyl alcohol, polyethylene glycol, polyglycerol and other alcohol lubricants; lauric acid, myristic acid, palmitic Metal soaps that are metal salts such as magnesium, calcium, cadmium, barium, zinc, lead such as acid, stearic acid, arachidic acid, behenic acid, ricinoleic acid, naphthenic acid; natural waxes such as carnauba wax, candelilla wax, beeswax, and montan wax And the like. These lubricants may be used alone or in combination of two or more.

  The surfactant is an amphiphilic substance having a hydrophobic group having no affinity for the solvent in the molecule and an amphiphilic group (usually a hydrophilic group) having an affinity for the solvent. The type of the surfactant is not particularly limited, and examples thereof include silicone surfactants and fluorine surfactants. Surfactants may be used alone or in combination of two or more.

  The antioxidant is not particularly limited, and examples thereof include organic phosphorus antioxidants such as triphenyl phosphate and phenylisodecyl phosphite; organic sulfur type such as distearyl-3,3′-thiodipropinate. Antioxidants; phenolic antioxidants such as 2,6-di-tert-butyl-p-cresol and the like.

  The light stabilizer is not particularly limited, and examples thereof include benzotriazole-based, benzophenone-based, salicylate-based, cyanoacrylate-based, nickel-based, and triazine-based ultraviolet absorbers, hindered amine-based light stabilizers, and the like.

  For the modified resin composition of the present invention or the modified resin composition of the present invention, an oxetane compound, phosphor, conductive metal powder, insulating powder, curing agent and curing accelerator (I), or photoacid generator Furthermore, if necessary, a curable resin composition containing a cationic polymerization catalyst, a modifier, a vinyl ether compound, an organic resin other than the epoxy resin (A), and a silane coupling agent is made into a cured product by a known method. be able to. Especially, the method of hardening by heating or the method of hardening by irradiating light is a method generally used as a hardening method of an epoxy resin, and can be illustrated as a preferable method in this invention. The temperature for curing by heating is not particularly limited because it depends on the epoxy resin or curing agent used, but is usually in the range of 20 to 200 ° C.

  On the other hand, the light used for curing by irradiation with light is preferably ultraviolet light or visible light, and more preferably ultraviolet light. Examples of the light source include low-pressure mercury lamp, medium-pressure mercury lamp, high-pressure mercury lamp, ultrahigh-pressure mercury lamp, UV lamp, xenon lamp, carbon arc lamp, metal halide lamp, fluorescent lamp, tungsten lamp, argon ion laser, helium cadmium laser, Examples of the light source include a helium neon laser, a krypton ion laser, various semiconductor lasers, a YAG laser, an excimer laser, a light emitting diode, a CRT light source, and a plasma light source.

  The curing reaction described above can be performed in air, or in an inert gas atmosphere such as nitrogen, helium, or argon as necessary.

  The modified resin composition of the present invention includes, for example, a) a modified resin composition of the present invention, b) a resin composition obtained by further adding an oxetane compound to the modified resin composition of the present invention, and c) the modified resin of the present invention. A fluorescent resin composition obtained by further adding a phosphor to the composition, or a resin composition obtained by further adding a curing agent to the above-mentioned a) to c) is excellent in adhesion to an element or a package material, Excellent light-emitting element sealing material that does not generate cracks and has little decrease in luminance over the long term, or can be injection-molded, is hard, has excellent step stability, and has light resistance after curing. It is usefully used as a raw material for a curable resin composition for producing a lens. Further, a curable resin composition in which a curing accelerator is further added to the resin composition obtained by further adding a curing agent to the above a) to c), or a photoacid in addition to the above a) to c). The photosensitive resin composition to which the generator is added can be usefully used as the light-emitting element sealing material, the curable resin composition for producing an optical lens, or the photosensitive resin composition. .

  A light-emitting component such as a light-emitting diode can be produced by sealing the light-emitting element with a curable resin composition containing the modified resin composition of the present invention. Furthermore, the modified resin composition obtained by the present invention has excellent transparency, heat-resistant yellowing, light resistance under heating conditions, and further resistance to cold and thermal shock. Lenses, lens materials for pickup lenses for CDs and DVDs, lenses for automobile headlamps, lenses for projectors, optical fibers, optical waveguides, optical filters, optical adhesives, optical disk substrates, display substrates, antireflection coatings, etc. It can be used as various optical members such as materials.

  Furthermore, the above light emitting diode and / or the above optical lens include, for example, a backlight such as a liquid crystal display, illumination, various sensors, a light source such as a printer and a copying machine, an instrument light source for vehicles, a signal light, an indicator light, and a display. It can be suitably used as a semiconductor device such as a device, a light source of a planar light emitter, a display, a decoration, and various lights.

  The emission wavelength of the light emitting device sealed using the sealing material for light emitting device comprising the curable resin composition containing the modified resin composition of the present invention is wide from infrared to red, green, blue, purple and ultraviolet. It can be used, and light having a wavelength of 250 nm to 550 nm, which is deteriorated due to insufficient light resistance, can be practically used. As a result, a white light-emitting diode having a long life, high energy efficiency, and high color reproducibility can be obtained. Here, the emission wavelength refers to the main emission peak wavelength.

  As a specific example of the light emitting element to be used, for example, a light emitting element formed by stacking semiconductor materials on a substrate can be exemplified. In this case, examples of the semiconductor material include GaAs, GaP, GaAlAs, GaAsP, AlGaInP, GaN, InN, AlN, InGaAlN, and SiC.

  Examples of the substrate include sapphire, spinel, SiC, Si, ZnO, and GaN single crystal. If necessary, a buffer layer may be formed between the substrate and the semiconductor material. Examples of these buffer layers include GaN and AlN.

  The method for laminating the semiconductor material on the substrate is not particularly limited, but for example, MOCVD method, HDVPE method, liquid phase growth method and the like are used.

  Examples of the structure of the light emitting element include a homojunction having a MIS junction, a PN junction, and a PIN junction, a heterojunction, and a double heterostructure. A single or multiple quantum well structure may also be used.

  A light emitting diode can be manufactured by sealing a light emitting element using the light emitting element sealing material which consists of curable resin composition containing the modified resin composition of this invention. In this case, the light-emitting element can be sealed only with the light-emitting element sealing material, but it is also possible to use another sealing material in combination. When other sealing material is used in combination, after sealing with a light emitting element sealing material obtained using the modified resin composition obtained by the present invention, the periphery is sealed with another sealing material, or After sealing with another sealing material, it is also possible to seal the periphery with a light emitting element sealing material obtained using the modified resin composition obtained by the present invention. Examples of the other sealing material include an epoxy resin, a silicone resin, an acrylic resin, a urea resin, an imide resin, and glass.

  As a method for sealing a light emitting element with a light emitting element sealing material obtained by using the modified resin composition of the present invention, for example, a light emitting element sealing material is injected in advance into a mold mold, and the light emitting element is inserted therein. Examples include a method in which a fixed lead frame or the like is immersed and cured, and a method in which a light emitting element sealing material is injected into a mold frame in which the light emitting element is inserted and cured. At this time, examples of the method for injecting the light-emitting element sealing material include injection by a dispenser, transfer molding, injection molding, and the like. Other sealing methods include a method in which a light emitting device sealing material is dropped onto the light emitting device, and stencil printing, screen printing, or a method of applying and curing through a mask, a cup in which the light emitting device is disposed in the lower part, etc. For example, a method of injecting a light-emitting element sealing material with a dispenser or the like and curing it.

  The curable resin composition containing the modified resin composition of the present invention can also be used as a die bond material for fixing a light emitting element to a lead terminal or a package, a passivation film on the light emitting element, and a package substrate. Examples of the shape of the sealing portion include a bullet-shaped lens shape, a plate shape, and a thin film shape.

  The performance of the light-emitting diode obtained using the modified resin composition of the present invention can be improved by a conventionally known method. As a method for improving the performance, for example, a method of providing a light reflecting layer or a light collecting layer on the back surface of the light emitting element, a method of forming a complementary colored portion on the bottom, and a layer that absorbs light having a wavelength shorter than the main emission peak is emitted. Method of providing on the element, sealing the light emitting element, molding with a hard material, inserting the light emitting diode into the through hole and fixing, connecting the light emitting element to the lead member by flip chip connection, etc. For example, a method of extracting light from the substrate direction.

  Moreover, to the modified resin composition of the present invention, a curable resin composition obtained by further adding a curing agent to the fluorescent resin composition obtained by further adding a phosphor, or the modified resin composition of the present invention, Further, by curing a photosensitive resin composition to which a photoacid generator is added, a phosphorescent material having excellent light emitting properties can be produced.

  Next, the phosphorescent material will be described. In general, a phosphorescent material is excited by light stimulation such as sunlight, fluorescent light, ultraviolet light, etc., energy is converted to emit light, and light is gradually emitted even after the excitation stop by the above light stimulation, for a long time. A material that continues to emit light.

  The use of the phosphorescent material using the modified resin composition of the present invention is not particularly limited. For example, indications at night and during power outages, disaster prevention / safety signs, clocks, wallpaper, electric switches, signs, clothing Examples thereof include reflectors for shoes, bicycles and motorcycles, adhesive tapes, fishing gear such as fishing hooks and floats, exercise equipment, accessories, toys and the like.

  Further, for example, (d) a conductive resin composition obtained by adding a conductive metal powder to the modified resin composition of the present invention is excellent in fluidity, conductivity and adhesiveness, and suppresses the generation of voids. On the other hand, as a raw material for the curable conductive resin composition to be used, (e) an insulating resin composition obtained by further adding an insulating powder to the modified resin composition of the present invention, or the above (d), ( The resin composition obtained by further adding a curing agent to e) is useful as a curable insulating resin composition raw material having excellent insulation and adhesiveness and suppressing generation of voids. Further, a curable resin composition in which a curing accelerator is further added to the resin composition obtained by further adding a curing agent to the above (d) and (e), or the above (d) and (e). Furthermore, the photosensitive resin composition to which a photoacid generator is further added can be usefully used as the curable conductive resin composition or the curable insulating resin composition.

  The use of the conductive resin composition using the modified resin composition of the present invention is not particularly limited. For example, adhesion between a semiconductor element and a peripheral member, formation of a conductor wiring, replacement of solder at the time of surface mounting ; Castings and circuit units for insulators, crystal resonators, AC transformers, switchgears, etc., packages of various parts, ICs, light emitting diodes, semiconductors, generators, rotating coils for motors, winding impregnation, printing Wiring board, glass substitute transparent board, electronic components such as medium-sized insulators, coils, connectors, terminals, etc., and adhesives and die-bonding agents used for the wiring; conductive paint, electrodes, printed circuit, conductive resin, etc. It can be illustrated.

  The use of the insulating resin composition using the modified resin composition of the present invention is not particularly limited. For example, mounting of a semiconductor chip in a semiconductor device; a semiconductor chip (IC, LSI, etc.), a ceramic case Examples thereof include a die bond agent and an adhesive for bonding to a lead frame, a substrate and the like. Furthermore, the present invention can be applied to applications requiring a highly heat-insulating insulating material such as an interposer for semiconductor packages, a printed circuit board, a display, a solar cell, a generator / motor board, an automobile board, and the like.

  Further, for example, (a) the modified resin composition of the present invention, (b) a resin composition obtained by adding an oxetane compound to the modified resin composition of the present invention, and (c) the modified resin composition of the present invention, Further, a curable resin composition obtained by adding a curing agent and a curing accelerator to (a) to (c) comprising a fluorescent resin composition obtained by adding a phosphor, or the above (a) to (c). A photosensitive resin composition in which a photoacid generator is further added, for example, (d) a conductive resin composition obtained by further adding a conductive metal powder to the modified resin composition of the present invention, (e) An insulating resin composition obtained by further adding an insulating powder to the modified resin composition of the present invention, a curable resin composition obtained by adding a curing agent and a curing accelerator to the above (d) and (e), Alternatively, the photosensitive resin composition in which a photoacid generator is further added to the above (d) and (e), is subject to polymerization inhibition by oxygen. It can be usefully used as a coating agent that is difficult to break.

  The coating agent in the present invention is not particularly limited as long as it is a material for forming a coating film on the surface of a substance and covering it, and the main use purpose is as follows, if necessary, It is also possible to mix pigments, pigments and the like with the coating agent and use them as paints and inks.

(1) Protection of coatings and substrates, imparting durability, maintaining aesthetics (protection from ultraviolet rays, infrared rays, oxidation, corrosion, scratches, dust, dirt, temperature, humidity, etc.)
(2) Glossiness imparted to coatings and substrates (3) Water repellent treatment to coatings and substrates (4) Non-slip processing for flooring, etc. (5) Sealing and insulation of electronic components

When used as a coating agent, it is also possible to use a resin composition obtained by further adding an oxetane compound to the modified resin composition of the present invention.
The coating agent of the present invention can be applied by a conventionally known method and then cured to form a coating film. At this time, the application methods include brush coating, roller coating, spray coating, bar coater, roll coater, baking coating, dip coating, electrodeposition coating, electrostatic coating, powder coating, vapor deposition, plating, and other coating techniques. Printing techniques such as inkjet, laser printing, rotary printing, gravure printing, and screen printing, on the other hand, as a method of forming a coating film, a method of curing by heating, or a method of curing by irradiating light, Each is preferably used.

  The use of the coating agent and the coating film of the present invention is not particularly limited. For example, the coating agent (painting, resin, plastic, metal, steel pipe, automobile, building, optical fiber use, etc.), optical disc (DVD, CD, Blu-ray disc, etc.) coating and adhesion, ink (inkjet printer, gravure printing, flexographic printing, resist for printed wiring board, UV printing, etc.), printing plate making material (PS flat plate, photosensitive resin relief plate, photosensitive for screen plate) Materials), photoresist (semiconductor resist, printed wiring board resist, photofabrication resist, etc.), printed wiring board, pattern formation of various electronic parts including IC, LSI, color for liquid crystal and PDP display Filter forming materials, liquid crystal and organic EL sealing materials, semi Body / light emitting diode peripheral materials (encapsulant, lens material, substrate material, die bond material, chip coating material, laminated plate, optical fiber, optical waveguide, optical filter, adhesive for electronic components, coating material, sealing material, insulating material , Photoresists, encap materials, potting materials, optical transmission layers and interlayer insulation layers of optical disks, printed wiring boards, laminates, light guide plates, antireflection films, etc.), paints (corrosion resistant paints, maintenance, marine paints, corrosion resistant linings) , Primers for automobiles and home appliances, Beverages / beer cans, Exterior lacquers, Extrusion tube coatings, General anticorrosion coatings, Maintenance lacquers, Lacquers for woodwork products, Electrodeposition primers for automobiles, Other industrial electrodeposition coatings, Beverages / beer cans Internal lacquer, coil coating, drum / can internal coating, wood coating, acid lining, wire enamel, insulating coating Automotive primer, exterior and anticorrosion coating of various metal products, pipe inner and outer surface coating, electrical component insulation coating, etc.), composite materials (chemical plant pipes and tanks, aircraft materials, automotive parts, various sporting goods, carbon fiber composites) Materials, aramid fiber composite materials, etc.), civil engineering and building materials (floor materials, pavement materials, membranes, anti-slip and thin-layer pavements, concrete jointing / uplifting, anchor embedding adhesion, precast concrete bonding, tile adhesion, concrete structures Repair of cracks, grouting and leveling of pedestals, anticorrosion and waterproofing of water and sewage facilities, anticorrosive laminated lining of tanks, anticorrosion of iron structures, mastic coating of exterior walls of buildings, etc., adhesives (metal, glass, ceramics, etc.) Adhesives of the same or different materials such as cement concrete, wood, plastic, etc., automobiles, railway vehicles, aircraft Assembling adhesives, prefabricated composite panel manufacturing adhesives, etc .: including one-pack type, two-pack type, and sheet type. ), Aircraft / automobile / plastic molding jigs (resin molds such as press molds, stretched dies, matched dies, vacuum molding / blow molding molds, master models, casting patterns, laminated jigs, various inspection jigs, etc.), It can be used as a modifier / stabilizer (fiber resin processing, stabilizer for polyvinyl chloride, additive to synthetic rubber, etc.) and the like. Among these, it is useful for coating agents, paints, adhesives, and optical modeling resin applications.

The present invention will be specifically described below.
The characteristics of the index and the modified resin composition used in the present invention are quantified by the following method.

<Calculation of mixing index α>
The mixing index α is calculated by the following general formula (2).
Mixing index α = (αc) / (αb) (2)
Here, αb and αc represent the following.
αb: In the general formula (1), n = 1 or 2, mol% of the alkoxysilane compound containing a group having at least one cyclic ether group as R ¹ [(B) in the present invention],
αc: In the general formula (1), n = 1 or 2, and R ¹ is mol% of an alkoxysilane compound containing a phenyl group having at least one fluorine atom as a substituent [(C) of the present invention] ].

<Calculation of mixing index β>
The mixing index β is calculated by the following general formula (3).
Mixing index β = {(βn2) / (βn0 + βn1)} (3)
Here, βn0, βn1, and βn2 represent the following.
βn2: mol% of the alkoxysilane compound in which n = 2 in the general formula (1),
βn0: mol% of the alkoxysilane compound in which n = 0 in the general formula (1),
βn1: mol% of the alkoxysilane compound in which n = 1 in the general formula (1).
However, 0 ≦ {(βn0) / (βn0 + βn1 + βn2)} ≦ 0.1.

<Calculation of mixing index γ>
The mixing index γ is calculated by the following general formula (4).
Mixing index γ = (γa) / (γs) (4)
Here, γa and γs represent the following.
γa: mass of epoxy resin (g),
γs: Mass (g) of the alkoxysilane compound in which n = 0 to 2 in the general formula (1).

<Calculation of mixing index ε>
The mixing index ε is calculated by the following general formula (7).
Mixing index ε = (εw) / (εs) (7)
Here, εw and εs represent the following.
εw: amount of water added (in mol),
.epsilon.s: The amount of the general formula ^{(1) (OR 2) (} mol number).

<Calculation of intermediate condensation rate>
The condensation rate of the intermediate was determined by the following procedure from the ²⁹ Si-NMR measurement result of the sample solution (intermediate) collected after the refluxing step.
Dissolve 0.15 g of the sample solution in 1 g of deuterated chloroform. A solution obtained by adding 0.015 g of Cr (acac) ₃ to the solution and dissolving is used as an NMR measurement solution. Using this NMR measurement solution, ²⁹ Si-NMR measurement under proton complete decoupling conditions is performed with 6,000 integrations (apparatus: α-400 manufactured by JASCO Corporation).

Based on the obtained spectrum, the condensation rate (%) of the intermediate was calculated according to the following formula (8).
Condensation rate (%) = (D1 × 1 + D2 × 2 + T1 × 1 + T2 × 2 + T3 × 3) /
{(D0 + D1 + D2) × 2 + (T0 + T1 + T2 + T3) × 3} × 100 (8)
Here, D0, D1, D2, T0, T1, T2, and T3 each represent the following.
D0: Sum of integral values of signals derived from the D0 structure shown in the following formula (9) derived from the alkoxysilane compound in which n = 1 in the formula (1).
D1: Total of integral values of signals derived from the D1 structure shown in the following formula (10) derived from the alkoxysilane compound in which n = 1 in the formula (1).
D2: Sum of integral values of signals derived from the D2 structure shown in the following formula (10) derived from the alkoxysilane compound in which n = 1 in the formula (1).
T0: Total of integral values of T0 structure-derived signals represented by the following formula (11) derived from alkoxysilane compounds with n = 2 in formula (1).
T1: Total of integral values of signals derived from the T1 structure shown in the following formula (12) derived from the alkoxysilane compound in which n = 2 in the formula (1).
T2: Total of integral values of signals derived from the T2 structure shown in the following formula (12) derived from the alkoxysilane compound in which n = 2 in the formula (1).
T3: Total of integral values of signals derived from the T3 structure shown in the following formula (12) derived from the alkoxysilane compound in which n = 2 in the formula (1).

前記式（９）中、Ｒは、任意の有機基又はＨである。

In said Formula (9), R is arbitrary organic groups or H.

前記式（１０）中、Ｒは、任意の有機基又はＨである。

In said formula (10), R is arbitrary organic groups or H.

前記式（１１）中、Ｒは、任意の有機基又はＨである。

In said Formula (11), R is arbitrary organic groups or H.

前記式（１２）中、Ｒは、任意の有機基又はＨである。

In said formula (12), R is arbitrary organic groups or H.

<Calculation of condensation rate of alkoxysilane compound of modified resin composition>
The condensation rate of the alkoxysilane compound of the modified resin composition was also calculated by the same method as the intermediate condensation rate calculation method from the ²⁹ Si-NMR measurement result of the sample solution collected after completion of the dehydration condensation step.

<Calculation of amount of residual alkoxy groups in modified resin composition>
Residual alkoxy group amount, from ^{the 1 H-NMR} measurement results of the samples taken after completion of the dehydration condensation step was determined by the following procedure.
The ¹ H-NMR measurement was performed according to the following procedure.
(1) In a sample bottle, 10 mg of the modified resin composition and 20 mg of an internal standard substance (1,1,2,2-tetrabromoethane; manufactured by Tokyo Chemical Industry Co., Ltd.) are weighed, and 970 mg of chloroform-d (Wako Pure Chemical Industries) is used. To prepare a solution.
(2) The solution of (1) was transferred to an NMR tube having a diameter of 5 mmφ, and H-NMR was measured under the following conditions.
Apparatus: Fourier transform nuclear magnetic resonance apparatus "α-400 type" manufactured by JEOL Ltd.
Nuclide: H
Number of integrations: 600 times From the above measurement results, the amount of residual alkoxy groups (%) was calculated according to the following procedure.
(3) The area value of the peak derived from the residual alkoxy group was calculated from the H-NMR chart.
(4) The area value of the peak derived from the internal standard substance was calculated from the H-NMR chart.
(5) The area value read in (3) and (4) above was substituted into the following formula to determine the amount of residual alkoxy groups (%).
Residual alkoxy group amount (%) = (Area value of peak derived from residual alkoxy group) / (Area value of peak derived from internal standard substance) × 100

Here, the area value of the peak derived from the residual alkoxy group was calculated by the following method.
<I> When the peak derived from the residual alkoxy group is a single peak, the area of the portion surrounded by the baseline and the peak was defined as the area value of the peak derived from the residual alkoxy group.
Depending on the type of the residual alkoxy group, there may be a plurality of peaks derived from the residual alkoxy group. In that case, the area value of the peak derived from the residual alkoxy group in the present invention was the sum of the areas of the peaks derived from the plurality of residual alkoxy groups.
<Ii> When the peak derived from the residual alkoxy group is a composite peak From the point where the slope is 0 between the peak derived from the residual alkoxy group and the peak derived from other than the residual alkoxy group, the peak derived from the residual alkoxy group A tangent line was drawn so that the peak area was minimized, and the area surrounded by the tangent line and the peak derived from the residual alkoxy group was defined as the area value of the peak derived from the residual alkoxy group.

  Here, the peak derived from the residual alkoxy group is the main component of the peak, and there is no point where the slope becomes 0 between the peak derived from the residual alkoxy group and the peak derived from other than the residual alkoxy group. The peak derived from other than the residual alkoxy group was not regarded as a peak, and all the peaks were regarded as the residual alkoxy group-derived peak. In addition, the peak derived from other than the residual alkoxy group is the main component of the peak, and there is no point where the slope becomes 0 between the peak derived from the residual alkoxy group and the peak derived from other than the residual alkoxy group The peak derived from the residual alkoxy group was not regarded as a peak.

<Epoxy equivalent (WPE)>
The epoxy equivalent is the mass (g) of the modified silicone containing 1 equivalent of an epoxy unit, and was measured according to JIS K-7236.

<Storage stability of resin composition>
The storage stability in the resin composition was evaluated by the storage stability index θ represented by the following general formula (10).
Storage stability index θ = (storage viscosity) / (starting viscosity) (10)
The container containing the resin composition immediately after production was sealed and the temperature was adjusted at 25 ° C. for 2 hours, and then the viscosity at 25 ° C. was measured, which was defined as “starting viscosity”. Further, the container containing the resin composition was sealed and stored in a constant temperature incubator at 25 ° C. for 2 weeks. After storage for a predetermined period, the viscosity at 25 ° C. was measured, and this was designated as “storage viscosity”.

When the resin composition has fluidity (viscosity is 1000 Pa · s or less) and the storage stability index θ is 4 or less, it is judged as having good storage stability, and the index θ is When exceeding 4, it was judged that there was no storage stability, and it was set as x.
The viscosity was measured by the following measurement method.
A 0.4 ml resin composition sample was placed in a rotary E-type viscometer (manufactured by Toki Sangyo Co., Ltd., “TV-22 type”, rotor: 3 ° × R14), and the resin composition was measured at a temperature of 25 ° C. did.

<Cold thermal shock test of cured product>
In the center of “Amodel A-4122NL WH 905” (15 mm × 15 mm × thickness 2 mm flat plate) manufactured by Solvay Advanced Polymers, a hollow with a diameter of 10 mm × depth of 1.2 mm was created, and then 5 mm × 5 mm × 0.2 mm. The silicon chip is placed, and the resin composition is cast and heated to obtain 10 cold shock samples for each test sample. The obtained sample was kept at −40 ° C. for 15 minutes in a thermal cycle tester (TSE-11-A manufactured by Espec Corp.), then heated to 120 ° C. in 3 minutes and then at 120 ° C. for 15 minutes. Hold and then subjected to a cycle test where the temperature is lowered to -40 ° C in 3 minutes.
During this test, the sample is taken out after 50 cycles and observed for any abnormalities such as peeling or cracking in the sample for thermal shock. Samples in which no abnormalities were confirmed were placed in the cooling / heating cycle tester again and evaluated by the same operation as described above, and then evaluated by the same method after 50 heat cycles. By repeating these operations, the evaluation was interrupted when abnormality was observed in 2 samples out of 10 samples, and “Cold thermal shock cycle number = (Number of interrupted heat cycles) − (50 times)” Asked. The case where the number of cycles of this thermal shock resistance test is less than 50 is D, the case of 50 or more and less than 150 is C, the case of 150 or more and less than 300 is B, and the case of 300 or more is A. .

<Light resistance test of cured product under heating conditions>
It is set so that UV light can be irradiated to a cured product having a thickness of 3 mm in a constant temperature dryer kept constant at 85 ° C. from a UV irradiation device (USHIO Corporation: SP-7) via an optical fiber. Using a 365 nm band pass filter, the light of 330-410 nm is irradiated so that it may become ² W / cm <2>.
Samples before UV irradiation and after UV irradiation under the above conditions were measured with a spectrocolorimeter (Nippon Denshoku Industries Co., Ltd., “SD5000”: integrating sphere opening diameter 10 mm), and the difference in yellowness (Δ YI) was calculated to evaluate the light resistance of the cured product under heating conditions.
When ΔYI is 10 or less, A is 10 and 15 or less, B is 15 and 20 or less is C, and 20 or more is D.

<Heat-resistant discoloration test of cured product>
Using a cured product having a thickness of 3 mm, the light transmittance at 400 nm in the thickness direction is measured with JASCO V-550 manufactured by JASCO Corporation. Next, this hardened | cured material is put into the form made from SUS316, and after subjecting to heating conditions at 120 ° C. for 100 hours under air, it is allowed to cool at room temperature. Thereafter, the light transmittance at 400 nm in the thickness direction of the sample is measured again, and the value of the light transmittance at 400 nm in the sample after the heat treatment is calculated with respect to the light transmittance at 400 nm in the sample before the heat treatment. The ratio of the light transmittance of the sample after the heat treatment to the light transmittance of the sample before the heat treatment obtained above is calculated as the light transmittance retention. The light transmission retention was 90% or more as A, 88% or more and less than 90% as B, 85% or more and less than 88% as C, and less than 85% as D.

[Example 1]
<Production 1a of Modified Resin Composition>
A 1.5 liter reactor with a reflux condenser, thermometer and stirrer is replaced with dry nitrogen. Under dry nitrogen conditions, 275 g of 3-glycidoxypropyltrimethoxysilane (hereinafter abbreviated as GPTMS), 4-fluorophenyl-trimethoxysilane (hereinafter referred to as 4FPTMS) under dry nitrogen. Abbreviated as 25), dimethyldimethoxysilane (hereinafter abbreviated as DDMMS) as 60 g, and a nuclear hydride of an aromatic epoxy resin as a trade name “YX8000” (hereinafter abbreviated as YX8000) manufactured by Japan Epoxy Resin. .) After charging 330 g of [epoxy equivalent (WPE): 205 g / eq, viscosity (25 ° C.): 1.8 Pa · s] and 180 g of tetrahydrofuran (hereinafter abbreviated as THF), the mixture was stirred at room temperature. To do. Subsequently, 100 g of water and 1.31 g of dibutyltin dilaurate (hereinafter abbreviated as DBTDL) were added, and the reactor was sealed with nitrogen and immersed in an oil bath at 80 ° C. with stirring. The reaction was carried out for 15 hours in a reflux state without distilling the solvent out of the reaction system (reflux process). After completion of the reaction, the mixture was cooled to room temperature, and a sample solution (intermediate) was collected.
The solution after completion of the above refluxing process is gradually reduced in pressure and heated using an evaporator and distilled off for 1 hour under the conditions of 400 Pa and 50 ° C., and then further reduced in pressure and heated to conditions of 80 ° C. and 1 Pa. For 5 hours to perform a dehydration condensation reaction (dehydration condensation step). After completion of the reaction, the mixture was cooled to room temperature to obtain a modified resin composition (1a).
The amount of residual alkoxy groups of this modified resin composition was 0%, and its viscosity was 100 Pa · s or less.
Table 1 shows the mixing index α, β, γ, ε, the condensation rate (%) of the intermediate, the condensation rate (%) of the alkoxysilane in the modified resin composition, the epoxy equivalent (WPE), and the storage stability index θ. .
<Manufacture of cured product and characteristic evaluation 1a>
100 parts by mass of the modified resin composition (1a) obtained above, as a curing agent (trade name) “Rikacid MH-700G” manufactured by Shin Nippon Rika Co., Ltd. [4-methylhexahydrophthalic anhydride and hexahydrophthalic anhydride] Mixture of 70 to 30% by mass] (hereinafter abbreviated as MH-700G) 63.6 parts by mass, “U-CAT 18X” (hereinafter referred to as U-CAT 18X) manufactured by San Apro Co., Ltd. as a curing accelerator Abbreviated.) 0.3 parts by mass were mixed under nitrogen, stirred until the whole became uniform, and then defoamed to obtain a curable composition. The curable composition obtained above was poured into a molding jig sandwiched between two stainless steel plates coated with a release agent with a U-shaped silicon rubber having a thickness of 3 mm under nitrogen. Curing reaction was performed for 5 hours at 110 ° C. for a further time to obtain a cured product. Table 1 shows the results of the thermal shock resistance test of the obtained cured product, the light resistance test result under the heating condition of the cured product, and the heat discoloration test result of the cured product.

[Example 2]
<Production 2a of Modified Resin Composition>
Using a reactor with an internal volume of 2 liters, using 20 g of GPTMS, using 330 g of 4FPTMS, using 100 g of DDMMS, using 600 g of YX8000, using 225 g of THF, 135 g of water A modified resin composition (2a) was produced in the same manner as in Example 1 except that 1.80 g of DBTDL was used.
The amount of residual alkoxy groups of this modified resin composition was 0%, and its viscosity was 100 Pa · s or less.
Table 1 shows the mixing index α, β, γ, ε, the condensation rate (%) of the intermediate, the condensation rate (%) of the alkoxysilane in the modified resin composition, the epoxy equivalent (WPE), and the storage stability index θ. .
<Manufacture of cured product and characteristic evaluation 2a>
Using 100 parts by mass of the modified resin composition (2a) obtained above, using 45.3 parts by mass of MH-700G, curing reaction conditions at 90 ° C. for 1 hour, and further at 100 ° C. for 5 hours. Except for the above, a curing reaction was carried out in the same manner as in Example 1 <Manufacture of cured product and property evaluation 1a> to obtain a cured product. Table 1 shows the results of the thermal shock resistance test of the obtained cured product, the light resistance test result under the heating condition of the cured product, and the heat discoloration test result of the cured product.

[Comparative Example 1]
<Production 1b of Modified Resin Composition>
Example 1 except that 275 g of GPTMS was used, 4FPTMS was not used, 330 g of YX8000 was used, 170 g of THF was used, 95 g of water was used, and 1.23 g of DBTDL was used. A modified resin composition (1b) was produced in the same manner.
The amount of residual alkoxy groups of this modified resin composition was 0%, and its viscosity was 100 Pa · s or less.
Table 1 shows the mixing indexes α, β, γ, ε, the condensation rate (%) of the intermediate, the condensation rate (%) of the alkoxysilane in the modified resin composition, the epoxy equivalent (WPE), and the storage stability index θ. Shown in
Since this modified resin composition (1b) had no storage stability, no subsequent cured product was prepared.

[Comparative Example 2]
<Production 2b of Modified Resin Composition>
22 g of GPTMS, 410 g of 4FPTMS, 24 g of DDMMS, 600 g of YX8000, 230 g of THF, 120 g of water, 1.61 g of DBTDL A modified resin composition (2b) was produced in the same manner as in Example 1 except for the above.
The amount of residual alkoxy groups of this modified resin composition was 0%, and its viscosity was 100 Pa · s or less.
Table 1 shows the mixing indexes α, β, γ, ε, the condensation rate (%) of the intermediate, the condensation rate (%) of the alkoxysilane in the modified resin composition, the epoxy equivalent (WPE), and the storage stability index θ. Shown in
<Manufacture of cured product and characteristic evaluation 2b>
100 parts by mass of the modified resin composition (2b) obtained above, 44.9 parts by mass of MH-700G were used, and the curing reaction conditions were 90 ° C. for 1 hour, and further 100 ° C. for 5 hours. Except for this, a curing reaction was carried out in the same manner as in Example 1 <Manufacture of cured product and property evaluation 1a> to obtain a cured product. Table 1 shows the results of the property tests of the obtained cured product.

[Comparative Example 3]
<Production 3b of Modified Resin Composition>
280 g of GPTMS, 65 g of phenyltrimethylsilane instead of 4FPTMS, 30 g of DMDMS, 200 g of YX8000, 190 g of THF, 100 g of water, DBTDL A modified resin composition (2b) was produced in the same manner as in Example 1 except that 1.31 g was used.
The amount of residual alkoxy groups of this modified resin composition was 0%, and its viscosity was 100 Pa · s or less.
Table 1 shows the mixing indexes α, β, γ, ε, the condensation rate (%) of the intermediate, the condensation rate (%) of the alkoxysilane in the modified resin composition, the epoxy equivalent (WPE), and the storage stability index θ. Shown in
Since this modified resin composition (3b) had no storage stability, no subsequent cured product was prepared.

[Example 3]
<Production 3a of Modified Resin Composition>
280 g of GPTMS, 65 g of 4FPTMS, 30 g of DDMMS, poly (bisphenol A-2-hydroxypropyl ether) instead of YX8000, trade name “AER2600” manufactured by Asahi Kasei Epoxy Corporation [ Epoxy equivalent (WPE): 187 g / eq, viscosity (25 ° C.): 14.3 Pa · s] 200 g, THF 188 g, water 95 g, DBTDL 1.28 g A modified resin composition (3a) was produced in the same manner as in Example 1 except for the above.
The amount of residual alkoxy groups of this modified resin composition was 0%, and its viscosity was 100 Pa · s or less.
Table 1 shows the mixing index α, β, γ, ε, the condensation rate (%) of the intermediate, the condensation rate (%) of the alkoxysilane in the modified resin composition, the epoxy equivalent (WPE), and the storage stability index θ. .
<Manufacture of cured product and characteristic evaluation 3a>
Except that 100 parts by mass of the modified resin composition (3a) obtained above and 61.7 parts by mass of MH-700G were used, the same as Example 1 <Production of cured product and property evaluation 1a> A curing reaction was performed to obtain a cured product. Table 1 shows the results of the thermal shock resistance test of the obtained cured product, the light resistance test result under the heating condition of the cured product, and the heat discoloration test result of the cured product.

[Example 4]
<Production 4a of Modified Resin Composition>
50 g of GPTMS, 205 g of 4FPTMS, 60 g of DDMMS, 350 g of YX8000, 160 g of THF, 95 g of water, 1.22 g of DBTDL A modified resin composition (4a) was produced in the same manner as in Example 1 except for the above.
The amount of residual alkoxy groups of this modified resin composition was 0%, and its viscosity was 100 Pa · s or less.
Table 1 shows the mixing index α, β, γ, ε, the condensation rate (%) of the intermediate, the condensation rate (%) of the alkoxysilane in the modified resin composition, the epoxy equivalent (WPE), and the storage stability index θ. .
<Manufacture of cured product and characteristic evaluation 4a>
100 parts by mass of the modified resin composition (4a) obtained above, 45.8 parts by mass of MH-700G, curing reaction conditions at 90 ° C. for 1 hour, and further at 100 ° C. for 5 hours Except for this, a curing reaction was carried out in the same manner as in Example 1 <Manufacture of cured product and property evaluation 1a> to obtain a cured product. Table 1 shows the results of the thermal shock resistance test of the obtained cured product, the light resistance test result under the heating condition of the cured product, and the heat discoloration test result of the cured product.

[Example 5]
<Production 5a of Modified Resin Composition>
280 g of GPTMS, 90 g of 4FPTMS, 40 g of DDMMS, 5 g of tetraethoxysilane as an alkoxysilane component, 330 g of YX8000, 210 g of THF, water A modified resin composition (5a) was produced in the same manner as in Example 1 except that 110 g of DBTDL was used and 1.44 g of DBTDL was used.
The amount of residual alkoxy groups of this modified resin composition was 0%, and its viscosity was 100 Pa · s or less.
Table 1 shows the mixing index α, β, γ, ε, the condensation rate (%) of the intermediate, the condensation rate (%) of the alkoxysilane in the modified resin composition, the epoxy equivalent (WPE), and the storage stability index θ. .
<Manufacture of cured product and characteristic evaluation 5a>
100 parts by mass of the modified resin composition (5a) obtained above and 72.2 parts by mass of MH-700G were mixed under nitrogen and stirred until the whole became uniform, and the modified resin composition (5a) And MH-700G curable resin composition. Subsequently, 0.2 parts by mass of U-CAT 18X was added to 100 parts by mass of the modified resin composition (5a) obtained above and the curable resin composition of MH-700G, and the whole was mixed under nitrogen. After stirring until uniform, defoaming was performed to obtain curable composition-1a. Thereafter, a curing reaction was carried out in the same manner as in Example 1 <Production of cured product and property evaluation 1a> to obtain a cured product. Table 1 shows the results of the thermal shock resistance test of the obtained cured product, the light resistance test result under the heating condition of the cured product, and the heat discoloration test result of the cured product.

[Example 6]
<Production 6a of Modified Resin Composition>
Example 1 A modified resin composition (6a) was produced in the same manner.
The amount of residual alkoxy groups of this modified resin composition was 0%, and its viscosity was 100 Pa · s or less.
Table 1 shows the mixing index α, β, γ, ε, the condensation rate (%) of the intermediate, the condensation rate (%) of the alkoxysilane in the modified resin composition, the epoxy equivalent (WPE), and the storage stability index θ. .
<Manufacture and characteristic evaluation 6a of cured product>
Using 100 parts by mass of the modified resin composition (6a) obtained above, using 50 parts by mass of MH-700G, and curing reaction conditions at 90 ° C. for 1 hour and further at 100 ° C. for 5 hours. Except for the above, a curing reaction was carried out in the same manner as in Example 1 <Manufacture of cured product and property evaluation 1a> to obtain a cured product. Table 1 shows the results of the thermal shock resistance test of the obtained cured product, the light resistance test result under the heating condition of the cured product, and the heat discoloration test result of the cured product.

[Example 7]
<Production 7a of Modified Resin Composition>
165 g of GPTMS was used, 205 g of 2,4-difluorophenyl-trimethoxysilane was used instead of 4FPTMS, 30 g of DDMMS was used, 3,4-epoxycyclohexylmethyl-3 ′, instead of YX8000 As 4′-epoxycyclohexylcarboxylate, 220 g of trade name “Celoxide 2021P” [Epoxy equivalent (WPE): 131 g / eq, viscosity (25 ° C.): 227 mPa · s] manufactured by Daicel Chemical Industries, Ltd.] was used. 200 g of water, 100 g of water, 1.3 g of DBTDL, and the reaction time in a reflux state (reflux process) without distilling water or solvent out of the reaction system was 10 hours. A modified resin composition (7a) was produced in the same manner as in Example 1 except that.
The amount of residual alkoxy groups of this modified resin composition was 0%, and its viscosity was 100 Pa · s or less.
Table 1 shows the mixing index α, β, γ, ε, the condensation rate (%) of the intermediate, the condensation rate (%) of the alkoxysilane in the modified resin composition, the epoxy equivalent (WPE), and the storage stability index θ. .
<Manufacture of cured product and characteristic evaluation 7a>
Cured in the same manner as in Example 1 <Manufacture of cured product and property evaluation 1a> except that 100 parts by mass of the modified resin composition (7a) obtained above was used and 59 parts by mass of MH-700G was used. Reaction was performed and the hardened | cured material was obtained. Table 1 shows the results of the thermal shock resistance test of the obtained cured product, the light resistance test result under the heating condition of the cured product, and the heat discoloration test result of the cured product.

[Example 8]
<Production 8a of Modified Resin Composition>
A 1.5 liter reactor with a reflux condenser, thermometer and stirrer is replaced with dry nitrogen. Under dry nitrogen conditions, the apparatus was charged with 120 g of GPTMS, 187 g of 2,4,6-trifluorophenyl-trimethoxysilane, 105 g of DDMMS, and 210 g of THF under dry nitrogen, and then at room temperature. Mix and stir. Subsequently, 116 g of water and 1.57 g of dibutyltin dilaurate (hereinafter abbreviated as DBTDL) were added, and the reactor was sealed with nitrogen and immersed in an 80 ° C. oil bath with stirring. The reaction was carried out for 15 hours in a reflux state without distilling the solvent out of the reaction system (reflux process). After completion of the reaction, the reaction mixture was cooled to room temperature, 400 g of YX8000 was added, and stirring was continued for 1 hour to dissolve uniformly, and then a sample solution (intermediate) was collected.
The above solution was gradually reduced in pressure and heated using an evaporator, distilled for 1 hour under conditions of 400 Pa and 50 ° C., and further treated under reduced pressure and heated for 5 hours under conditions of 80 ° C. and 1 Pa. Then, a dehydration condensation reaction was performed (dehydration condensation step). After completion of the reaction, the mixture was cooled to room temperature to obtain a modified resin composition (1a).
The amount of residual alkoxy groups of this modified resin composition was 0%, and its viscosity was 100 Pa · s or less.
Table 1 shows the mixing index α, β, γ, ε, the condensation rate (%) of the intermediate, the condensation rate (%) of the alkoxysilane in the modified resin composition, the epoxy equivalent (WPE), and the storage stability index θ. .
<Manufacture and characteristic evaluation 8a of cured product>
100 parts by mass of the modified resin composition (8a) obtained above, 48 parts by mass of MH-700G were used, and the curing reaction conditions were 90 ° C. for 1 hour, and further 100 ° C. for 5 hours. Except for the above, a curing reaction was carried out in the same manner as in Example 1 <Production of cured product and property evaluation 1a> to obtain a cured product. Table 1 shows the results of the thermal shock resistance test of the obtained cured product, the light resistance test result under the heating condition of the cured product, and the heat discoloration test result of the cured product.

[Example 9]
90 parts by mass of the modified resin composition (6a) obtained in Example 6, trade name “Celoxide 2021P” manufactured by Daicel Chemical Industries, Ltd. [epoxy equivalent (WPE): 131 g / eq, viscosity (25 ° C.): 227 mPa 10 parts by mass of s] were mixed under nitrogen and stirred until the whole became uniform to obtain a modified resin composition (9a).
100 parts by mass of the modified resin composition (9a) obtained above, 53.8 parts by mass of MH-700G, curing reaction conditions at 90 ° C. for 1 hour, and further at 100 ° C. for 5 hours Except for this, a curing reaction was carried out in the same manner as in Example 1 <Manufacture of cured product and property evaluation 1a> to obtain a cured product. Table 1 shows the results of the thermal shock resistance test of the obtained cured product, the light resistance test result under the heating condition of the cured product, and the heat discoloration test result of the cured product.

[Example 10]
100 parts by mass of the modified resin composition (5a) obtained in Example 5 and 10 parts by mass of “YAG: Ce3 + phosphor” manufactured by Kasei Optonics Co., Ltd. were mixed under nitrogen. After adding 72.2 parts by mass of MH-700G and 0.3 parts by mass of U-CAT 18X to the obtained mixture, the mixture was mixed under nitrogen, stirred until the whole became uniform, then defoamed and cured. Sex composition (10a) was obtained.
The curable composition obtained above was poured into a bullet-shaped mold form having a diameter of 4 mm, and a lead frame on which a light emitting element having an emission wavelength of 400 nm was fixed was immersed therein, and after degassing in a vacuum, 90 A curing reaction was carried out at 1 ° C. for 1 hour and further at 110 ° C. for 5 hours to obtain a light emitting diode. Even when the light-emitting diode (10c) obtained by this operation was energized at room temperature at 20 mA for 200 hours, peeling between the element and the sealing portion and a decrease in luminance were not observed.
Ten light-emitting diodes (10c) obtained by the above operation are used in the test method 307 (thermal shock test) of “EIAJ ED-4701 / 300 (Semiconductor device environment and durability test method (strength test I)”). Accordingly, the evaluation was performed under the following conditions.
“-10 ° C. (5 minutes) to 100 ° C. (5 minutes)” was taken as one cycle. After 100 cycles of thermal shock, lighting of the light emitting diodes was confirmed.
Further, the ten light-emitting diodes (10c) obtained by the above-described operation were subjected to test method 105 (temperature cycle test) of “EIAJ ED-4701 / 100 (Semiconductor device environment and durability test method (life test I)”). ) And evaluated under the following conditions.
“-40 ° C. (30 minutes) to 85 ° C. (5 minutes) to 100 ° C. (30 minutes) to 25 ° C. (5 minutes)” is taken as one cycle, and after 100 temperature cycles are applied, the light-emitting diodes are turned on. As a result, all 10 lights were turned on.

[Example 11]
100 parts by mass of the modified resin composition (7a) obtained in Example 7 and 10 parts by mass of “YAG: Ce3 + phosphor” manufactured by Kasei Optonics Co., Ltd. were mixed under nitrogen. To the obtained mixture, 59 parts by mass of MH-700G and 0.3 part by mass of U-CAT 18X were added, mixed under nitrogen, stirred until the whole became uniform, defoamed and curable composition The product (11a) was obtained.
The curable composition obtained above was poured into a bullet-shaped mold form having a diameter of 4 mm, and a lead frame on which a light emitting element having an emission wavelength of 400 nm was fixed was immersed therein, and after degassing in a vacuum, 90 A curing reaction was carried out at 1 ° C. for 1 hour and further at 110 ° C. for 5 hours to obtain a light emitting diode. Even when the light-emitting diode (11c) obtained by this operation was energized at room temperature at 20 mA for 200 hours, peeling between the element and the sealing portion and reduction in luminance were not observed.
Ten light-emitting diodes (11c) obtained by the above operation are used as test method 307 (thermal shock test) of “EIAJ ED-4701 / 300 (Semiconductor device environment and durability test method (strength test I)”). Accordingly, the evaluation was performed under the following conditions.
“-10 ° C. (5 minutes) to 100 ° C. (5 minutes)” was taken as one cycle. After 100 cycles of thermal shock, lighting of the light emitting diodes was confirmed.
Further, the ten light-emitting diodes (11c) obtained by the above-described operation are connected to test method 105 (temperature cycle test) of “EIAJ ED-4701 / 100 (Semiconductor device environment and durability test method (life test I)”). ) And evaluated under the following conditions.
“-40 ° C. (30 minutes) to 85 ° C. (5 minutes) to 100 ° C. (30 minutes) to 25 ° C. (5 minutes)” is taken as one cycle, and after 100 temperature cycles are applied, the light-emitting diodes are turned on. As a result, all 10 lights were turned on.

[Example 12]
100 parts by mass of the modified resin composition (8a) obtained in Example 7 and 10 parts by mass of “YAG: Ce3 + phosphor” manufactured by Kasei Optonics Co., Ltd. were mixed under nitrogen. After adding 48 parts by mass of MH-700G and 0.3 part by mass of U-CAT 18X to the obtained mixture, the mixture was mixed under nitrogen, stirred until the whole became uniform, defoamed and curable composition A product (12a) was obtained.
The curable composition obtained above was poured into a bullet-shaped mold form having a diameter of 4 mm, and a lead frame on which a light emitting element having an emission wavelength of 400 nm was fixed was immersed therein, and after degassing in a vacuum, 90 A curing reaction was carried out at 1 ° C. for 1 hour and further at 110 ° C. for 5 hours to obtain a light emitting diode. Even when the light-emitting diode (12c) obtained by this operation was energized at room temperature for 20 hours at 20 mA, peeling between the element and the sealing portion and a decrease in luminance were not observed.
Ten light-emitting diodes (12c) obtained by the above operation are used as test method 307 (thermal shock test) of “EIAJ ED-4701 / 300 (Semiconductor device environment and durability test method (strength test I)”). Accordingly, the evaluation was performed under the following conditions.
“-10 ° C. (5 minutes) to 100 ° C. (5 minutes)” was taken as one cycle. After 100 cycles of thermal shock, lighting of the light emitting diodes was confirmed.
Further, the ten light-emitting diodes (12c) obtained by the above-mentioned operation were tested using the test method 105 (temperature cycle test) of “EIAJ ED-4701 / 100 (Semiconductor device environment and durability test method (life test I)” ) And evaluated under the following conditions.
“-40 ° C. (30 minutes) to 85 ° C. (5 minutes) to 100 ° C. (30 minutes) to 25 ° C. (5 minutes)” is taken as one cycle, and after 100 temperature cycles are applied, the light-emitting diodes are turned on. As a result, all 10 lights were turned on.

  It has good transparency, can form cured products that have both excellent heat-resistant yellowing, light resistance under heating conditions, and resistance to thermal shock in thermal cycle, and good storage It becomes possible to provide a modified resin composition having stability.

  Furthermore, by using the modified resin composition of the present invention, <a> excellent light-emitting components such as light-emitting diodes, which have excellent adhesion to elements and package materials, are free of cracks, and have little decrease in luminance over a long period of time, , An optical lens that can be injection-molded, is hard after curing, has excellent step stability, and has light resistance, and a semiconductor device using the light-emitting component and / or optical lens, <b> oxygen A photosensitive composition that can suppress polymerization inhibition due to the light-sensitive material, has excellent adhesion, a coating agent containing the composition, a coating film obtained by curing the coating agent, and <c> fluorescence excellent in dispersion stability of the phosphor A resin composition, a phosphorescent material using the fluorescent resin composition, <d> a conductive resin composition excellent in fluidity, conductivity and adhesiveness and free of voids, <e> fluidity, insulation and Contact Excellent sex, and the insulating resin composition voids are not generated such, it is possible to provide a.

Claims (17)

A modified resin composition obtained by reacting an alkoxysilane compound represented by the following general formula (1) in the presence of an epoxy resin (A),
_{^{(R 1) n -Si- (OR}} 2) 4-n ··· (1)
(Wherein n represents an integer of 0 or more and 3 or less. In addition, each R ¹ is independently a hydrogen atom or a) selected from an unsubstituted or substituted structure group consisting of a chain, a branch, and a ring. An organic group containing a cyclic ether group having an aliphatic hydrocarbon unit having one or more kinds of structures, 4 to 24 carbon atoms, and 1 to 5 oxygen atoms, b) unsubstituted Or a substituted aliphatic hydrocarbon unit having one or more structures selected from the group consisting of a chain, a branched chain and a ring, having 1 to 24 carbon atoms and 0 oxygen atoms A monovalent aliphatic organic group that is 5 or less, and c) an unsubstituted or substituted aromatic hydrocarbon unit that is unsubstituted or substituted as necessary, from a chain, branched, and cyclic An aliphatic hydrocarbon unit comprising at least one structure selected from the group consisting of And at least one organic group selected from the group consisting of monovalent aromatic organic groups having 6 to 24 carbon atoms and 0 to 5 oxygen atoms. On the other hand, each R ² independently has a hydrogen atom or d) an unsubstituted or substituted aliphatic hydrocarbon unit having one or more types of structures selected from a chain, branched, or cyclic structure group. And a monovalent organic group having 1 to 8 carbon atoms. )
The alkoxysilane compound is
(B) n = 1 or 2, and at least one alkoxysilane compound containing a group having at least one cyclic ether group as R ¹ ;
(C) an alkoxysilane compound containing n = 1 or 2 and a phenyl group having at least one fluorine atom as a substituent as R ¹ ;
Including
A modified resin composition represented by the following general formula (2), wherein a mixing index α of the alkoxysilane compound is 0.001 or more and 19 or less.
Mixing index α = (αc) / (αb) (2)
(In the formula (2), αb is represented by the general formula (1), the content (mol%) of the component (B) in the alkoxysilane compound, and αc is represented by the general formula (1). The content (mol%) of the component (C) in the alkoxysilane compound is shown.)   The modified resin composition according to claim 1, wherein the amount of residual alkoxy groups in the modified resin composition is 5% or less.   The modified resin composition of Claim 1 or 2 whose condensation rate of the said alkoxysilane compound is 80% or more.   The epoxy resin (A) is selected from the group consisting of an alicyclic epoxy resin, an aliphatic epoxy resin, a polyfunctional epoxy resin composed of a glycidyl etherified product of a polyphenol compound, and a nuclear hydride of an aromatic epoxy resin. It is the above polyfunctional epoxy resin, The modified resin composition of any one of Claims 1-3 characterized by the above-mentioned. The modified resin composition according to any one of claims 1 to 4, wherein a mixing index β of the alkoxysilane compound represented by the following general formula (3) is 0.01 or more and 1.4 or less.
Mixing index β = {(βn2) / (βn0 + βn1)} (3)
(In the formula (3), βn2 is the content (mol%) of the alkoxysilane compound in which n = 2 in the alkoxysilane compound represented by the general formula (1), and βn0 is the general formula (1). The content (mol%) of the alkoxysilane compound in which n = 0 in the alkoxysilane compound represented by the formula: βn1 is the alkoxysilane in which n = 1 in the alkoxysilane compound represented by the general formula (1) The content (mol%) of the compound is shown, and 0 ≦ {(βn0) / (βn0 + βn1 + βn2)} ≦ 0.1. The modified resin according to any one of claims 1 to 5, wherein a mixing index γ of the epoxy resin (A) represented by the following general formula (4) and the alkoxysilane compound is 0.02 to 15. Composition.
Mixing index γ = (γa) / (γs) (4)
(Here, in formula (4), γa is the mass (g) of the epoxy resin (A), and γs is an alkoxysilane compound in which n = 0 to 2 in the alkoxysilane compound represented by the general formula (1). The mass (g) of each is shown.) In the presence of the epoxy resin (A), the alkoxysilane compound represented by the following general formula (1) containing at least the following (B) component and (C) component is accompanied by distillation of water or a solvent out of the reaction system. A step (a) of producing an intermediate by cohydrolysis by a non-refluxing step, and a step (b) of subjecting the intermediate produced by the step (a) to a dehydration condensation reaction,
And the modified index of the alkoxysilane compound represented by the following general formula (2) is 0.001 or more and 19 or less.
_{^{(R 1) n -Si- (OR}} 2) 4-n ··· (1)
(Wherein n represents an integer of 0 or more and 3 or less. In addition, each R ¹ is independently a hydrogen atom or a) selected from an unsubstituted or substituted structure group consisting of a chain, a branch, and a ring. An organic group containing a cyclic ether group having an aliphatic hydrocarbon unit having one or more kinds of structures, 4 to 24 carbon atoms, and 1 to 5 oxygen atoms, b) unsubstituted Or a substituted aliphatic hydrocarbon unit having one or more structures selected from the group consisting of a chain, a branched chain and a ring, having 1 to 24 carbon atoms and 0 oxygen atoms A monovalent aliphatic organic group that is 5 or less, and c) an unsubstituted or substituted aromatic hydrocarbon unit that is unsubstituted or substituted as necessary, from a chain, branched, and cyclic An aliphatic hydrocarbon unit comprising at least one structure selected from the group consisting of And at least one organic group selected from the group consisting of monovalent aromatic organic groups having 6 to 24 carbon atoms and 0 to 5 oxygen atoms. On the other hand, each R ² independently has a hydrogen atom or d) an unsubstituted or substituted aliphatic hydrocarbon unit having one or more types of structures selected from a chain, branched, or cyclic structure group. And a monovalent organic group having 1 to 8 carbon atoms. )
(B) n = 1 or 2, and at least one alkoxysilane compound containing a group having at least one cyclic ether group as R ¹ .
(C) An alkoxysilane compound containing n = 1 or 2 and a phenyl group having at least one fluorine atom as a substituent as R ¹ .
Mixing index α = (αc) / (αb) (2)
(Here, in the formula (2), αb represents the content (mol%) of the component (B), and αc represents the content (mol%) of the component (C).) The alkoxysilane compound represented by the following general formula (1) containing at least the following component (B) and component (C) is cohydrolyzed by a refluxing step that does not involve distillation of water or a solvent out of the reaction system. A step (c) of producing an intermediate, and a step (d) of performing a dehydration condensation reaction in the presence of an epoxy resin (A) in the intermediate produced by the step (c),
And the modified index of the alkoxysilane compound represented by the following general formula (2) is 0.001 or more and 19 or less.
_{^{(R 1) n -Si- (OR}} 2) 4-n ··· (1)
(Wherein n represents an integer of 0 or more and 3 or less. In addition, each R ¹ is independently a hydrogen atom or a) selected from an unsubstituted or substituted structure group consisting of a chain, a branch, and a ring. An organic group containing a cyclic ether group having an aliphatic hydrocarbon unit having one or more kinds of structures, 4 to 24 carbon atoms, and 1 to 5 oxygen atoms, b) unsubstituted Or a substituted aliphatic hydrocarbon unit having one or more structures selected from the group consisting of a chain, a branched chain and a ring, having 1 to 24 carbon atoms and 0 oxygen atoms A monovalent aliphatic organic group that is 5 or less, and c) an unsubstituted or substituted aromatic hydrocarbon unit that is unsubstituted or substituted as necessary, from a chain, branched, and cyclic An aliphatic hydrocarbon unit comprising at least one structure selected from the group consisting of And at least one organic group selected from the group consisting of monovalent aromatic organic groups having 6 to 24 carbon atoms and 0 to 5 oxygen atoms. On the other hand, each R ² independently has a hydrogen atom or d) an unsubstituted or substituted aliphatic hydrocarbon unit having one or more types of structures selected from a chain, branched, or cyclic structure group. And a monovalent organic group having 1 to 8 carbon atoms. )
(B) n = 1 or 2, and at least one alkoxysilane compound containing a group having at least one cyclic ether group as R ¹ .
(C) An alkoxysilane compound containing n = 1 or 2 and a phenyl group having at least one fluorine atom as a substituent as R ¹ .
Mixing index α = (αc) / (αb) (2)
(Here, in the formula (2), αb represents the content (mol%) of the component (B), and αc represents the content (mol%) of the component (C).) The method for producing a modified resin composition according to claim 7 or 8, wherein a mixing index β of the alkoxysilane compound represented by the following general formula (3) is 0.01 to 1.4;
Mixing index β = {(βn2) / (βn0 + βn1)} (3)
(In the formula (3), βn2 is the content (mol%) of the alkoxysilane compound in which n = 2 in the alkoxysilane compound represented by the general formula (1), and βn0 is the general formula (1). The content (mol%) of the alkoxysilane compound in which n = 0 in the alkoxysilane compound represented by the formula: βn1 is the alkoxysilane in which n = 1 in the alkoxysilane compound represented by the general formula (1) The content (mol%) of the compound is shown, and 0 ≦ {(βn0) / (βn0 + βn1 + βn2)} ≦ 0.1. The modified resin according to any one of claims 7 to 9, wherein a mixing index γ of the epoxy resin (A) represented by the following general formula (4) and the alkoxysilane compound is 0.02 to 15. A method for producing the composition;
Mixing index γ = (γa) / (γs) (4)
(In the formula (4), γa is the mass (g) of the epoxy resin (A), and γs is an alkoxysilane compound in which n = 0 to 2 in the alkoxysilane represented by the general formula (1). (The mass (g) is shown respectively.)   The manufacturing method of the modified resin composition of any one of Claims 7-10 whose temperature in the recirculation | reflux process without distilling water and a solvent out of the reaction system is 50-100 degreeC.   The modification | denaturation of any one of Claims 7-11 whose condensation rate of the intermediate body obtained by cohydrolyzing by the recirculation | reflux process without distilling water and a solvent out of the reaction system is 70% or more. A method for producing a resin composition.   The manufacturing method of the modified resin composition of any one of Claims 7-12 using an alkoxide type | system | group organic tin as a catalyst in the case of the said cohydrolysis.   A curable resin composition obtained by further adding a curing agent to the modified resin composition according to claim 1.   A curable resin composition obtained by further adding a curing accelerator to the curable resin composition according to claim 14.   The light emitting component manufactured using the curable resin composition of Claim 15.   A semiconductor device comprising the light emitting component according to claim 16.