JP7000857B2 - Adhesive composition and structure - Google Patents

Description

The present invention relates to adhesive compositions and structures.

In semiconductor elements and liquid crystal display elements (display display elements), various adhesives have been conventionally used for the purpose of binding various members in the elements. The properties required for adhesives range from adhesiveness to heat resistance and reliability in high temperature and high humidity conditions. The adherend used for adhesion includes a printed wiring board, an organic base material (for example, a polyimide base material), a metal (titanium, copper, aluminum, etc.), ITO, IZO, IGZO, _SiNX , SiO. A base material having a wide variety of surface states such as No. ₂ is used, and it is necessary to design the molecule of the adhesive according to each adherend.

Conventionally, a thermosetting resin (epoxy resin, acrylic resin, etc.) exhibiting high adhesiveness and high reliability has been used as an adhesive for a semiconductor element or a liquid crystal display element. As a constituent component of the adhesive using an epoxy resin, an epoxy resin and a latent curing agent that generates a cationic species or an anionic species having reactivity with the epoxy resin by heat or light are generally used. The latent curing agent is an important factor that determines the curing temperature and the curing rate, and various compounds have been used from the viewpoint of storage stability at room temperature and curing rate at the time of heating. In the actual step, the desired adhesiveness was obtained by curing under the curing conditions of, for example, a temperature of 170 to 250 ° C. for 10 seconds to 3 hours.

Further, in recent years, with the high integration of semiconductor elements and the high definition of liquid crystal display elements, the pitch between elements and between wirings has become narrower, and the heat during curing may adversely affect peripheral members. Further, in order to reduce the cost, it is necessary to improve the throughput, and adhesion at a low temperature (90 to 170 ° C.) and a short time (within 1 hour, preferably within 10 seconds, more preferably within 5 seconds). In other words, adhesion by low temperature short time curing (low temperature fast curing) is required. In order to achieve this low-temperature short-time curing, it is necessary to use a thermal latent catalyst with low activation energy, but it is known that it is very difficult to combine storage stability near room temperature. ..

Therefore, in recent years, a radical curing adhesive using a (meth) acrylate derivative and a peroxide as a radical polymerization initiator, an epoxy resin, and a cationic curing system using an onium salt as a cationic polymerization initiator in combination. Adhesives and the like are attracting attention. In the radical curing system, the radical, which is a reaction active species, is extremely reactive, so that it can be cured in a short time, and the peroxide is stably present below the decomposition temperature of the radical polymerization initiator. It is a curing system that achieves both low-temperature short-time curing and storage stability (for example, storage stability near room temperature). In the cation curing system, the onium salt, which is a reaction active species, is highly reactive, so that it can be cured in a short time, and since the cation species is stably present at the decomposition temperature of the onium salt or lower, the cation species is stably present at a low temperature for a short time. It is a curing system that has both curing and storage stability.

On the other hand, the above-mentioned adhesive has a low molecular weight that can interact with the surface of the adherend by covalent bond, hydrogen bond, hydrophobic interaction by van der Waals force, etc. in order to realize strong adhesion with the adherend. A coupling agent or the like may be used as an additive for the above. As the coupling agent, for example, a silane coupling agent; a compound containing a phosphoric acid group, a carboxyl group, or the like is used. In particular, an alkoxysilane or a coupling agent that interacts with an organic functional group (for example, an organic functional group typified by an epoxy group, an acryloyl group, a vinyl group, etc.) incorporated into the resin matrix after curing (for example, an alkoxysilane or a coupling agent) that interacts with the surface of the adherend. For example, when a coupling agent having a functional group typified by a phosphoric acid group or the like is used, the adherend and the adhesive can be more firmly bonded (see, for example, Patent Document 1 below).

Japanese Unexamined Patent Publication No. 2013-191625 International Publication No. 2009/0638227

By the way, the adhesive composition containing a silane compound is required to have excellent adhesive strength after a reliability test of holding under high temperature and high humidity conditions such as 85 ° C. 85% RH and 60 ° C. 95% RH. Has been done.

An object of the present invention is to provide an adhesive composition having excellent adhesive strength after a reliability test, and a structure using the same.

（式中、Ｘは有機基を示し、Ｒ^１及びＲ^２はそれぞれ独立にアルキル基を示し、ｍは０～２の整数を示し、ｓは６以上の整数を示す。）The adhesive composition of the present invention contains a silane compound having a structure represented by the following general formula (I).

(In the formula, X represents an organic group, R ¹ and R ² each independently represent an alkyl group, m represents an integer of 0 to 2, and s represents an integer of 6 or more.)

By the way, conventionally, an adhesive containing a silane compound having an alkoxysilyl group and an organic group bonded to the alkoxysilyl group via an alkylene group may be used. On the other hand, the present inventor has found the following findings regarding such a silane compound. That is, in the conventional silane compound, the carbon number of the alkylene group existing between the Si of the alkoxysilyl group and the organic group is small (for example, the number of methylene groups (CH ₂ ) is as short as 3 or less). Therefore, when the first functional group of one of the alkoxysilyl group and the organic group reacts with one of the constituent components (resin or the like) of the adhesive and one of the adherends, the alkoxysilyl group and the organic group are sufficiently separated from each other. Due to the difficulty, the steric freedom of the second functional group of the other of the alkoxysilyl group and the organic group is low, so that the second functional group, the constituent components of the adhesive (resin, etc.) and the other of the adherend are present. The reaction with the above was not sufficiently carried out, and the effect as a silane compound could not be sufficiently exhibited. As a result, there are problems that sufficient adhesive strength cannot be obtained, and that the adhesive strength is lowered after the reliability test of leaving the product under high temperature and high humidity conditions such as 85 ° C. 85% RH and 60 ° C. 95% RH.

On the other hand, the adhesive composition of the present invention has excellent adhesive strength after the reliability test. Further, the adhesive composition of the present invention is applied to an adherend composed of various materials (for example, inorganic substances (oxides, metals, etc.), organic substances, and composites thereof) before and after the reliability test. Nevertheless, it has excellent adhesive strength.

The organic group X preferably contains at least one selected from the group consisting of a (meth) acryloyl group, a vinyl group, an epoxy group, a nitrogen atom-containing group and a sulfur atom-containing group.

The adhesive composition of the present invention may further contain an epoxy resin and a latent curing agent.

The adhesive composition of the present invention may further contain a radically polymerizable compound and a curing agent that generates radicals by heat or light.

The adhesive composition of the present invention may further contain conductive particles.

The adhesive composition of the present invention may be for circuit connection (circuit connection adhesive composition).

The structure of the present invention comprises the adhesive composition or a cured product thereof.

The structure of the present invention is between a first circuit member having a first circuit electrode, a second circuit member having a second circuit electrode, and the first circuit member and the second circuit member. The first circuit electrode and the second circuit electrode are electrically connected to each other, and the circuit connection member includes the adhesive composition or a cured product thereof. It may be an embodiment.

According to the present invention, it is possible to provide an adhesive composition having excellent adhesive strength after a reliability test and a structure using the same. Further, according to the present invention, there is provided an adhesive composition having excellent adhesive strength before and after a reliability test for an adherend made of various materials, and a structure using the same. be able to.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide an adhesive composition or a cured product thereof for the manufacture of a structure or a structure thereof. INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide an adhesive composition or a cured product thereof for circuit connection. INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide an application of an adhesive composition or a cured product thereof to a circuit connection structure or a manufacturing thereof.

It is a schematic cross-sectional view which shows one Embodiment of the structure of this invention. It is a schematic sectional drawing which shows the other embodiment of the structure of this invention.

Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to these embodiments.

As used herein, the term "(meth) acrylate" means at least one of an acrylate and a corresponding methacrylate. The same applies to other similar expressions such as "(meth) acryloyl" and "(meth) acrylic acid". Unless otherwise specified, the materials exemplified below may be used alone or in combination of two or more. The content of each component in the composition means the total amount of the plurality of substances present in the composition when a plurality of substances corresponding to each component are present in the composition, unless otherwise specified. The numerical range indicated by using "-" indicates a range including the numerical values before and after "-" as the minimum value and the maximum value, respectively. "A or B" may include either A or B, and may include both. "Room temperature" means 25 ° C.

In the numerical range described stepwise in the present specification, the upper limit value or the lower limit value of the numerical range of one step may be replaced with the upper limit value or the lower limit value of the numerical range of another step. Further, in the numerical range described in the present specification, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples.

The adhesive composition of the present embodiment contains a silane compound having a structure represented by the following general formula (I) (hereinafter, sometimes referred to as "silane compound A"). According to the adhesive composition of the present embodiment, the alkoxysilyl group and the organic group X are easily separated from each other by replacing the alkylene group having a small number of carbon atoms with the alkylene group having 6 or more carbon atoms. Even after one of the functional groups of the organic group X has reacted, the steric freedom of the other functional group can be ensured, so that high adhesive strength to various adherends is exhibited and after the reliability test. Also has sufficient adhesive strength. Such an adhesive composition can be suitably used as an adhesive composition for circuit connection.

（式中、Ｘは有機基を示し、Ｒ^１及びＲ^２はそれぞれ独立にアルキル基を示し、ｍは０～２の整数を示し、ｓは６以上の整数を示す。Ｒ^１が複数存在する場合、各Ｒ^１は、互いに同じであってもよく、異なっていてもよい。Ｒ^２が複数存在する場合、各Ｒ^２は、互いに同じであってもよく、異なっていてもよい。Ｒ^１、Ｒ^２及びＣ_ｓＨ_２ｓのそれぞれは、分岐していてもよい。）

(In the formula, X indicates an organic group, R ¹ and R ² each independently indicate an alkyl group, m indicates an integer of 0 to 2, and s indicates an integer of 6 or more. There are a plurality of R ¹ . In this case, each R ¹ may be the same as or different from each other. If there are a plurality of R ² , each R ² may be the same as or different from ^each other. , R ² and C _s H _2s may each be branched.)

The alkylene group of the silane compound A may be either a linear alkylene group or a branched chain alkylene group. When the alkoxysilyl group and the organic group X in the linear alkylene group and the branched chain alkylene group have the same number of carbon atoms, the linear alkylene group is preferable from the viewpoint of more easily securing a steric degree of freedom. When the silane compound A having a linear alkylene group is used, the conventionally short number of methylene groups is 6 or more, so that even after one functional group of the alkoxysilyl group and the organic group X reacts, the steric structure of the other functional group is used. Since it is possible to secure a certain degree of freedom, it exhibits high adhesive strength to various adherends and has sufficient adhesive strength even after the reliability test.

Examples of the constituent components of the adhesive composition of the present embodiment include (a) an epoxy resin (hereinafter, sometimes referred to as “(a) component”) and (b) a latent curing agent (a latent curing agent for an epoxy resin). (Hereinafter, sometimes referred to as "(b) component"), (c) radically polymerizable compound (hereinafter, sometimes referred to as "(c) component"), and (d) heat (heating) or light (light irradiation). Examples thereof include a curing agent (hereinafter, in some cases, referred to as “component (d)”) that generates a radical (free radical). The first aspect of the adhesive composition of this embodiment contains a component (a) and a component (b). The second aspect of the adhesive composition of the present embodiment contains the component (c) and the component (d). The third aspect of the adhesive composition of the present embodiment contains (a) component, (b) component, (c) component and (d) component.

Hereinafter, each component will be described.

(Silane compound)
Examples of the organic group X of the silane compound A having the structure represented by the formula (I) include an ethylenically unsaturated bond-containing group (a group containing an ethylenically unsaturated bond) and a nitrogen atom-containing group (a group containing a nitrogen atom). , Sulfur atom-containing group (group containing sulfur atom), epoxy group and the like. Examples of the ethylenically unsaturated bond-containing group include a (meth) acryloyl group, a vinyl group, and a styryl group. Examples of the nitrogen atom-containing group include an amino group, a mono-substituted amino group, a di-substituted amino group, an isocyanato group, an imidazole group, a ureido group, a maleimide group and the like. Examples of the mono-substituted amino group include an alkylamino group (methylamino group and the like), a benzylamino group, a phenylamino group, a cycloalkylamino group (cyclohexylamino group and the like) and the like. Examples of the di-substituted amino group include an acyclic di-substituted amino group and a cyclic di-substituted amino group. Examples of the acyclic di-substituted amino group include a dialkylamino group (dimethylamino group and the like). Examples of the cyclic di-substituted amino group include a morpholino group and a piperazino group. Examples of the sulfur atom-containing group include a mercapto group. The epoxy group may be contained in an epoxy group-containing group (group containing an epoxy group) such as a glycidyl group and a glycidoxy group. The (meth) acryloyl group may be contained in the (meth) acryloyloxy group.

The organic group X preferably has reactivity with components of the adhesive composition other than the silane compound. The organic group X is composed of a (meth) acryloyl group, a vinyl group, an epoxy group, a nitrogen atom-containing group and a sulfur atom-containing group from the viewpoint of further improving the reactivity with the components of the adhesive composition other than the silane compound. It is preferable to include at least one selected from the group.

The alkyl groups of R ¹ and R ² have, for example, 1 to 20 carbon atoms. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group and a tetradecyl group. , Pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group and the like. As R ¹ and R ² , each structural isomer of the alkyl group can be used. The number of carbon atoms of the alkyl group of R ¹ is preferably 1 to 10 from the viewpoint of further improving the adhesion to the adherend because the alkoxysilyl group portion is less likely to cause steric hindrance when reacting with the adherend. 5 is more preferable. The number of carbon atoms of the alkyl group of ^R2 is preferably 1 to 10 and more preferably 1 to 5 from the viewpoint of further improving the adhesiveness to the adherend.

m is an integer of 0 to 2. m is preferably 0 to 1 and more preferably 0 from the viewpoint of further improving the adhesiveness to the adherend. s is an integer of 6 or more. For s, an integer of 6 to 20 is preferable, and an integer of 6 to 10 is more preferable, from the viewpoint of widening the physical distance between the organic group X and the alkoxysilyl group and improving the reactivity of the functional groups of both. From the same viewpoint, the carbon number of the carbon chain (linear moiety) between the organic group X and the alkoxysilyl group in the formula (I) is preferably 6 to 20, more preferably 6 to 10.

Examples of the silane compound A include glycidoxyalkyltrialkoxysilane, glycidoxyalkyldialkoxysilane, (meth) acryloxyalkyltrialkoxysilane, (meth) acryloxydialkyldialkoxysilane, alkenyltrialkoxysilane, and styrylalkyltri. Alkoxysilane, N-2- (aminoethyl) -8-aminooctylmethyldimethoxysilane, N-2- (aminoethyl) -8-aminooctyltrimethoxysilane, 3-aminooctyltrimethoxysilane, 3-aminooctylli Alkoxysilane, 3-triethoxysilyl-N- (1,3-dimethylbutylidene) octylamine, N-phenyl-8-aminooctyltrimethoxysilane, 8-ureidooctylmethyldiethoxysilane, 8-mercaptooctylmethyldimethoxysilane , 8-Mercaptooctyltrimethoxysilane, 8-isocyanate octyltrimethoxysilane, 8-isocyanate octyltriethoxysilane, and the like.

Examples of the glycidoxyalkyltrialkoxysilane include 8-glycidoxyoctyltriethoxysilane and 8-glycidoxyoctyltriethoxysilane. Examples of the glycidoxyalkyldialkoxysilane include 8-glycidoxyoctylmethyldimethoxysilane and 8-glycidoxyoctylmethyldiethoxysilane. Examples of the (meth) acryloxyalkyltrialkoxysilane include 8- (meth) acryloxyoctyltriethoxysilane and 8- (meth) acryloxyoctyltriethoxysilane. Examples of the (meth) acryloxidialkyldialkoxysilane include 8- (meth) acryloxioctylmethyldimethoxysilane and 8- (meth) acryloxyoctylmethyldiethoxysilane. Examples of the alkenyltrialkoxysilane include octenyltrialkoxysilane and octenylalkyldialkoxysilane. Examples of the octenyltrialkoxysilane include 7-octenyltrimethoxysilane and 7-octenyltriethoxysilane. Examples of the octenylalkyldialkoxysilane include 7-octenylmethyldimethoxysilane and 7-octenylmethyldiethoxysilane. Examples of the styrylalkyltrialkoxysilane include p-styryloctyltrialkoxysilane.

The silane compound A can be synthesized, for example, by reacting organochlorosilane with an alcohol. The silane compound A may be used alone or in combination of two or more. The adhesive composition of the present embodiment may further contain a silane compound having s of 0 to 5 in the formula (I).

The content of the silane compound A is an adhesive composition from the viewpoint that the adhesive force at the interface between the adherend (circuit member, etc.) and the adhesive composition or its cured product (circuit connection member, etc.) tends to be stronger. The following range is preferable based on the total mass of the adhesive component (solid content other than conductive particles in the adhesive composition; the same applies hereinafter) in the material. The content of the silane compound A is preferably 0.1% by mass or more, more preferably 0.25% by mass or more, still more preferably 0.5% by mass or more. The content of the silane compound A is preferably 20% by mass or less, more preferably 10% by mass or less, and further preferably 5% by mass or less. From these viewpoints, the content of the silane compound A is preferably 0.1 to 20% by mass, more preferably 0.25 to 10% by mass, and even more preferably 0.5 to 5% by mass.

((A) component: epoxy resin)
The components (a) include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, naphthalene type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolak type epoxy resin, and bisphenol. Examples thereof include F novolak type epoxy resin, alicyclic epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, hydridein type epoxy resin, isocyanurate type epoxy resin, and aliphatic chain epoxy resin. The component (a) may be halogenated or hydrogenated. The component (a) may be used alone or in combination of two or more.

The content of the component (a) is preferably in the following range based on the total mass of the adhesive component of the adhesive composition from the viewpoint of further improving the adhesiveness to the adherend. The content of the component (a) is preferably 5% by mass or more, more preferably 10% by mass or more, and further preferably 15% by mass or more. The content of the component (a) is preferably 90% by mass or less, more preferably 80% by mass or less, and further preferably 70% by mass or less. From these viewpoints, the content of the component (a) is preferably 5 to 90% by mass, more preferably 10 to 80% by mass, still more preferably 15 to 70% by mass.

((B) component: latent curing agent)
The component (b) is not particularly limited as long as it can cure the epoxy resin. As the component (b), a curing agent capable of generating anionic species by heat or light (anionic polymerizable catalytic curing agent, etc.) and a curing agent capable of generating cationic species by heat or light (cationic polymerization). (Neutral catalyst type curing agent, etc.), heavy addition type curing agent, etc. can be mentioned. The component (b) may be used alone or in combination of two or more. The component (b) is preferably a curing agent capable of generating anionic or cationic species by heat or light from the viewpoint of excellent quick curing and no need for consideration of chemical equivalents, and is preferably anionic polymerizable or A cationically polymerizable catalytic curing agent is more preferable.

Anion-polymerizable catalytic curing agents include imidazole-based curing agents, hydrazide-based curing agents, boron trifluoride-amine complexes, amineimides, tertiary amines, diaminomaleonitrile, melamine and its derivatives, polyamine salts, and the like. Examples thereof include dicyandiamide, and these variants can also be used. Examples of the cationically polymerizable catalytic curing agent include diazonium salts and sulfonium salts, and modified products thereof can also be used. Examples of the heavy addition type curing agent include polyamines, polymercaptans, polyphenols, acid anhydrides and the like.

When a tertiary amine, an imidazole-based curing agent, or the like is used as an anionic polymerizable catalytic curing agent, the epoxy resin can be cured by heating at a medium temperature of about 160 to 200 ° C. for several tens of seconds to several hours. .. Therefore, the pot life can be relatively long.

As the cationically polymerizable catalytic curing agent, for example, a photosensitive onium salt (aromatic diazonium salt, aromatic sulfonium salt, etc.) capable of curing the epoxy resin by irradiation with energy rays is preferable. In addition to energy ray irradiation, aliphatic sulfonium salts and the like can be mentioned as ones that are activated by heat and cure the epoxy resin. Such a curing agent is preferable because it has a quick curing property.

A curing agent in which the component (b) is coated with a polymer substance (polyurethane-based, polyester-based, etc.), a thin film of a metal (nickel, copper, etc.), an inorganic substance (calcium silicate, etc.) and microencapsulated is usable. It is preferable because the time can be extended.

The content of the component (b) is preferably in the following range with respect to 100 parts by mass of the component (a) from the viewpoint of further improving the adhesiveness with the adherend. The content of the component (b) is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and further preferably 30 parts by mass or more. The content of the component (b) is preferably 500 parts by mass or less, more preferably 100 parts by mass or less, and further preferably 70 parts by mass or less. From these viewpoints, the content of the component (b) is preferably 10 to 500 parts by mass, more preferably 20 to 100 parts by mass, and even more preferably 30 to 70 parts by mass.

The content of the component (b) is as follows with respect to a total of 100 parts by mass of the component (a) and the film forming material (component to be blended if necessary) from the viewpoint of further improving the adhesiveness with the adherend. The range is preferred. The content of the component (b) is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and further preferably 30 parts by mass or more. The content of the component (b) is preferably 90 parts by mass or less, more preferably 80 parts by mass or less, and further preferably 70 parts by mass or less. From these viewpoints, the content of the component (b) is preferably 10 to 90 parts by mass, more preferably 20 to 80 parts by mass, and even more preferably 30 to 90 parts by mass.

(Component (c): radically polymerizable compound)
The component (c) is a compound having a functional group capable of radical polymerization. Examples of the component (c) include (meth) acrylate compounds, maleimide compounds, citraconic imide resins, nadiimide resins and the like. The "(meth) acrylate compound" means a compound having a (meth) acryloyl group. The component (c) may be used in the state of a monomer or an oligomer, and the monomer and the oligomer may be used in combination. The component (c) may be used alone or in combination of two or more.

Specific examples of the (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, isobutyl (meth) acrylate, ethylene glycol di (meth) acrylate, and diethylene glycol di (meth) acrylate. Trimethylol Propane Tri (meth) Acrylate, Tetramethylol Methantetra (Meta) Acrylate, 2-Hydroxy-1,3-di (Meta) Acryloxy Propane, 2,2-Bis [4-((Meta) Acryloxymethoxy) Phenyl] propane, 2,2-bis [4-((meth) acryloxypolyethoxy) phenyl] propane, dicyclopentenyl (meth) acrylate, tricyclodecanyl (meth) acrylate, tris ((meth) acryloyloxy) Examples thereof include ethyl) isocyanurate, isocyanuric acid EO-modified di (meth) acrylate, and urethane (meth) acrylate. As the radically polymerizable compound other than the (meth) acrylate compound, for example, the compound described in Patent Document 2 (International Publication No. 2009/0638227) can be preferably used. The (meth) acrylate compound may be used alone or in combination of two or more.

As the component (c), a (meth) acrylate compound is preferable, and urethane (meth) acrylate is more preferable, from the viewpoint of excellent reactivity and stress relaxation. From the viewpoint of improving heat resistance, the (meth) acrylate compound preferably has at least one substituent selected from the group consisting of a dicyclopentenyl group, a tricyclodecanyl group and a triazine ring.

Further, as the component (c), it is preferable to use a radically polymerizable compound having a phosphoric acid ester structure represented by the following general formula (II), and the radically polymerizable compound such as a (meth) acrylate compound and the formula (c) are used. It is more preferable to use in combination with a radically polymerizable compound having a phosphoric acid ester structure represented by II). In these cases, the adhesive strength to the surface of the inorganic substance (metal or the like) is improved, so that it is suitable for adhesion between circuit electrodes, for example.

［式中、ｐは１～３の整数を示し、Ｒは、水素原子又はメチル基を示す。］

[In the formula, p represents an integer of 1 to 3, and R represents a hydrogen atom or a methyl group. ]

The radically polymerizable compound having a phosphoric acid ester structure can be obtained, for example, by reacting anhydrous phosphoric acid with 2-hydroxyethyl (meth) acrylate. Specific examples of the radically polymerizable compound having a phosphoric acid ester structure include mono (2- (meth) acryloyloxyethyl) acid phosphate, di (2- (meth) acryloyloxyethyl) acid phosphate and the like. .. The radically polymerizable compound having a phosphoric acid ester structure represented by the formula (II) may be used alone or in combination of two or more.

The content of the radically polymerizable compound having a phosphoric acid ester structure represented by the formula (II) is a radically polymerizable compound (a component corresponding to the radically polymerizable compound) from the viewpoint of further improving the adhesiveness with the adherend. 0.1 to 1000 parts by mass is preferable, and 1 to 100 parts by mass is more preferable with respect to 100 parts by mass. The content of the radically polymerizable compound having a phosphoric acid ester structure represented by the formula (II) is a radically polymerizable compound and a film forming material (used as necessary) from the viewpoint of further improving the adhesiveness to the adherend. It is preferably 0.01 to 50 parts by mass, and more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the total components.

The radically polymerizable compound may contain an allyl (meth) acrylate. In this case, the content of the allyl (meth) acrylate is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass in total of the radically polymerizable compound and the film forming material (components used as necessary). More preferably, 5 to 5 parts by mass.

The content of the component (c) is preferably in the following range based on the total mass of the adhesive component of the adhesive composition from the viewpoint of further improving the adhesiveness to the adherend. The content of the component (c) is preferably 10% by mass or more, more preferably 20% by mass or more, and further preferably 30% by mass or more. The content of the component (c) is preferably 90% by mass or less, more preferably 80% by mass or less, and further preferably 70% by mass or less. From these viewpoints, the content of the component (c) is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and even more preferably 30 to 70% by mass.

(Component (d): Curing agent that generates radicals by heat or light)
As the component (d), a curing agent (d1) that generates free radicals by heat (hereinafter, sometimes referred to as “(d1) component”) or a curing agent that generates free radicals by (d2) light (hereinafter, referred to as “component”). In some cases, "(d2) component") can be used. The component (d1) is a curing agent that decomposes by heat to generate free radicals. Examples of the component (d1) include peroxides (organic peroxides and the like), azo compounds and the like. From the viewpoint of high reactivity and improvement of pot life, the component (d1) is preferably an organic peroxide having a half-life of 10 hours of 40 ° C. or higher and a half-life of 1 minute of 180 ° C. or lower, preferably halved. More preferably, an organic peroxide having a temperature of 60 ° C. or higher for a period of 10 hours and a temperature of 170 ° C. or lower for a half-life of 1 minute is more preferable.

Specific examples of the component (d1) include diacyl peroxide (benzoyl peroxide and the like), peroxydicarbonate, peroxyester, peroxyketal, dialkyl peroxide, hydroperoxide, silyl peroxide and the like.

As the component (d1), a curing agent having a concentration of chlorine ions and organic acids of 5000 ppm or less is preferable from the viewpoint of suppressing corrosion of electrodes (circuit electrodes, etc.), and curing with less organic acid generated after thermal decomposition. The agent is more preferred. Specific examples of such the component (d1) include peroxyesters, dialkyl peroxides, hydroperoxides, silyl peroxides and the like, and peroxyesters are more preferable from the viewpoint of obtaining high reactivity.

Peroxyesters include cumylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, and t-hexyl. Peroxyneodecanoate, t-butylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-di (2-) Ethylhexanoylperoxy) hexane, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate Ate, t-butylperoxyisobutyrate, 1,1-bis (t-butylperoxy) cyclohexane, t-hexylperoxyisopropylmonocarbonate, t-butylperoxy-3,5,5-trimethylhexanoate , T-Butylperoxylaurate, 2,5-dimethyl-2,5-di (m-toloil peroxy) hexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate , T-hexyl peroxybenzoate, t-butyl peroxyacetate and the like. As the component (d1) other than the peroxyester, for example, the compound described in Patent Document 2 (International Publication No. 2009/0638227) can be preferably used. The peroxy ester may be used alone or in combination of two or more.

The component (d2) is a curing agent that is decomposed by light to generate free radicals. As the component (d2), a compound that generates free radicals by irradiation with light having a wavelength of 150 to 750 nm can be used. Examples of such a compound include Photoinitiation, Photopolymation, and Photocuring, J. Mol., From the viewpoint of high sensitivity to light irradiation. -P. The α-acetaminophenone and phosphine oxide derivatives described in Foausier, Hanser Publicers (1995), p17-p35 are preferred. The component (d2) may be used alone or in combination of two or more. The component (d2) and the component (d1) (the above-mentioned peroxide, azo compound, etc.) may be used in combination. The component (d1) or the component (d2) may be used in combination with a curing agent that generates free radicals by ultrasonic waves, electromagnetic waves, or the like.

(D) The component is appropriately selected according to the target connection temperature, connection time, pot life, and the like. The component (d) may be used alone or in combination of two or more. The component (d) may be used in combination with a decomposition accelerator, a decomposition inhibitor, or the like. Further, the component (d) may be coated with a polyurethane-based or polyester-based polymer substance or the like and microencapsulated. Microencapsulated hardeners are preferred because of their extended pot life.

The content of the component (d) is preferably in the following range from the viewpoint that a sufficient reaction rate can be easily obtained when the connection time is 25 seconds or less. The content of the component (d) is preferably 0.1 part by mass or more, and more preferably 1 part by mass or more with respect to 100 parts by mass of the component (c). The content of the component (d) is preferably 40 parts by mass or less, and more preferably 20 parts by mass or less with respect to 100 parts by mass of the component (c). From these viewpoints, the content of the component (d) is preferably 0.1 to 40 parts by mass, more preferably 1 to 20 parts by mass with respect to 100 parts by mass of the component (c).

The content of the component (d) is preferably in the following range from the viewpoint that a sufficient reaction rate can be easily obtained when the connection time is 25 seconds or less. The content of the component (d) is preferably 0.1 part by mass or more with respect to 100 parts by mass in total of the component (c) and the film forming material (component used as necessary), and is preferably 1 part by mass or more. Is more preferable. The content of the component (d) is preferably 40 parts by mass or less, preferably 20 parts by mass or less, based on 100 parts by mass of the total of the component (c) and the film forming material (components used as necessary). Is more preferable. From these viewpoints, the content of the component (d) may be 0.1 to 40 parts by mass with respect to 100 parts by mass in total of the component (c) and the film forming material (component used as necessary). It is preferably 1 to 20 parts by mass, and more preferably 1 to 20 parts by mass.

When the connection time is not limited, the content of the component (d) is preferably in the following range from the viewpoint that a sufficient reaction rate can be easily obtained. The content of the component (d) is preferably 0.01 part by mass or more, and more preferably 0.1 part by mass or more with respect to 100 parts by mass of the component (c). The content of the component (d) is preferably 30 parts by mass or less, and more preferably 15 parts by mass or less with respect to 100 parts by mass of the component (c). From these viewpoints, the content of the component (d) is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 15 parts by mass with respect to 100 parts by mass of the component (c). preferable.

When the connection time is not limited, the content of the component (d) is preferably in the following range from the viewpoint that a sufficient reaction rate can be easily obtained. The content of the component (d) is preferably 0.01 part by mass or more, preferably 0.1 part by mass, based on 100 parts by mass of the total of the component (c) and the film forming material (component used as necessary). It is more preferable that the amount is more than one part. The content of the component (d) is preferably 30 parts by mass or less, preferably 15 parts by mass or less, based on 100 parts by mass of the total of the component (c) and the film forming material (components used as necessary). Is more preferable. From these viewpoints, the content of the component (d) may be 0.01 to 30 parts by mass with respect to a total of 100 parts by mass of the component (c) and the film forming material (component used as necessary). It is preferably 0.1 to 15 parts by mass, more preferably 0.1 to 15 parts by mass.

(Film forming material)
The adhesive composition of the present embodiment may contain a film-forming material, if necessary. The film-forming material improves the handleability of the film under normal conditions (normal temperature and pressure) when the liquid adhesive composition is solidified into a film, and has characteristics such as resistance to tearing, resistance to cracking, and resistance to stickiness. Can be applied to the film. Examples of the film forming material include phenoxy resin, polyvinyl formal, polystyrene, polyvinyl butyral, polyester, polyamide, xylene resin, polyurethane and the like. Among these, phenoxy resin is preferable from the viewpoint of excellent adhesiveness, compatibility, heat resistance and mechanical strength. The film forming material may be used alone or in combination of two or more.

Examples of the phenoxy resin include a resin obtained by double-adding a bifunctional epoxy resin and a bifunctional phenol, and a resin obtained by reacting the bifunctional phenol with epihalohydrin until polymerization. Can be mentioned. The phenoxy resin contains, for example, 1 mol of bifunctional phenol and 0.985 to 1.015 mol of epihalohydrin at a temperature of 40 to 120 ° C. in a non-reactive solvent in the presence of a catalyst such as an alkali metal hydroxide. It can be obtained by reacting. As the phenoxy resin, from the viewpoint of excellent mechanical and thermal properties of the resin, the compounding equivalent ratio of the bifunctional epoxy resin and the bifunctional phenols is particularly set to epoxy group / phenol hydroxyl group = 1 / 0.9 to. It is set to 1 / 1.1, and organic solvents (amide-based, ether-based, ketone-based, lactone-based, alcohol-based) having a boiling point of 120 ° C. or higher in the presence of catalysts such as alkali metal compounds, organic phosphorus compounds, and cyclic amine compounds. Etc.), a resin obtained by heating to 50 to 200 ° C. under the condition that the reaction solid content is 50% by mass or less and performing a heavy addition reaction is preferable. The phenoxy resin may be used alone or in combination of two or more.

Examples of the bifunctional epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, bisphenol S type epoxy resin, biphenyl diglycidyl ether, and methyl-substituted biphenyl diglycidyl ether. Bifunctional phenols are compounds having two phenolic hydroxyl groups. Bifunctional phenols include hydroquinones, bisphenol A, bisphenol F, bisphenol AD, bisphenol S, bisphenol fluorene (4,4'-(9-fluorenylidene) diphenol, etc.), methyl-substituted bisphenol fluorene, dihydroxybiphenyl, methyl-substituted. Examples thereof include bisphenols such as dihydroxybiphenyl. The phenoxy resin may be modified (for example, epoxy-modified) with a radically polymerizable functional group or other reactive compound.

The content of the film-forming material is preferably 10 to 90 parts by mass, more preferably 20 to 60 parts by mass with respect to 100 parts by mass of the adhesive component of the adhesive composition.

(Conductive particles)
The adhesive composition of the present embodiment may further contain conductive particles. Examples of the constituent material of the conductive particles include gold (Au), silver (Ag), nickel (Ni), copper (Cu), metals such as solder, and carbon. Further, coated conductive particles in which a non-conductive resin, glass, ceramic, plastic or the like is used as a core and the core is coated with the metal (metal particles or the like) or carbon may be used. Since the coated conductive particles or the heat-melted metal particles are deformable by heating and pressurizing, the height variation of the circuit electrode is eliminated at the time of connection, and the contact area with the electrode is increased at the time of connection, so that the reliability is improved. preferable.

The average particle size of the conductive particles is preferably 1 to 30 μm from the viewpoint of excellent dispersibility and conductivity. The average particle size of the conductive particles can be measured using, for example, instrumental analysis such as laser diffraction. From the viewpoint of excellent conductivity, the content of the conductive particles is preferably 0.1 part by mass or more, and more preferably 1 part by mass or more with respect to 100 parts by mass of the adhesive component of the adhesive composition. The content of the conductive particles is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, based on 100 parts by mass of the adhesive component of the adhesive composition, from the viewpoint of easily suppressing a short circuit of the electrodes (circuit electrodes, etc.). preferable.

(Other ingredients)
The adhesive composition of the present embodiment may appropriately contain a polymerization inhibitor such as hydroquinone and methyl ether hydroquinone, if necessary.

The adhesive composition of the present embodiment is a homopolymer or a copolymer obtained by polymerizing at least one monomer component selected from the group consisting of (meth) acrylic acid, (meth) acrylic acid ester and acrylonitrile. It may be further contained. From the viewpoint of excellent stress relaxation, the adhesive composition of the present embodiment preferably contains acrylic rubber or the like, which is a copolymer obtained by polymerizing a glycidyl (meth) acrylate having a glycidyl ether group. The weight average molecular weight of the acrylic rubber is preferably 200,000 or more from the viewpoint of enhancing the cohesive force of the adhesive composition.

The adhesive composition of the present embodiment may contain coated fine particles in which the surface of the conductive particles is coated with a polymer resin or the like. When such coated fine particles are used in combination with the conductive particles, even when the content of the conductive particles is increased, it is easy to suppress a short circuit due to contact between the conductive particles. Can be improved. The coated fine particles may be used alone without using the conductive particles, or the coated fine particles and the conductive particles may be used in combination.

The adhesive composition of the present embodiment includes rubber fine particles, a filler, a softener, an accelerator, an antiaging agent, a colorant, a flame retardant, a thixotropic agent, a coupling agent, a phenol resin, a melamine resin, and isocyanates. Etc. can also be contained. The adhesive composition of the present embodiment may appropriately contain additives such as an adhesion improver (excluding a coupling agent), a thickener, a leveling agent, a colorant, and a weather resistance improver.

The rubber fine particles have an average particle size of 2 times or less the average particle size of the conductive particles, and the storage elastic modulus at room temperature is 1/2 of the storage elastic modulus of the conductive particles and the adhesive composition at room temperature. The following particles are preferred. In particular, when the material of the rubber fine particles is silicone, acrylic emulsion, SBR, NBR or polybutadiene rubber, it is preferable to use the rubber fine particles alone or in combination of two or more. The three-dimensionally crosslinked rubber fine particles have excellent solvent resistance and are easily dispersed in the adhesive composition.

The filler can improve the electrical characteristics (connection reliability, etc.) between the circuit electrodes. As the filler, for example, particles having an average particle size of 1/2 or less of the average particle size of the conductive particles can be preferably used. When non-conductive particles are used in combination with a filler, particles having an average particle size or less of the non-conductive particles can be used as the filler. The content of the filler is preferably 5 to 60 parts by mass with respect to 100 parts by mass of the adhesive component of the adhesive composition. When the content is 60 parts by mass or less, the effect of improving the connection reliability tends to be further sufficiently obtained. When the content is 5 parts by mass or more, the effect of adding the filler tends to be sufficiently obtained.

The adhesive composition of the present embodiment can be used in the form of a paste when it is liquid at room temperature. When it is solid at room temperature, it may be heated and used, or it may be made into a paste using a solvent. The solvent that can be used is not particularly limited as long as it is a solvent that is not reactive with the adhesive composition and additives and exhibits sufficient solubility, but has a boiling point of 50 to 150 ° C. at normal pressure. The solvent is preferable. When the boiling point is 50 ° C. or higher, the solvent is poorly volatile at room temperature, so that it can be used even in an open system. When the boiling point is 150 ° C. or lower, it is easy to volatilize the solvent, so that good reliability can be obtained after bonding.

The adhesive composition of the present embodiment may be in the form of a film. The solution obtained by adding a solvent or the like to the adhesive composition as needed is applied onto a fluororesin film, a polyethylene terephthalate film, a releaseable base material (release paper, etc.), and then the solvent or the like is removed. This makes it possible to obtain a film. Further, a film can be obtained by impregnating a base material such as a non-woven fabric with the solution, placing the solution on the peelable base material, and then removing the solvent or the like. When used in the form of a film, it is more convenient from the viewpoint of excellent handleability and the like.

The adhesive composition of the present embodiment can be adhered by applying pressure together with heating or light irradiation. By using both heating and light irradiation, adhesion can be performed at a lower temperature in a short time. The light irradiation is preferably light in the wavelength range of 150 to 750 nm. It can be cured with an irradiation amount of 0.1 to 10 J / cm ² using a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp (ultra-high pressure mercury lamp, etc.), a xenon lamp, a metal halide lamp, or the like. The heating temperature is not particularly limited, but is preferably a temperature of 50 to 170 ° C. The pressure is not particularly limited as long as it does not damage the adherend, but is preferably 0.1 to 10 MPa. Heating and pressurization are preferably performed in the range of 0.5 seconds to 3 hours.

The adhesive composition of the present embodiment can be used as an adhesive for different kinds of adherends having different coefficients of thermal expansion. Specifically, it is used as a circuit connection material typified by an anisotropic conductive adhesive, a silver paste, a silver film, etc .; an elastomer for CSP, an underfill material for CSP, a semiconductor element adhesive material typified by LOC tape, etc. be able to. The adhesive composition of the present embodiment is applied to an adherend composed of various materials (for example, inorganic substances (oxides, metals, etc.), organic substances, and composites thereof) before and after the reliability test. Has excellent adhesive strength.

<Structure and its manufacturing method>
The structure of the present embodiment includes the adhesive composition of the present embodiment or a cured product thereof. The structure of this embodiment is, for example, a semiconductor device such as a circuit connection structure. As one aspect of the structure of the present embodiment, the circuit connection structure includes a first circuit member having a first circuit electrode, a second circuit member having a second circuit electrode, and a first circuit member. And a circuit connecting member arranged between the second circuit members. The first circuit member has, for example, a first substrate and a first circuit electrode arranged on the first substrate. The second circuit member has, for example, a second substrate and a second circuit electrode arranged on the second substrate. The first circuit electrode and the second circuit electrode are opposed to each other and electrically connected to each other. The circuit connection member contains the adhesive composition of the present embodiment or a cured product thereof. The structure according to the present embodiment may include the adhesive composition according to the present embodiment or a cured product thereof, and instead of the circuit member of the circuit connection structure, a member having no circuit electrode ( A substrate or the like) may be used.

The method for producing a structure of the present embodiment includes a step of curing the adhesive composition of the present embodiment. As one aspect of the method for manufacturing the structure of the present embodiment, the method for manufacturing the circuit connection structure includes a first circuit member having a first circuit electrode and a second circuit member having a second circuit electrode. In the arrangement step of arranging the adhesive composition of the present embodiment between the two, the first circuit member and the second circuit member are pressurized to electrically press the first circuit electrode and the second circuit electrode. It also comprises a heating and pressurizing step of heating and curing the adhesive composition. In the arrangement step, the first circuit electrode and the second circuit electrode can be arranged so as to face each other. In the heating and pressurizing step, the first circuit member and the second circuit member can be pressurized in opposite directions.

Hereinafter, a circuit connection structure and a method for manufacturing the circuit connection structure will be described as one aspect of the present embodiment with reference to the drawings. FIG. 1 is a schematic cross-sectional view showing an embodiment of a structure. The circuit connection structure 100a shown in FIG. 1 includes a circuit member (first circuit member) 20 and a circuit member (second circuit member) 30 facing each other, and is between the circuit member 20 and the circuit member 30. Is arranged with a circuit connecting member 10 for connecting them. The circuit connection member 10 contains a cured product of the adhesive composition of the present embodiment.

The circuit member 20 includes a substrate (first substrate) 21 and a circuit electrode (first circuit electrode) 22 arranged on the main surface 21a of the substrate 21. In some cases, an insulating layer (not shown) may be arranged on the main surface 21a of the substrate 21.

The circuit member 30 includes a substrate (second substrate) 31 and a circuit electrode (second circuit electrode) 32 arranged on the main surface 31a of the substrate 31. In some cases, an insulating layer (not shown) may be arranged on the main surface 31a of the substrate 31.

The circuit connection member 10 contains an insulating substance (cured product of a component excluding conductive particles) 10a and conductive particles 10b. The conductive particles 10b are arranged at least between the circuit electrodes 22 and the circuit electrodes 32 facing each other. In the circuit connection structure 100a, the circuit electrode 22 and the circuit electrode 32 are electrically connected via the conductive particles 10b.

The circuit members 20 and 30 have one or more circuit electrodes (connection terminals). As the circuit members 20 and 30, for example, members having electrodes that require electrical connection can be used. As the circuit member, a chip component such as a semiconductor chip (IC chip), a resistor chip, or a capacitor chip; a printed circuit board, a substrate such as a semiconductor mounting substrate, or the like can be used. Examples of the combination of the circuit members 20 and 30 include a semiconductor chip and a semiconductor mounting substrate. Examples of the material of the substrate include inorganic substances such as semiconductors, glass and ceramics; organic substances such as polyimide, polyethylene terephthalate, polycarbonate, (meth) acrylic resin and cyclic olefin resin; and composites such as glass / epoxy. The substrate may be a plastic substrate.

FIG. 2 is a schematic cross-sectional view showing another embodiment of the structure. The circuit connection structure 100b shown in FIG. 2 has the same configuration as the circuit connection structure 100a except that the circuit connection member 10 does not contain the conductive particles 10b. In the circuit connection structure 100b shown in FIG. 2, the circuit electrode 22 and the circuit electrode 32 are in direct contact with each other and are electrically connected without interposing conductive particles.

The circuit connection structures 100a and 100b can be manufactured, for example, by the following method. First, when the adhesive composition is in the form of a paste, the resin layer containing the adhesive composition is arranged on the circuit member 20 by applying and drying the adhesive composition. When the adhesive composition is in the form of a film, the resin layer containing the adhesive composition is arranged on the circuit member 20 by attaching the film-like adhesive composition to the circuit member 20. Subsequently, the circuit member 30 is placed on the resin layer arranged on the circuit member 20 so that the circuit electrode 22 and the circuit electrode 32 are arranged so as to face each other. Then, by heat-treating or irradiating the resin layer containing the adhesive composition with light, the adhesive composition is cured to obtain a cured product (circuit connection member 10). As a result, the circuit connection structures 100a and 100b can be obtained.

Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to the following examples.

<Preparation of film-shaped adhesive composition>
[Example 1]
A phenoxy resin was synthesized from a bisphenol A type epoxy resin and a phenol compound (4,4'-(9-fluorenelidene) -diphenol) having a fluorene ring structure in the molecule. This phenoxy resin was dissolved in a mixed solvent of toluene / ethyl acetate = 50/50 (mass ratio) to prepare a solution having a solid content of 40% by mass. Next, acrylic rubber (copolymer of 40 parts by mass of butyl acrylate-30 parts by mass of ethyl acrylate-30 parts by mass of acrylonitrile-3 parts by mass of glycidyl methacrylate, weight average molecular weight 800,000) was prepared as a rubber component, and this acrylic rubber was prepared. A solution having a solid content of 15% by mass was prepared by dissolving in a mixed solvent of toluene / ethyl acetate = 50/50 (mass ratio). Further, a liquid curing agent containing a microcapsule type latent curing agent (microencapsulated amine-based curing agent), a bisphenol F type epoxy resin, and a naphthalene type epoxy resin at a mass ratio of 34:49:17. A contained epoxy resin (epoxy equivalent: 202) was prepared. Further, as a silane compound, 8-glycidoxyoctyltrimethoxysilane (product name: KBM4803, manufactured by Shin-Etsu Chemical Co., Ltd.) was prepared.

These materials are blended so that the mass ratio (solid content) of the phenoxy resin, acrylic rubber, the curing agent-containing epoxy resin and the silane compound is 20:30:47: 3, and the varnish A1 (adhesive composition-containing liquid) is blended. ) Was prepared. Further, conductive particles A having a nickel layer having a thickness of 0.2 μm provided on the surface of the particles having polystyrene as the core were prepared. The average particle size of the conductive particles was 5 μm, and the specific gravity was 2.5. The conductive particles A were blended in an amount of 5 parts by mass with respect to 100 parts by mass of the solid content of the varnish A1 to prepare a varnish B1 (circuit connection material-containing liquid). Varnish B1 is applied to a polyethylene terephthalate (PET) film having a thickness of 50 μm on one side using a coating device, and then dried with hot air at 70 ° C. for 3 minutes to form a film-like adhesive having a thickness of 20 μm. The composition was formed on a PET film.

[Comparative Example 1]
Same as Example 1 except that 3-glycidoxypropyltrimethoxysilane (product name: KBM403, manufactured by Shin-Etsu Chemical Co., Ltd.) was used as the silane compound instead of 8-glycidoxyoctyltrimethoxysilane. To prepare a film-like adhesive composition.

[Example 2]
A phenoxy resin solution having a solid content of 40% by mass by dissolving 50 g of a phenoxy resin (product name: PKHC, manufactured by Union Carbide Co., Ltd., weight average molecular weight 45,000) in a mixed solvent of toluene / ethyl acetate = 50/50 (mass ratio). Was prepared. As radically polymerizable compounds, isocyanuric acid EO-modified diacrylate (product name: M-215, manufactured by Toa Synthetic Co., Ltd.), 2- (meth) acryloyloxyethyl phosphate (product name: P-2M, manufactured by Kyoeisha Chemical Co., Ltd.) ) And urethane acrylate (product name: U-2PPA, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) were used. As a silane compound, 7-octenyltrimethoxysilane (product name: KBM1083, manufactured by Shin-Etsu Chemical Co., Ltd.) was prepared. Benzoyl peroxide (product name: Niper BMT-K40, manufactured by NOF CORPORATION) was prepared as a radical generator.

The mass ratio (solid content) of these materials to phenoxy resin, isocyanuric acid EO-modified diacrylate, 2- (meth) acryloyloxyethyl phosphate, urethane acrylate, silane compound and radical generator is 50:19: 3: 20. A varnish B1 (adhesive composition-containing liquid) was prepared by blending in a ratio of 3: 5. Further, the conductive particles A were blended in an amount of 5 parts by mass with respect to 100 parts by mass of the solid content of the varnish B1 to prepare a varnish B2 (circuit connection material-containing liquid). Varnish B2 is applied to a polyethylene terephthalate (PET) film having a thickness of 50 μm on one side using a coating device, and then dried with hot air at 70 ° C. for 3 minutes to form a film-like adhesive having a thickness of 20 μm. The composition was formed on a PET film.

[Comparative Example 2]
As the silane compound, vinyl trimethoxysilane (product name: KBM103, manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of 7-octenyltrimethoxysilane, but the film-like adhesion was carried out in the same manner as in Example 2. An agent composition was prepared.

[Example 3]
As the silane compound, 8-methacryloxyoctyltrimethoxysilane (product name: KBM5803, manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of 7-octenyltrimethoxysilane in the same manner as in Example 2. A film-shaped adhesive composition was prepared.

[Comparative Example 3]
As the silane compound, 3-methacryloxypropyltrimethoxysilane (product name: KBM503, manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of 7-octenyltrimethoxysilane in the same manner as in Example 2. A film-shaped adhesive composition was prepared.

<Evaluation of adhesive strength>
As the first circuit member, a flexible circuit board (FPC) having 500 copper circuits having a line width of 75 μm, a pitch of 150 μm, and a thickness of 18 μm was prepared. As the second circuit member, a glass (thickness 0.7 mm) having a thin layer of 0.5 μm silicon nitride (SiN _x ) formed was prepared. A thermocompression bonding device (heating method: constant heat type) with the film-shaped adhesive composition of Examples 1 to 3 or Comparative Examples 1 to 3 interposed between the first circuit member and the second circuit member. , Toray Engineering Co., Ltd.) was used to heat and pressurize at 170 ° C. and 3 MPa for 20 seconds to connect over a width of 2 mm to prepare a circuit connection structure (connection body).

Regarding this circuit connection structure, the adhesive strength immediately after adhesion (after heating and pressurizing at 170 ° C. and 3 MPa for 20 seconds) and the adhesive strength after being left in an 85 ° C., 85% RH constant temperature and humidity chamber for 100 hours. Was measured by a 90-degree peeling method according to JISZ0237. Here, as the adhesive strength measuring device, Tensilon UTM-4 (peeling speed 50 mm / min, 25 ° C.) manufactured by Toyo Baldwin Co., Ltd. was used.

Table 1 shows the results of the measurements performed as described above.

From the above, in each of Examples 1 to 3, the adhesive strength immediately after bonding is higher than that in Comparative Examples 1 to 3, and even after the reliability test (high temperature and high humidity treatment), the surface of the substrate (inorganic substrate) is reached. It was confirmed that the adhesive strength of the product can be kept good.

10 ... Circuit connection member, 10a ... Insulating material, 10b ... Conductive particles, 20 ... First circuit member, 21 ... First substrate, 21a ... Main surface, 22 ... First circuit electrode, 30 ... Second Circuit member, 31 ... second substrate, 31a ... main surface, 32 ... second circuit electrode, 100a, 100b ... circuit connection structure.

Claims (9)

An adhesive composition containing a silane compound having a structure represented by the following general formula (I), for circuit connection, and in the form of a film.

(In the formula, X represents an organic group, R ¹ and R ² each independently represent an alkyl group, m represents an integer of 0 to 2, s represents an integer of 6 or more, and the organic group X represents the organic group. Contains at least one selected from the group consisting of an ethylenically unsaturated bond-containing group, an epoxy group, a nitrogen atom-containing group and a sulfur atom-containing group, and the nitrogen atom-containing group is an amino group, a mono-substituted amino group or a di-substituted group. It is an amino group, an isocyanato group, an imidazole group, a ureido group or a maleimide group, and the sulfur atom-containing group is a mercapto group .) The adhesive composition according to claim 1, further comprising conductive particles. An adhesive that contains a silane compound having a structure represented by the following general formula (I) and conductive particles of 100 parts by mass or less with respect to 100 parts by mass of the adhesive component of the adhesive composition, and is in the form of a film. Composition.

(In the formula, X represents an organic group, R ¹ and R ² each independently represent an alkyl group, m represents an integer of 0 to 2, s represents an integer of 6 or more, and the organic group X represents the organic group. Contains at least one selected from the group consisting of an ethylenically unsaturated bond-containing group, an epoxy group, a nitrogen atom-containing group and a sulfur atom-containing group, and the nitrogen atom-containing group is an amino group, a mono-substituted amino group or a di-substituted group. It is an amino group, an isocyanato group, an imidazole group, a ureido group or a maleimide group, and the sulfur atom-containing group is a mercapto group .) The adhesive composition according to claim 3, which is used for circuit connection. Any one of claims 1 to 4, wherein the organic group X comprises at least one selected from the group consisting of a (meth) acryloyl group, a vinyl group, an epoxy group, the nitrogen atom-containing group and the sulfur atom-containing group. The adhesive composition according to the section. The adhesive composition according to any one of claims 1 to 5, further comprising an epoxy resin and a latent curing agent. The adhesive composition according to any one of claims 1 to 6, further comprising a radically polymerizable compound and a curing agent that generates radicals by heat or light. A structure comprising the adhesive composition according to any one of claims 1 to 7 or a cured product thereof. With the first circuit member having the first circuit electrode,
A second circuit member with a second circuit electrode, and
A circuit connecting member arranged between the first circuit member and the second circuit member is provided.
The first circuit electrode and the second circuit electrode are electrically connected to each other.
A structure in which the circuit connecting member comprises the adhesive composition according to any one of claims 1 to 7 or a cured product thereof.

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