CN103140535A

CN103140535A - Epoxy resin of low leachability and partially esterified epoxy resin thereof, production method therefor, and curable resin composition comprising same

Info

Publication number: CN103140535A
Application number: CN2011800476845A
Authority: CN
Inventors: 臼井大晃; 森本正浩
Original assignee: Kyoritsu Chemical and Co Ltd
Current assignee: Kyoritsu Chemical and Co Ltd
Priority date: 2010-10-01
Filing date: 2011-09-14
Publication date: 2013-06-05
Anticipated expiration: 2031-09-14
Also published as: WO2012043222A1; TW201619231A; KR20130118324A; JP2012077202A; JP5736613B2; CN105131251B; TWI534170B; TWI588173B; CN105131251A; KR101812832B1; CN103140535B; TW201229081A

Abstract

The purpose of the invention is to obtain an epoxy resin and a partially esterified epoxy resin, which have reduced solubility in liquid crystals and are capable of preventing liquid crystal contamination and of being used as an oligomer component of a high quality sealing compound. The invention is a novel epoxy resin, wherein the structure of the epoxy resin has been modified with a certain structure, a partially esterified epoxy resin wherein the epoxy resin has been partially esterified, and a production method therefor.

Description

Low stripping property epoxy resin and partial esterification epoxy resin, their manufacture method and the curable resin composition that contains them

Technical field

The present invention relates to low stripping property epoxy resin and partial esterification epoxy resin, their manufacture method and the curable resin composition that contains them.

Background technology

In the manufacture method of liquid crystal display device, the technique of dripping be a kind of can the closed loop by the sealing agent that under vacuum, liquid crystal directly dripped in, make its applying, carry out vacuum open, thereby make the technique of panel.This technique of dripping has the consumption that reduces liquid crystal, shortens liquid crystal to the many merits such as injection length of panel, and the manufacture method as the liquid crystal panel of present use large substrate has become main flow.In the method that comprises the technique of dripping, coating sealing agent/liquid crystal makes its applying, then carries out gap formation, position adjustment, mainly carries out the curing of sealing agent by ultraviolet curing.

At present, the position of drawing of sealing agent is in the position that light shines fully, so present situation is that sealing be difficult for to produce uncured part, thereby does not have the problem of polluting liquid crystal, but in recent years along with the needs on narrow limit, sealing station is in more the trend near display pixel.Therefore, due to the pollution that comes self-sealing substance, impact and easily cause and show bad trend so be in electrical characteristic to display pixel section.Particularly in small panel, the distance from display part to sealing agent is narrow, and the bad generation of the demonstration that causes because of contaminative is more obvious.Thus, sealing agent that need to be few to liquid crystal pollution.

Up to the present, as the method that reduces the contaminative of liquid crystal, various researchs have been carried out.

Proposed by using crystallinity epoxy resin, thereby be reduced in the scheme (patent documentation 1) of the stripping of resin in the liquid crystal in curing process when making liquid crystal panel.

As epoxy resin, for bisphenol S type, ether type, thioether-type and fluorenes type epoxy resin and in having the compound of epoxy alkane unit, proposed to have suppressed the sealing agent (patent documentation 2) of the contaminative of liquid crystal.

In addition, as the raw material of sealing agent, also studied the situation of using partial esterification epoxy resin.

Proposed by make 3 officials can epoxy resin or 4 officials can epoxy resin generation part acryloyl, thereby reduce the ratio of the compound that the propylene acidylate does not occur, the scheme (patent documentation 3) of the stripping when reducing thermofixation.

Proposed by (methyl) acrylic acid derivative that utilization has a carboxyl make 3 officials can phenol novolak type epoxy resin or 4 officials can phenol novolak type epoxy resin occur partially modified, thereby the title complex with epoxy resin and acrylic resin improves liquid stabilising, improves the scheme (patent documentation 4) of the orientation characteristic of liquid crystal.

The prior art document

Patent documentation

Patent documentation 1: TOHKEMY 2006-23583 communique

Patent documentation 2: No. 4211942 communique of Japan's special permission

Patent documentation 3: TOHKEMY 2008-3260 communique

Patent documentation 4: TOHKEMY 2008-179796 communique

Summary of the invention

Invent problem to be solved

But, because the epoxy resin of record in patent documentation 1 is crystalline, so there is the possibility of separating out for the possibility that need to mix with liquid resin as liquid sealant or because of intermiscibility.

In patent documentation 3 and 4, the epoxy resin of the epoxy resin of 3 officials' energy of record and 4 officials energy is high viscosity, is perhaps solids as a rule, thereby limited as the use of sealing agent.

In addition, with regard to sealing agent, in the situation that the UV irradiation dose is low, relevant contaminative is not enough under existing conditions.

The solvability that the object of the invention is to obtain in liquid crystal is suppressed and can prevents epoxy resin and the partial esterification epoxy resin that oligopolymer pollution, that can be used as high-quality sealing agent of liquid crystal becomes to assign to use.

Be used for solving the means of problem

The inventor etc. are in order to improve liquid crystal panel with the desired characteristic of the sealing material that drips, be conceived to as the epoxy resin of the main component of the sealing material contaminative to liquid crystal, conduct in-depth research, found that, by with certain ad hoc structure, the structure as the epoxy resin of main component being carried out modification, thereby can reduce the solvability/stripping property of oligopolymer in liquid crystal itself, thereby complete the present invention.

That is, the present invention relates to a kind of epoxy resin, described epoxy resin is by general formula (1), general formula (2) or general formula (3) expression,

In general formula (1), general formula (2) and general formula (3),

X is-O-, the alkylene base of carbonatoms 1～4 or the alkylidene of carbonatoms 2～4,

Y be carbonatoms 1～4 alkylene base-carbonatoms 6～20 arylidene-carbonatoms 1～4 alkylene base, carbonatoms 1～4 alkylene base-carbonatoms 6～20 arylidene or by-R ⁷-(O-R ⁷) _nThe group of-expression (in formula, R ⁷Be the alkylene base of carbonatoms 1～4, n is 0 or 1～6 integer),

R ¹, R ², R ³, R ⁴, R ⁵And R ⁶Be hydrogen, glycidyl or methyl glycidyl independently of each other,

Each R ²¹Be hydrogen or methyl separately independently of each other,

R ¹, R ², R ³, R ⁴, R ⁵And R ⁶In at least 2 be glycidyl or methyl glycidyl.

The present invention relates to a kind of partial esterification epoxy resin, described partial esterification epoxy resin is by general formula (4), general formula (5) or general formula (6) expression,

In general formula (4), general formula (5) and general formula (6),

X, Y and R ²¹As described in above-mentioned definition,

R ¹¹, R ¹², R ¹³, R ¹⁴, R ¹⁵And R ¹⁶For hydrogen, glycidyl, methyl glycidyl or by-Z-R ⁸(in formula, Z is 2-hydroxyl trimethylene base or 2-methyl-2-hydroxyl trimethylene base to the group of expression, R ⁸Be acryl or methacryloyl),

R ¹¹, R ¹², R ¹³, R ¹⁴, R ¹⁵And R ¹⁶In at least 2 be glycidyl, methyl glycidyl or by-Z-R ⁸The group of expression,

Glycidyl and methyl glycidyl, with the ratio of acryl and methacryloyl, that is, and glycidyl+methyl glycidyl/with acryl+methacryloyl, be 10: 90～90: 10.

The present invention relates to a kind of manufacture method of epoxy resin, the manufacture method of described epoxy resin comprises operation (1A)～(1B),

Operation (1A): make have the epoxy group(ing) more than 2 in molecule the multi-functional epoxy compound under the existence of metal catalyst with molecule in have a hydroxyl more than 2 polyol react, obtain the operation of multi-functional epoxy compound's epoxy addition body, and

Operation (1B): make the hydroxyl of the multi-functional epoxy compound's who obtains in operation (1A) epoxy addition body that epoxidised operation occur.

The present invention relates to the manufacture method according to epoxy resin described above, it is for the manufacture of the method for above-mentioned epoxy resin by the expression of general formula (1)～general formula (3), comprises following operation (2A)～(2B),

Operation (2A): the epoxy compounds by general formula (7a), general formula (8a) or general formula (9a) expression is reacted with the dihydroxy compound that is represented by following general formula (10) under the existence of metal catalyst, obtain the operation by the epoxy addition body of general formula (7b), general formula (8b) or general formula (9b) expression

In general formula (7a), general formula (8a) and general formula (9a),

X and R ²¹As described in above-mentioned definition,

HO-Y-OH (10)

In general formula (10), Y is as described in above-mentioned definition,

In general formula (7b), general formula (8b) and general formula (9b), X, Y and R ²¹As described in above-mentioned definition; With

Operation (2B): make the hydroxyl initial ring oxidation by the epoxy addition body of general formula (7b)～general formula (9b) expression that obtains in operation (2A), obtain the operation by the epoxy resin of general formula (1)～general formula (3) expression.

The present invention relates to a kind of manufacture method of partial esterification epoxy resin, the manufacture method of described partial esterification epoxy resin comprises operation (1C),

Operation (1C): the operation that the epoxy resin that makes by above-mentioned manufacture method is reacted with (methyl) vinylformic acid under the existence of basic catalyst.

The present invention relates to the manufacture method according to partial esterification epoxy resin described above, it is for the manufacture of the method for above-mentioned partial esterification epoxy resin by the expression of general formula (4)～general formula (6), comprises operation (2C),

Operation (2C): the epoxy resin by general formula (1), general formula (2) or general formula (3) expression that makes by above-mentioned manufacture method is reacted with (methyl) vinylformic acid under the existence of basic catalyst, obtain the operation by the partial esterification epoxy resin of general formula (4)～general formula (6) expression

In general formula (1), general formula (2) and general formula (3),

X, Y, R ¹, R ², R ³, R ⁴, R ⁵, R ⁶, R ²¹As described in above-mentioned definition,

The present invention relates to a kind of solidification compound, described solidification compound contains and is selected from (a) above-mentioned epoxy resin by general formula (1), general formula (2) and general formula (3) expression, (b) above-mentioned partial esterification epoxy resin by general formula (4), general formula (5) and general formula (6) expression, (c) epoxy resin that makes by above-mentioned manufacture method, and the resin more than a kind in the partial esterification epoxy resin that (d) makes by above-mentioned manufacture method.

The effect of invention

According to the present invention, the solvability that can obtain in liquid crystal is suppressed and can prevents epoxy resin and the partial esterification epoxy resin that oligopolymer liquid crystal pollution, that can be used as high-quality sealing agent becomes to assign to use.

Description of drawings

Fig. 1 means the microscope figure of orientation of the corner part of the liquid crystal under illumination 1000mJ.

Fig. 2 means the microscope figure of orientation of the line part of the liquid crystal under illumination 1000mJ.

Fig. 3 means the microscope figure of orientation of the corner part of the liquid crystal under illumination 50mJ.

Fig. 4 means the microscope figure of orientation of the line part of the liquid crystal under illumination 50mJ.

Fig. 5 means the microscope figure of orientation of the corner part of the liquid crystal under illumination 0mJ.

Fig. 6 means the microscope figure of orientation of the line part of the liquid crystal under illumination 0mJ.

Embodiment

Below suitable embodiment of the present invention is described.

Epoxy resin of the present invention is the compound by general formula (1), general formula (2) and general formula (3) expression.

The alkylene base of carbonatoms 1～4 can list methylene radical, ethylene group, trimethylene base and fourth support base, is preferably methylene radical and ethylene group.

The alkylidene of carbonatoms 2～4 can list ethidine, propylidene base, isopropylidene, methyl propylidene base and fourth fork base, is preferably ethidine and isopropylidene.

The arylidene of carbonatoms 6～20 is aryl of monocycle or many rings, can list phenylene, naphthylidene and anthrylene, is preferably phenylene.

The illustration of the alkylene base of the carbonatoms 1～4 in the arylidene of the alkylene base-carbonatoms 6～20 of carbonatoms 1～4 and the arylidene of carbonatoms 6～20 is as described in above-mentioned definition.Arylidene as the alkylene base-carbonatoms 6～20 of carbonatoms 1～4 can preferably list methylene radical-phenylene.In the present invention, with the arylidene of the alkylene base-carbonatoms 6～20 of carbonatoms 1～4 in the bonding order of each group can choose wantonly.For example, for being bonded to R ¹～R ⁶Sauerstoffatom, can with the arylidene of the alkylene base-carbonatoms 6～20 of carbonatoms 1～4 in the alkylene base bonding of carbonatoms 1～4, can also with the arylidene bonding of carbonatoms 6～20.

The illustration of the alkylene base of the carbonatoms 1～4 in the alkylene base of the arylidene-carbonatoms 1～4 of the alkylene base-carbonatoms 6～20 of carbonatoms 1～4 and the arylidene of carbonatoms 6～20 is as described in above-mentioned definition.Alkylene base as the arylidene-carbonatoms 1～4 of the alkylene base-carbonatoms 6～20 of carbonatoms 1～4 can preferably list phenylene two (methylene radical).

In the present invention, R ¹～R ⁶In at least 2 be glycidyl or methyl glycidyl.In the present invention, so-called epoxy group(ing) comprise glycidyl and methyl glycidyl the two.Here, glycidyl is 2,3-epoxypropyl, and the methyl glycidyl is 2,3-epoxy group(ing)-2-methyl-propyl.In the present invention, preferred R ¹～R ⁶Among be glycidyl or methyl glycidyl, more preferably R more than 3 ¹～R ⁶Among be all glycidyl or methyl glycidyl.In addition, in the present invention, preferred glycidyl and methyl glycidyl are present in and R ⁴, R ⁵And R ⁶Be on the Sauerstoffatom of primary carbon atom bonding, more preferably glycidyl and methyl glycidyl are present in and R ¹～R ⁶Be on the Sauerstoffatom of primary carbon atom and secondary carbon(atom) bonding.

In the present invention, can pass through high performance liquid chromatography (HPLC) by the quantity of the glycidyl in the epoxy resin of general formula (1)～general formula (3) expression and methyl glycidyl calculates.Particularly, can obtain the peak corresponding with the number of glycidyl and methyl glycidyl by HPLC, calculate according to peak area separately glycidyl and methyl glycidyl number have a ratio.Can calculate thus the glycidyl that contains in compound and the number of methyl glycidyl.In addition, in the situation that be mixture by the epoxy resin of general formula (1)～(3) expressions, the quantity of glycidyl and methyl glycidyl can be calculated with the form of the mean value of mixture.That is, with regard to the quantity of epoxy group(ing), the mass analysis (LC-MS) at each peak that can be by carrying out HPLC judges molecular weight, according to the existence of each composition in mixture than the average quantity of calculating the epoxy group(ing) in mixture.For example, comprise epoxy group(ing) in the mixture of existence by the epoxy resin of general formula (1) and general formula (2) expression and be 3 and 4 s' compound and polymer thereof, comprise epoxy group(ing) in the epoxy resin that is represented by general formula (3) and be 3,4,5 and 6 s' compound and polymeric situation thereof.

Bonding position by the X of the compound of general formula (1) expression is preferably 4, and in other words 4 '-position, is the compound with bisphenol-type epoxy resin skeleton.In addition, the bonding position by the naphthalene nucleus in the compound of general formula (2) expression is preferably 1,6-bonding.

In the present invention, the number-average molecular weight by the compound of general formula (1)～general formula (3) expression is preferably 200～5,000.If in such scope, cementability is good, and the contaminative of liquid crystal further is inhibited.In the present invention, number-average molecular weight is the number-average molecular weight that adopts gel permeation chromatography (GPC) to calculate by polystyrene conversion.

In the present invention, be preferably 100～3,000g/eq. by the epoxy equivalent (weight) of the epoxy compounds of general formula (1)～general formula (3) expression, more preferably 200～1,000g/eq..If in such scope, cementability is good, and the contaminative of liquid crystal further is inhibited.In the present invention, in the situation that epoxy resin is mixture, epoxy equivalent (weight) can be with the form of the mean value of mixture and is obtained.In the present invention, epoxy equivalent (weight) can be obtained according to JIS K 7236:2001 (corresponding ISO3001:1999).

In the present invention, partial esterification epoxy resin is by general formula (4), general formula (5) and general formula (6) expression.In the partial esterification epoxy resin by general formula (4)～general formula (6) expression, R ¹¹, R ¹², R ¹³, R ¹⁴, R ¹⁵And R ¹⁶In at least 2 for glycidyl, methyl glycidyl or contain (methyl) acryl by-Z-R ⁸The group of expression.That is, the partial esterification epoxy resin by the expression of general formula (4)～general formula (6) of the present invention be a part by the glycidyl of the epoxy resin of general formula (1)～general formula (3) expression and methyl glycidyl by (methyl) acryl and epoxy resin.

In the present invention, preferred R ¹¹～R ¹⁶Among more than 3 be glycidyl, methyl glycidyl or contain (methyl) acryl by-Z-R ⁸The group of expression, more preferably R ¹¹R ¹⁶Among be glycidyl, methyl glycidyl or contain (methyl) acryl by-Z-R ⁸The group of expression.In addition, in the present invention, preferred glycidyl, methyl glycidyl and (methyl) acryl are present in and R ¹⁴, R ¹⁵And R ¹⁶Be on the Sauerstoffatom of primary carbon atom bonding, more preferably glycidyl, methyl glycidyl and (methyl) acryl are present in and R ¹¹～R ¹⁶Be on the Sauerstoffatom of primary carbon atom and secondary carbon(atom) bonding.

Can be calculated by HPLC by the glycidyl in the partial esterification epoxy resin of general formula (4)～general formula (6) expression and the quantity of methyl glycidyl and the quantity of (methyl) acryl.Particularly, can obtain the peak corresponding with the quantity of the quantity of each epoxy group(ing) and each (methyl) acryl by HPLC, calculate the ratio that exists of number separately according to peak area separately.Obtain thus by glycidyl, methyl glycidyl in the partial esterification epoxy resin of general formula (4)～general formula (6) expression, contain (methyl) acryl by-Z-R ⁸The number of the group of expression.In addition, in the situation that be mixture by the partial esterification epoxy resin of general formula (4)～(6) expressions, the quantity of glycidyl and methyl glycidyl and (methyl) acryl can be calculated with the form of the mean value of mixture.For example; comprise the resin that is become (methyl) acryl by the part of the mixture of the epoxy resin of general formula (1) and general formula (2) expression and their epoxy group(ing) in the mixture of existence by the partial esterification epoxy resin of general formula (4) and general formula (5) expression, a part that comprises the mixture of the epoxy resin that is represented by general formula (3) and their epoxy group(ing) by the partial esterification epoxy resin of general formula (6) expression becomes the situation of the resin of (methyl) acryl.

In the partial esterification epoxy resin by general formula (4)～general formula (6) expression; the ratio of glycidyl and methyl glycidyl and acryl and methacryloyl; that is, the ratio of epoxy group(ing) and (methyl) acryl is 10: 90～90: 10.Here, epoxy group(ing) can be obtained by HPLC and epoxy equivalent (weight) with the ratio of (methyl) acryl.Particularly, the part that has only reduced by partial esterification due to the epoxy equivalent (weight) as the epoxy resin of raw material, thus can be by measuring the epoxy equivalent (weight) of partial esterification epoxy resin, thus calculate which kind of degree of esterified one-tenth.In addition, the mass analysis (LC-MS) at each peak that can be by carrying out HPLC, and obtain the molecular weight of various compositions and have ratio, thereby obtain the epoxy group(ing) of various compositions and the ratio of acryl.

In the present invention, be preferably 500～10 by the number-average molecular weight of the partial esterification epoxy resin of general formula (4)～general formula (6) expression, 000, more preferably 800～5,000.In addition, be preferably 1,000～1 by the partial esterification epoxy resin of general formula (4)～general formula (6) expression the viscosity of 20 ℃, 000,000mPs, more preferably 40,000～600,000mPs.If in such scope, be difficult for occuring to flow when coating liquid crystal, can suppress the pollution to liquid crystal.It should be noted that, in the present invention, viscosity is to use E type viscometer, is the value that records under 2.5rpm at the rotating speed of bell-shaped rotor.

The manufacture method of epoxy resin

Manufacture method to epoxy resin of the present invention describes.In the manufacture method of epoxy resin of the present invention, comprise following operation: based on as the reaction of the multi-functional epoxy compound of raw material and polyol and the open loop operation of the multi-functional epoxy compound's who carries out epoxy group(ing), and the hydroxyl of the epoxy addition body that generates of the open loop by epoxy group(ing) and be derived from the epoxidation process of the hydroxyl of polyol.In the present invention, epoxidation comprise glycidyl and methyl glycidylization the two.

The manufacture method of epoxy resin of the present invention comprises following operation (1A)～(1B):

(1A) make have the epoxy group(ing) more than 2 in molecule the multi-functional epoxy compound under the existence of metal catalyst with molecule in have a hydroxyl more than 2 polyol react, obtain the operation of multi-functional epoxy compound's epoxy addition body, and

(1B) make the hydroxyl of the multi-functional epoxy compound's who obtains in operation (1A) epoxy addition body that epoxidised operation occur.

Operation (1A)

In operation (1A), the multi-functional epoxy compound who has the epoxy group(ing) more than 2 in the molecule as starting compound forms hydroxyl by the open loop of epoxy group(ing), and forms the hydroxyl that is derived from polyol.Here, so-called multi-functional epoxy compound's open loop body refer to the multi-functional epoxy compound the whole open loops of epoxy group(ing) and compound.

The multi-functional epoxy compound is so long as have the epoxy compounds of the epoxy group(ing) more than 2, just without particular determination in 1 molecule.As the multi-functional epoxy compound, can list following compound.

As the multi-functional epoxy compound, can enumerate many alkylene glycols classes such as the ethylene glycol of sening as an envoy to, glycol ether, triglycol, propylene glycol, dipropylene glycol, tripropylene glycol, the polyalcohols such as dihydroxy methylpropane, TriMethylolPropane(TMP), the spiroglycol, glycerine and Epicholorohydrin react and the polynary glycidyl ether compound of aliphatics.

As the multi-functional epoxy compound, can enumerate the aromatic diol class such as the dihydroxyphenyl propane of sening as an envoy to, bisphenol S, Bisphenol F, dihydroxyphenyl propane D and to they carry out ethylene glycol, propylene glycol, alkylene glycol modification and glycols react with Epicholorohydrin and must the polynary glycidyl ether compound of aromatic series.

As the multi-functional epoxy compound, can enumerate the aromatic dicarboxylic acid such as the hexanodioic acid of sening as an envoy to, methylene-succinic acid and Epicholorohydrin to react and the polynary glycidyl ether compound of aliphatics, the aromatic dicarboxylic acids such as m-phthalic acid, terephthalic acid, pyromellitic acid and Epicholorohydrin are reacted and must the polynary epihydric alcohol ester compound of aromatic series.

As the multi-functional epoxy compound, can enumerate that the aromatic amine such as the diaminodiphenyl-methane of sening as an envoy to, aniline, m-xylene diamine and Epicholorohydrin react and the polynary Racemic glycidol amine compound of aromatic series.

As the multi-functional epoxy compound, can enumerate the polynary glycidyl compound of glycolylurea type that send as an envoy to glycolylurea and derivative and Epicholorohydrin thereof react and get.

As the multi-functional epoxy compound, phenol resins, novolac resin and the Epicholorohydrin that can enumerate sends as an envoy to is gone out by phenol or cresols and formaldehyde-derived react and the polynary glycidyl ether compound of phenol type, the polynary glycidyl ether compound of phenolic varnish type.

In the present invention, as the multi-functional epoxy compound, the epoxy compounds that is preferably represented by following general formula (7a), general formula (8a) or general formula (9a),

In general formula (7a), general formula (8a) and general formula (9a),

X and R ²¹As described in definition in general formula (1).

As preferred multi-functional epoxy compound of the present invention, by the epoxy compounds of general formula (7a)～general formula (9a) expression, for example can list EPICLON 850 (DAINIPPON INK﹠amp as commercially available product; CHEMICALS, the INC manufacturing), EPIKOTE 828EL, EPIKOTE 1004 (are JAPAN EPOXY RESIN CO., LTD. make) etc. bisphenol A type epoxy resin, EPIKOTE 806, EPIKOTE 4004 (are JAPAN EPOXY RESIN CO., LTD. make) etc. bisphenol f type epoxy resin, EPICLON HP4032, EPICLON EXA-4700 (are DAINIPPON INK ﹠amp; CHEMICALS, INC makes) etc. naphthalene type epoxy resin, 3 officials' energy epoxy resin such as VG-3101 (Mitsui Petrochemical Ind., Ltd.'s manufacturings).

In the present invention, has the polyol of the hydroxyl more than 2 in molecule so long as contain the compound of the hydroxyl more than 2 in molecule, just without particular determination.As the concrete example of polyol, can list following compound.

as the compound that has 2 hydroxyls in molecule, can list ethylene glycol, glycol ether, triglycol, propylene glycol, dipropylene glycol, neopentyl glycol, 1, 4-butyleneglycol and 1, single alkylene glycol and many alkylene glycols such as 6-hexylene glycol, pyrocatechol, 1, the 2-dihydroxy naphthlene, 2, the 3-dihydroxy naphthlene, 1, 2-dihydroxyanthraquinone and 2, the aromatic hydroxy compound that 3-dihydroxyl quinoxaline etc. are 2 yuan, benzene-1, the 4-dimethanol, benzene-1, the 3-dimethanol, benzene-1, the aromatic alcohols such as 4-di-alcohol, the 4-methylolphenol, the 3-methylolphenol, the hydroxyalkyl phenol such as 4-hydroxyethyl phenol and 3-hydroxyethyl phenol.

As the compound that has 3 hydroxyls in molecule, can list glycerine, TriMethylolPropane(TMP), 2-methyl-2-methylol-1, ammediol, 2,4-dihydroxyl-3-methylol pentane, 1,2,6-hexane three pure and mild 1,1,3 yuan of alcohol such as 1-three (methylol) propane, pyrogallol, 3,4,5-trihydroxytoluene, 1, the aromatic polyhydroxy compounds that the gallic acid ester cpds such as 2,4-trihydroxyanthraquinone, gallic acid and methyl gallate, Tenox PG and Stabilizer GA 8 etc. are 3 yuan.

As the compound that has the hydroxyl more than 4 in molecule, can list tetramethylolmethane, diglycerol, tetramethylol methane, alkylene glycosides (methyl glucoside, ethyl glycosides etc.).In addition, can list the aromatic polyhydroxy compounds more than 4 yuan such as calixarene compound of 2,3,4,4'-Tetrahydroxybenzophenone, ellagic acid, hexahydroxybenzene, tannic acid and pyrocatechol or pyrogallol.

In the present invention, having the polyol of the hydroxyl of 2～6 in the preferred molecule of polyol, more preferably have the polyol of the hydroxyl of 2～4 in molecule, is particularly preferably the dihydroxy compound by following general formula (10) expression,

HO-Y-OH (10)

In general formula (10), Y is as described in definition in general formula (1).

As the dihydroxy compound by general formula (10) expression, can preferably list ethylene glycol, propylene glycol, butane-1, single alkylene glycol and many alkylene glycols such as 4-glycol glycol ether, triglycol, benzene-1,4-dimethanol, benzene-1,3-dimethanol, benzene-Isosorbide-5-Nitrae-aromatic alcohols such as di-alcohol, (2-hydroxy phenyl) methyl alcohol, (2-hydroxy phenyl)-hydroxyl alkylene base phenol such as 2-ethanol.

Metal catalyst just can be chosen use wantonly, such as listing by metal and BF such as copper, zinc, iron, magnesium, silver, calcium, tin so long as be used for the catalyzer of the ring-opening reaction of epoxy group(ing) ₄ ^-, SiF ₆ ^2-Or PF ₆ ^-, CF ₃SO ₂ ^-Metal catalyst Deng the negatively charged ion formation.Be preferably stannous fluoboric acid (Sn (BF ₄) 2).

In the present invention, with respect to the epoxy group(ing) in the polyfunctional epoxy compound of 1 equivalent, the consumption of polyol is 1 equivalent～10 equivalents, is preferably 4 equivalents～8 equivalents.In the present invention, can adopt high performance liquid chromatography (HPLC), the disappearance at the peak by the multi-functional epoxy compound in raw material and single end reaction thing, thus confirm that all epoxy group(ing) and polyol react and generate the epoxy addition body.Here, whole epoxy group(ing) that so-called single end reaction thing refers to the multi-functional epoxy compound are the reactant of open loop not, for example by general formula (7a) and (8a) compound of 1 epoxy group(ing) generation open loop only in the compound of expression, and in by the compound of general formula (9a) expression the compound of 1 or 2 epoxy group(ing) generation open loop only.

In the present invention, metal catalyst is 10～1,000ppm for the weight of complete reaction mixture, is preferably 20～200ppm.

Operation (1A) although in temperature of reaction without particular restriction, be 50 ℃～130 ℃, preferred 70 ℃～120 ℃.Reaction in operation (1A) can under the existence of organic solvent or do not have organic solvent under carry out.As spendable organic solvent, can list the aromatic hydrocarbons as benzene and toluene and so on, for example ring type aliphatic ketone of pimelinketone and so on, and the dihydroxy compound in starting raw material.

Operation (1B)

By operation (1B), make the hydroxyl initial ring oxidation of the multi-functional epoxy compound's who obtains epoxy addition body in operation (1A).In operation (1B), part or all initial ring oxidation of the hydroxyl in multi-functional epoxy compound's epoxy addition body.In the present invention, 50%～100% initial ring oxidation of the hydroxyl of preferred multi-functional epoxy compound's epoxy addition body, more preferably 75%～100% initial ring oxidation.

Multi-functional epoxy compound's epoxy addition body is the starting compound in operation (1B), can list above-mentioned multi-functional epoxy compound the whole open loops of epoxy group(ing) and compound.Preferably as by the epoxy addition body of the epoxy compounds of general formula (7a)～general formula (9a) expression, by the multi-functional epoxy compound's of following general formula (7b), general formula (8b) or general formula (9b) expression epoxy addition body,

In formula, X, Y and R ²¹As described in above-mentioned definition.

In operation (1B), epoxidation can adopt and known the epoxidised reaction of hydroxyl for example can be listed Epicholorohydrin method and oxidation style, is preferably the Epicholorohydrin method.

The Epicholorohydrin method is a kind of by reacting with Epicholorohydrin or methyl epichlorohydrin under the existence of epoxy addition body at alternate transfer catalyst that makes the multi-functional epoxy compound who obtains in operation (1A), thereby with the hydroxyl process for epoxidation of multi-functional epoxy compound's epoxy addition body.

In the Epicholorohydrin method, can make with the mole number that reaches required epoxy group(ing) quantity the reaction of Epicholorohydrin or methyl epichlorohydrin.The hydroxyl of the epoxy addition body of the multi-functional epoxy compound with respect to 1 mole, the amount of Epicholorohydrin or methyl epichlorohydrin are 0.5～5 mole, are preferably 0.5～2.5.For example, have the compound by general formula (7b) and general formula (8b) expression of 4 hydroxyls in the molecule with respect to 1 mole, the amount of Epicholorohydrin or methyl epichlorohydrin is 2～20 moles, preferred 2～10 moles.Have the compound by general formula (9b) expression of 6 hydroxyls in molecule with respect to 1 mole, the amount of Epicholorohydrin or methyl epichlorohydrin is 3～30 moles, preferred 3～15 moles.

Alternate transfer catalyst can list the tetra-alkyl ammonium chloride as methyl tricapryl ammonium chloride, methyl three decyl ammonium chlorides and tetramethyl ammonium chloride and so on, and as the quaternary ammonium salts such as aralkyl tri alkyl ammomium chloride of benzyl trimethyl ammonium chloride and so on, preferred benzyl trimethyl ammonium chloride.The consumption of alternate transfer catalyst is 0.1～5 % by weight based on the gross weight of reactant, more preferably 0.5～2.0 % by weight.

Reaction can be as hydrocarbon such as hexane and pentanes, the ethers such as diethyl ether, t-butyl methyl ether and diisopropyl ether, or carry out under the existence of the solvent of ketone such as acetone and methylethylketone and so on, but also can use excessive Epicholorohydrin and methyl epichlorohydrin as solvent.Temperature of reaction is 30～90 ℃, preferred 40～65 ℃, most preferably can approximately 50 react to the temperature of about 55 ℃ of scopes.

Oxidation style is a kind of method that comprises following operation, the allylation in addition of the hydroxyl of the multi-functional epoxy compound's who soon obtains in operation (1A) epoxy addition body, obtain the operation of diallyl ether compound, and with the allyl group of diallyl ether compound or the 2-methyl-2-propenyl operation of oxidation in addition.In the present invention, the allylation of hydroxyl comprises and makes hydroxyl be converted into allyl group or 2-methyl-2-propenyl.

In the present invention, the operation that obtains the diallyl ether compound is a kind of epoxy addition body and allyl halide or 2-methyl-2-propenyl halide reaction by making the multi-functional epoxy compound, thereby the hydroxyl of multi-functional epoxy compound's epoxy addition body is converted into the operation of allyl group or 2-methyl-2-propenyl.Particularly, after multi-functional epoxy compound's epoxy addition body and allyl halide are dissolved in dimethyl sulfoxide (DMSO), add quaternary ammonium salt, drip alkali aqueous solution when temperature of reaction being remained on below 40 ℃, after dripping end, carry out the approximately reaction of 6 hours in 30～40 ℃.

Halogen as in allyl halide and 2-methyl-2-propenyl halogenide can list chlorine and bromine.The hydroxyl of the epoxy addition body of the multi-functional epoxy compound with respect to 1 mole, allyl halide and 2-methyl-halid addition of 2-propenyl is preferably 3～30 moles.

As quaternary ammonium salt, such as listing the four aryl ammonium halides such as the quaternary alkylammonium halides such as Tetrabutyl amonium bromide or tetraphenylphosphonichloride chloride ammonium.The epoxy addition body of multi-functional epoxy compound with respect to 1 mole, the addition of quaternary ammonium salt are preferably 0.001 mole～0.1 mole.

As alkali aqueous solution, can list calcium hydroxide, potassium hydroxide and sodium hydroxide.With respect to the hydroxyl of the multi-functional epoxy compound's of 1 equivalent epoxy addition body, the alkali-metal consumption that uses is preferably 2～8 equivalents.

The operation that allyl group or the 2-methyl-2-propenyl of diallyl ether compound carried out oxidation is a kind of operation that the diallyl ether compound is reacted with aquae hydrogenii dioxidi under the existence of salt of wormwood.Particularly, with the hydroxyl of multi-functional epoxy compound's epoxy addition body in addition allylation and the diallyl ether compound in, add nitrile equal solvent and the salt of wormwood such as the alcohol such as methyl alcohol, ethanol or acetonitrile, benzonitrile, under agitation drip 5～40%, preferred 30～35% aquae hydrogenii dioxidi, after dripping end, carry out the oxidizing reaction of 0.5～10 hour, preferred 1～6 hour.

The addition of aquae hydrogenii dioxidi preferably with respect to 1 mole with the hydroxyl of multi-functional epoxy compound's epoxy addition body in addition allylation and the diallyl ether compound for be added into 5～15 moles.Temperature of reaction is for example below 45 ℃, preferred 20～40 ℃.

The manufacture method of epoxy resin of the present invention is preferably the manufacture method of the epoxy resin by the expression of general formula (1)～general formula (3) of the present invention, and the manufacture method of described epoxy resin comprises following operation (2A)～(2B):

(2A) by the epoxy compounds by general formula (7a), general formula (8a) or general formula (9a) expression is reacted with the dihydroxy compound that is represented by following general formula (10) under the existence of metal catalyst, thereby obtain the operation by the epoxy addition body of following general formula (7b), general formula (8b) or general formula (9b) expression

In general formula (7a), general formula (8a) and general formula (9a),

X and R ²¹As described in definition in general formula (1),

HO-Y-OH (10)

In general formula (10), Y is as described in definition in general formula (1),

In general formula (7b), general formula (8b) and general formula (9b),

X, Y and R ²¹As described in above-mentioned definition; With

(2B) make the hydroxyl initial ring oxidation by the epoxy addition body of general formula (7b)～general formula (9b) expression that obtains in operation (2A), obtain the operation by the epoxy resin of general formula (1)～general formula (3) expression.

The manufacture method of partial esterification epoxy resin

Then, the manufacture method of partial esterification epoxy resin of the present invention described.The manufacture method of partial esterification epoxy resin of the present invention comprises operation (1C):

The operation that (1C) epoxy resin that makes by the manufacture method that comprises above-mentioned operation (1A)～(1B) is reacted under the existence of basic catalyst with (methyl) vinylformic acid.

Operation (1C)

In operation (1C), make the glycidyl of the epoxy resin that makes by the manufacture method that comprises above-mentioned operation (1A)～(1B) and methyl glycidyl that (methyl) acryl occur.As the epoxy resin that makes by the manufacture method that comprises operation (1A)～(1B), be preferably the epoxy resin by general formula (1)～general formula (3) expression.

As (methyl) vinylformic acid, without particular determination, for example can use commercially available acrylic or methacrylic acid.

In the present invention, in the operation that the epoxy resin that makes by the manufacture method that comprises operation (1A)～(1B) and (methyl) vinylformic acid are reacted, for the epoxy group(ing) of the epoxy resin that passes through to comprise that the manufacture method of operation (1A)～(1B) makes of 1 equivalent, (methyl) vinylformic acid that reacts is preferably 10～90 equivalent %, 20～80 equivalent % more preferably, more preferably 30～70 equivalent %, be particularly preferably 40～60 equivalent %.In the manufacture method of partial esterification epoxy resin, because glycidyl and methyl glycidyl and (methyl) acrylic acid reaction are carried out quantitatively, so the esterification yield of the partial esterification epoxy resin that obtains also can be inferred according to epoxy equivalent (weight).

Epoxy group(ing) with respect to the epoxy resin that passes through to comprise that the manufacture method of operation (1A)～(1B) makes of 1 equivalent, if (methyl) vinylformic acid is reacted, can obtain partial esterification epoxy resin, this partial esterification epoxy resin is can temporarily obtain regularly good resin properties when the polymerization that unsaturated group is reacted, and can not producing when after polymerization is separated etc. just forms the partial esterification epoxy resin of uniform polymkeric substance.

As basic catalyst, can use the known basic catalyst that uses based on epoxy resin and (methyl) acrylic acid reaction.In addition, also can use the Polymer Supported type basic catalyst that basic catalyst is equipped on polymkeric substance and gets.

As basic catalyst, be preferably organo phosphorous compounds and/or the amine compound of 3 valencys.The alkaline atom of basic catalyst is phosphorus and/or nitrogen.

Organo phosphorous compounds as 3 valencys, can list alkylphosphines class and salt thereof as triethyl phosphine, three n-propyl phosphines, tri-n-butyl phosphine and so on, triphenylphosphine, three tolylphosphine, three-(2, the 6-Dimethoxyphenyl) aryl phosphine class and the salt thereof such as phosphine, the tris phosphite class such as triphenyl phosphite, triethyl-phosphite, tricresyl phosphite (nonyl phenyl ester) and salt thereof etc.Salt as the organo phosphorous compounds of 3 valencys can list ethyltriphenylphosphonium bromide, butyl triphenyl bromide phosphine, octyl group triphenyl bromide phosphine, decyl triphenyl bromide phosphine, isobutyl-triphenyl bromide phosphine, propyl group triphenyl phosphine dichloride, amyl group triphenyl phosphine dichloride, hexyl triphenyl bromide phosphine etc.Wherein, be preferably triphenylphosphine.

as amine compound, can list the secondary amine such as diethanolamine, trolamine, dimethyl benzylamine, three (dimethylaminomethyl) phenol, the tertiary amines such as three (diethylamino methyl) phenol, 1, 5, 7-three azabicyclos [4.4.0] last of the ten Heavenly stems-5-alkene (TBD), the 7-methyl isophthalic acid, 5, 7-three azabicyclos [4.4.0] last of the ten Heavenly stems-5-alkene (Me-TBD), 1, 8-diazabicyclo [5.4.0] 11 carbon-7-alkene (DBU), 6-dibutylamino-1, 8-diazabicyclo [5.4.0] 11 carbon-7-alkene, 1, 5-diazabicyclo [4.3.0] ninth of the ten Heavenly Stems-5-alkene (DBN), 1, 1, 3, strong basicity amine and the salt thereof such as 3-tetramethyl guanidine.Wherein, preferred 1,5,7-three azabicyclos [4.4.0] last of the ten Heavenly stems-5-alkene (TBD).As the salt of amine compound, can list benzyl trimethyl ammonium chloride, benzyltriethylammoinium chloride.

As the polymkeric substance that supports basic catalyst, without particular determination, can use by Vinylstyrene make the crosslinked polymkeric substance that gets of polystyrene or make the crosslinked polymkeric substance that gets of acrylic resin etc. by Vinylstyrene.These polymkeric substance are insoluble in the solvent (such as methylethylketone, methyl iso-butyl ketone (MIBK), toluene etc.) that uses in the epoxy resin that makes by the manufacture method that comprises operation (1A)～(1B) and (methyl) acrylic acid reaction and raw material, resultant.

Polymer Supported type basic catalyst is by making basic catalyst and insoluble polymer generation chemical bonding, or after basic catalyst is imported monomer, then monomer polymerization is carried out by cross-linking monomers such as Vinylstyrenes three-dimensionally crosslinked, thereby can make the Polymer Supported type basic catalyst that is insoluble to methylethylketone, methyl iso-butyl ketone (MIBK), toluene equal solvent.

As Polymer Supported type basic catalyst, particularly, can list diphenylphosphine base polystyrene, 1,5,7-three azabicyclos [4.4.0] last of the ten Heavenly stems-5-alkene polystyrene, N, N-(di-isopropyl) aminomethylpolystyre.e, N-(methylated polystyrene)-4-(methylamino) pyridine etc.These Polymer Supported type basic catalysts can use separately or share more than 2 kinds and use.

Polymer Supported type basic catalyst can use commercially available product.Polymer Supported type basic catalyst as commercially available for example can list PS-PPh ₃(diphenylphosphine base polystyrene, BIOTAGE JAPAN LTD. make), PS-TBD (1,5,7-, three azabicyclos [4.4.0] last of the ten Heavenly stems-5-alkene polystyrene, BIOTAGE JAPAN LTD. makes).

The usage ratio of Polymer Supported type basic catalyst is, for the epoxy group(ing) of the epoxy resin that passes through to comprise that the manufacture method of operation (1A)～(1B) makes of 1 equivalent, Polymer Supported type basic catalyst is preferably 0.5～5.0 milliequivalent, more preferably 1.0～3.0 milliequivalents.If the usage ratio of Polymer Supported type basic catalyst is in above-mentioned scope, from the viewpoint of reactivity, reaction times and catalyzer cost and preferred.

In manufacture method of the present invention, the epoxy resin that obtains by the manufacture method that comprises operation (1A)～(1B) is preferably 60～120 ℃ with temperature in (methyl) acrylic acid reaction process, more preferably 80～120 ℃, more preferably 90～110 ℃.

In the situation that catalyzer makes the epoxy resin that obtains by the manufacture method that comprises operation (1A)～(1B) react with (methyl) vinylformic acid under existing, for preventing gelation, need suitably to guarantee in reaction system and the oxygen concn of the gas phase on reaction system.For example, owing to causing active reduction in the situation that be blown into energetically the oxidation that air causes catalyzer sometimes in the reaction system, so should be noted that.

With regard to the epoxy resin and (methyl) acrylic acid reaction that obtain by the manufacture method that comprises operation (1A)～(1B), because the partial esterification epoxy resin that gets by this reaction solidifies because of ultraviolet isoreactivity energy-ray, so wish to react in covering ultraviolet container.In addition, for preventing vapour phase polymerization, the epoxy resin that obtains by the manufacture method that comprises operation (1A)～(1B) also can carry out under the reflux solvent that epoxy resin is presented good solvent exists with (methyl) acrylic acid reaction, but owing to need to finishing rear desolventizing in reaction in the case, so preferably carry out under solvent-free.As reflux solvent, can list acetone, methylethylketone etc.

In manufacture method of the present invention, after the epoxy resin that obtains by the manufacture method that comprises operation (1A)～(1B) is reacted with (methyl) vinylformic acid, obtain partial esterification epoxy resin by removing Polymer Supported type basic catalyst.As the method for removing Polymer Supported type basic catalyst, the preferred employing filtered or centrifugation.

As the method for filtering Polymer Supported type basic catalyst, for example can list and use the aperture is the method that the nylon mesh NY-10HC (manufacturing of Switzerland Sefar company) of 10 μ m filters out Polymer Supported type basic catalyst.

As with the Polymer Supported type basic catalyst method of centrifugation in addition, can list by using separating centrifuge to carry out solid-liquid separation, thereby remove the method for Polymer Supported type basic catalyst.

Thus, the manufacture method of partial esterification epoxy resin of the present invention is preferably the manufacture method of partial esterification epoxy resin described above, it is for the manufacture of the method for the partial esterification epoxy resin that is represented by general formula (4)～general formula (6), comprises operation (2C):

(2C) epoxy resin by general formula (1), general formula (2) or general formula (3) expression that the manufacture method of the operation by comprising operation (2A)～(2B) gets is reacted under the existence of basic catalyst with (methyl) vinylformic acid, obtain the operation by the partial esterification epoxy resin of general formula (4)～general formula (6) expression.

Solidification compound

Solidification compound of the present invention is described, described curable resin contains and is selected from (a) by the epoxy resin of general formula (1), general formula (2) and general formula (3) expression, (b) the partial esterification epoxy resin that is represented by general formula (4), general formula (5) and general formula (6), (c) epoxy resin that gets by the manufacture method that comprises operation (1A)～(1B), and the resin more than a kind in the partial esterification epoxy resin that (d) gets by the manufacture method that comprises operation (1C).In the present invention, the resin as the matrix oligopolymer composition that contains in curable resin is the resin more than a kind that is selected from epoxy resin of the present invention and partial esterification epoxy resin of the present invention.For example, can use separately by the epoxy resin of general formula (1), general formula (2) or general formula (3) expression or by the partial esterification epoxy resin of general formula (4), general formula (5) or general formula (6) expression, perhaps can be with by the epoxy resin of general formula (1), general formula (2) or general formula (3) expression or by using the mixing more than 2 kinds of partial esterification epoxy resin of general formula (4), general formula (5) or general formula (6) expression.

As the composition that contains in solidification compound of the present invention, except epoxy resin of the present invention and partial esterification epoxy resin, also can list solidifying agent, polymerization starter, weighting agent, coupling agent.

As solidifying agent, without particular determination, can use as solidifying agent and known compound.As solidifying agent, can list amine is solidifying agent, such as organic acid dihydrazide compound, imidazole and its derivants, Dyhard RU 100, aromatic amine, epoxide modified polyamines and poly-Urea,amino-etc., particularly preferably as the VDH (1 of organic acid dihydrazide, two (diazanyl carbonyl the ethyl)-5-sec.-propyl glycolylurea of 3-), ADH (adipic dihydrazide), UDH (7,11-octadecane diene-1,18-pair (diazanyl carbonyl)) and LDH (octadecane-1,18-diformazan acid dihydrazide).These solidifying agent can use separately or share multiple.For the epoxy resin and partial esterification epoxy resin of 100 weight parts, the use level of initiator is preferably 1～25 weight part, more preferably 5～15 weight parts.

Polymerization starter refers to activate by light absorbing energy, thereby produces the compound of free radical.Polymerization starter can use as polymerization starter and known compound without particular determination.as polymerization starter, can list the bitter almond oil camphor class, acetophenones, benzophenone, the thioxanthene ketone, α-acyl group oxime ester class (α-アシロキシ system エステ Le Class), oxoethanoic acid phenyl ester class (Off エニ Le グリオキシレ one ト Class), the benzil class, the azo based compound, the diphenyl sulfide based compound, the acylphosphine oxide based compound, the bitter almond oil camphor class, benzoin ethers and Anthraquinones polymerization starter, the solvability that is preferably in liquid crystal is low, and himself has when rayed a not polymerization starter of the reactive group of generating gasification of resolvent.As preferred polymerization starter of the present invention, for example can list EY resin KR-2 (KSM CO., LTD. makes) etc.For the epoxy resin and partial esterification epoxy resin of 100 weight parts, the use level of polymerization starter is preferably 0.1～5 weight part, more preferably 1～5 weight part.

Weighting agent with the viscosity of controlling solidification compound or raising, solidification compound is solidified and the intensity of cured article, or the Cohesion reliability etc. that improves solidification compound by suppressing linear expansion adds for purpose.Weighting agent can use known inorganic filler and the organic filler that uses for the composition that contains epoxy resin.As inorganic filler, can list calcium carbonate, magnesiumcarbonate, barium sulfate, sal epsom, pure aluminium silicate, titanium oxide, aluminum oxide, zinc oxide, silicon-dioxide, kaolin, talcum, granulated glass sphere, sericite activated clay, wilkinite, aluminium nitride and silicon nitride.As organic filler, can list polymethylmethacrylate, polystyrene, make consist of them monomer with other monomer copolymerization and must multipolymer, polyester micropartical, polyurethane particulate and rubber particle.In the present invention, particularly preferably inorganic filler, for example silicon-dioxide and talcum.For the epoxy resin and partial esterification epoxy resin of 100 weight parts, the use level of weighting agent is preferably 2～40 weight parts, more preferably 5～30 weight parts.

Coupling agent is so that more well add for purpose with the cohesiveness of liquid crystal display substrate.As coupling agent, without particular determination, such as listing gamma-amino propyl trimethoxy silicane, γ mercaptopropyitrimethoxy silane, γ-isocyanate group propyl trimethoxy silicane and 3-glycidoxypropyltrime,hoxysilane etc.These silane coupling agents can use separately or share more than 2 kinds and use.For the epoxy resin and partial esterification epoxy resin of 100 weight parts, the use level of silane coupling agent is preferably 0.1～10 weight part, more preferably 0.5～2 weight part.

Solidification compound of the present invention is by irradiation ultraviolet radiation homenergic ray, by heating or by solidifying at irradiation ultraviolet radiation homenergic ray post-heating.Can obtain the cured article of solidification compound of the present invention thus.Therefore, the method that the solidification compound that contains epoxy resin of the present invention and partial esterification epoxy resin is cured is comprised: to containing the solidification compound irradiation ultraviolet radiation homenergic ray of epoxy resin of the present invention and partial esterification epoxy resin, heat, or the operation that heats after irradiation ultraviolet radiation homenergic ray.

Epoxy resin of the present invention and the stripping property of partial esterification epoxy resin in liquid crystal are extremely low.In addition, with regard to the liquid crystal display device that has used the solidification compound that contains epoxy resin of the present invention and partial esterification epoxy resin, even in the situation that the UV irradiation dose is low, the orientation of liquid crystal is still good, produce demonstration bad, therefore, can be used as the liquid crystal sealing agent.

Embodiment

Next, by embodiment, the specific embodiment of the present invention is described in detail, but the present invention is not subjected to the restriction of these embodiment.

The manufacturing of [synthesis example 1] compound 1c

(1-1) (the ethylene glycol open loop body of bisphenol A type epoxy resin is that X is that the bonding position of isopropylidene, X is 4,4 '-position, R in general formula (7b) to compound 1a ²¹Be hydrogen, Y is the compound of ethylene group) synthetic

45% stannous fluoboric acid (II) aqueous solution of the ethylene glycol of 500g (Tokyo changes into company and makes), 1.0g (gloomy field chemical industrial company make) is added in eggplant type flask.Hold it in 80 ℃ when stirring the bisphenol A type epoxy resin of 340g (EXA850CRP, Dainippon Ink Chemicals makes), slowly add with 1 hour, from add finish stirring 1 hour under 80 ℃.Reaction mixture is cooled to room temperature, adds the methylene dichloride of 1L, the water washing of use 1L 6 times.Remove the solvent of the organic phase of gained by underpressure distillation, obtain the open loop body (compound 1a) of the water white transparency dope of 410g.Need to prove, by high performance liquid chromatography (HPLC), according to the epoxy resin in raw material and only 1 epoxy group(ing) the disappearance at peak of the compound of open loop has occured, thereby confirm that open loop all occurs all epoxy group(ing).

(1-2) (in general formula (1), X is isopropylidene to compound 1b, and the bonding position of X is 4,4 '-position, R ²¹Be hydrogen, Y is ethylene group, R ¹, R ², R ⁴And R ⁵Among 3.8 be the compound of glycidyl) synthetic

The Epicholorohydrin (company makes with the pure medicine of light) of compound 1a (EXA850CRP-ethylene glycol open loop body), the 590g of 232g, the benzyl trimethyl ammonium chloride (Tokyo changes into company and makes) of 50g are joined in the three neck round-bottomed flasks of 2 liters that mechanical stirrer, thermometer, thermoswitch, condenser, Dean-Stark water trap and dropping funnel are installed.Then, be heated to approximately 50 to 55 ℃ when mixture is stirred under the high vacuum of 70 holders (torr), make the Epicholorohydrin vigorous reflux.The 48% solution NaOH (manufacturing of Northeast chemical company) of 160g was slowly added in mixture with 2 hours.After generating azeotrope, send Epicholorohydrin back to reaction system among water/Epicholorohydrin mixture, meanwhile continue to stir.After adding end, continue to stir 3 hours.Then, reaction mixture is cooled to room temperature, adds the methylene dichloride of 1L, the water washing of use 1L 6 times.Remove the solvent of the organic phase that obtains by underpressure distillation, obtain the glycidyl ether body (compound 1b) of the faint yellow transparent dope of 245g.According to HPLC, the epoxy group(ing) in molecule is 3.8.

(1-3) (be in general formula (4), X is isopropylidene to compound 1c, and the bonding position of X is 4,4 '-position, R ²¹Be hydrogen, Y is ethylene group, R ¹¹, R ¹², R ¹⁴And R ¹⁵Among 1.9 be glycidyl and methacryloyl, the ratio of glycidyl and methacryloyl is the compound of 50: 50) synthetic

With the methacrylic acid (Tokyo changes into company and makes) of compound 1b, the 88.7g of 210g, the PS-PPh of 4.7g ₃The BHT of the PS-TBD of (BIOTAGE JAPAN LTD. manufacturing), 10.3g (BIOTAGE JAPAN LTD. manufacturing), 100mg mixes, and stirs 6 hours in 100 ℃.After reaction finishes, by removing by filter catalyzer, obtain the part methyl acrylated epoxy resins.

The manufacturing of [synthesis example 2] compound 2c

(2-1) (2-of bisphenol A type epoxy resin (4-hydroxy phenyl) ethanol open loop body is that X is that the bonding position of isopropylidene, X is 4,4 '-position, R in general formula (7b) to compound 2a ²¹For hydrogen, Y are the compound of methylene radical-phenylene) synthetic

With the bisphenol A type epoxy resin (EXA850CRP, Dainippon Ink Chemicals makes) of 170g, 2-(4-hydroxy phenyl) ethanol (Tokyo changes into company and makes) of 138g, the PS-PPh of 2.3g ₃The toluene of the PS-TBD of (BIOTAGE JAPAN LTD. manufacturing), 4.2g (BIOTAGE JAPAN LTD. manufacturing), 500ml joins in eggplant type flask, stirs 24 hours in 100 ℃.Reaction solution is cooled to room temperature, removes catalyzer by filtration.Remove the solvent of the mixture that obtains by underpressure distillation, obtain the open loop body of the faint yellow transparent dope of 285g.

(2-2) (be that X is isopropylidene in general formula (1), the bonding position of X is 4,4 '-position to compound 2b, R ²¹Be hydrogen, Y is methylene radical-phenylene, R ¹, R ², R ⁴And R ⁵Among 3.6 be the compound of glycidyl) synthetic

The Epicholorohydrin (company makes with the pure medicine of light) of compound 2a (EXA850CRP-2-(4-hydroxy phenyl) ethanol open loop body), the 590g of 185g, the benzyl trimethyl ammonium chloride (Tokyo changes into company and makes) of 22g are joined in the 2L three neck round-bottomed flasks that mechanical stirrer, thermometer, thermoswitch, condenser, Dean-Stark water trap and dropping funnel are installed.Then, be heated to approximately 50 to 55 ℃ when mixture is stirred under the high vacuum of 70 holders (torr), make the Epicholorohydrin vigorous reflux.The 48% solution NaOH (manufacturing of Northeast chemical company) of 185g was slowly added in mixture with 2 hours.After generating azeotrope, among water/Epicholorohydrin mixture, continue to stir when sending Epicholorohydrin back to reaction system.After adding end, continue to stir 4 hours.Then, reaction mixture is cooled to room temperature, adds the methylene dichloride of 1L, the water washing of use 1L 6 times.Remove the solvent of the organic phase that obtains by underpressure distillation, obtain the glycidyl ether body (compound 2b) of the yellow transparent dope of 233g.According to HPLC, the epoxy group(ing) in molecule is 3.6.

(2-3) (be that X is isopropylidene in general formula (4), the bonding position of X is 4,4 '-position to compound 2c, R ²¹Be hydrogen, Y is methylene radical-phenylene, R ¹, R ², R ⁴And R ⁵Among 1.8 be glycidyl and methacryloyl, the ratio of glycidyl and methacryloyl is the compound of 50: 50) synthetic

With the methacrylic acid (Tokyo changes into company and makes) of compound 2b, the 36g of 180g, the PS-PPh of 1.9g ₃The BHT of the PS-TBD of (BIOTAGE JAPAN LTD. manufacturing), 8.3g (BIOTAGE JAPAN LTD. manufacturing), 85mg (company makes with the pure medicine of light) mixes, and stirs 6 hours in 100 ℃.After reaction finishes, remove catalyzer by filtration, obtain the part methyl acrylated epoxy resins.

The manufacturing of [synthesis example 3] compound 3c

(3-1) (the ethylene glycol open loop body of naphthalene type epoxy resin is R in general formula (8b) to compound 3a ²¹The bonding position that is ethylene group, naphthalene nucleus for hydrogen, Y is the compound of 1,6-position) synthetic

45% stannous fluoboric acid (II) aqueous solution of the ethylene glycol of 500g (Tokyo changes into company and makes), 1.0g (gloomy field chemical industrial company make) is added in eggplant type flask.Naphthalene type epoxy resin (HP-4032D, Dainippon Ink Chemicals make) 282g is remained on 100 ℃ when stirring, slowly add with 1 hour, finish to arise from 100 ℃ of stirrings 3 hours from adding.Reaction mixture is cooled to room temperature, adds the methylene dichloride of 1L, the water washing of use 1L 6 times.Remove the solvent of the organic phase that obtains by underpressure distillation, obtain the open loop body (compound 3a) of the yellow transparent dope of 390g.

(3-2) compound 3b (is R in general formula (2) ²¹Be hydrogen, Y is ethylene group, and the bonding position of naphthalene nucleus is 1,6-position, R ¹, R ², R ⁴And R ⁵Among 3.9 be the compound of glycidyl) synthetic

The Epicholorohydrin (company makes with the pure medicine of light) of compound 3a (HP4032D-ethylene glycol open loop body), the 590g of 112g, the benzyl trimethyl ammonium chloride (Tokyo changes into company and makes) of 21g are joined in the three neck round-bottomed flasks of 2 liters that mechanical stirrer, thermometer, thermoswitch, condenser, Dean-Stark water trap and dropping funnel are installed.Then, mixture is stirred under 70 holder (torr) high vacuum, meanwhile be heated to approximately 50 to 55 ℃, make the Epicholorohydrin vigorous reflux.The 48% solution NaOH (manufacturing of Northeast chemical company) of 188g was slowly added in mixture through 2 hours.After generating azeotrope, among water/Epicholorohydrin mixture, continue to stir when sending Epicholorohydrin back to reaction system.After adding end, continue to stir 4 hours.Then, reaction mixture is cooled to room temperature, adds the methylene dichloride of 1L, the water washing of use 1L 6 times.Remove the solvent of the organic phase that obtains by underpressure distillation, obtain the glycidyl ether body (compound 3b) of the faint yellow transparent dope of 179g.According to HPLC, the epoxy group(ing) in molecule is 3.9.

(3-3) compound 3c (is R in general formula (5) ²¹Be hydrogen, Y is ethylene group, and the bonding position of naphthalene nucleus is 1,6-position, R ¹¹, R ¹², R ¹⁴And R ¹⁵Among 1.9 be glycidyl and methacryloyl, the ratio of glycidyl and methacryloyl is the compound of 50: 50) synthetic

With the methacrylic acid (Tokyo changes into company and makes) of compound 3b, the 11.8g of 50g, the PS-PPh of 154mg ₃The BHT of the PS-TBD of (BIOTAGE JAPAN LTD. manufacturing), 341mg (BIOTAGE JAPAN LTD. manufacturing), 12mg mixes, and stirs 6 hours in 100 ℃.After reaction finishes, remove catalyzer by filtration, obtain part methyl acrylated epoxy resins (compound 3c).

The manufacturing of [synthesis example 4] compound 4c

(4-1) (the propylene glycol open loop body of VG3101L is R in general formula (9b) to compound 4a ²¹Be hydrogen, Y is the compound of propylidene) synthetic

The propylene glycol (manufacturing of Northeast chemical company) of TECHMORE VG3101L (PRINTEC CORPORATION manufacturing), the 456g of 148g, 45% stannous fluoboric acid (II) aqueous solution of 130mg (gloomy field chemical industrial company make) are added in eggplant type flask, stirred 20 hours in 100 ℃.Reaction mixture is cooled to room temperature, adds the methylene dichloride of 1L, the water washing of use 1L 6 times.Remove the solvent of the organic phase that obtains by underpressure distillation, obtain the open loop body of the yellow dope of 190g.

(4-2) compound 4b (is R in general formula (3) ²¹Be hydrogen, Y is propylidene, R ¹～R ⁶Among 5.8 be the compound of glycidyl) synthetic

The Epicholorohydrin (company makes with the pure medicine of light) of compound 4a (VG3101L-propylene glycol open loop body), the 590g of 160g, the benzyl trimethyl ammonium chloride (Tokyo changes into company and makes) of 22g are joined in the three neck round-bottomed flasks of 2 liters that mechanical stirrer, thermometer, thermoswitch, condenser, Dean-Stark water trap and dropping funnel are installed.Then, be heated to approximately 50 to 55 ℃ when mixture is stirred under the high vacuum of 70 holders (torr), make the Epicholorohydrin vigorous reflux.The 48% solution NaOH (manufacturing of Northeast chemical company) of 117g was slowly added in mixture with 2 hours.After generating azeotrope, among water/Epicholorohydrin mixture, continue to stir when sending Epicholorohydrin back to reaction system.After adding end, continue to stir 4 hours.Then, reaction mixture is cooled to room temperature, adds the methylene dichloride of 1L, the water washing of use 1L 6 times.Remove the solvent of the organic phase that obtains by underpressure distillation, obtain the glycidyl ether body (compound 4b) of the yellow dope of 207g.According to HPLC, the epoxy group(ing) in molecule is 5.8.

(4-3) compound 4c (is R in general formula (6) ²¹Be hydrogen, Y is propylidene, R ¹¹R ¹⁶Among 5.8 be glycidyl and methacryloyl, the ratio of glycidyl and methacryloyl is the compound of 75: 25) synthetic

With the methacrylic acid (Tokyo changes into company and makes) of compound 4b, the 3.2g of 34g, the PS-PPh of 41mg ₃The BHT of the PS-TBD of (BIOTAGE JAPAN LTD. manufacturing), 75mg (BIOTAGE JAPAN LTD. manufacturing), 10mg mixes, and stirs 6 hours under 100 ℃.After reaction finishes, remove catalyzer by filtration, obtain the part methyl acrylated epoxy resins.

[relatively synthesis example 1]

(5-1) comparative compound 5c's (the part methyl acrylated epoxy resins of the bisphenol A type epoxy resin that uses in synthesis example 1) is synthetic

With the bisphenol A type epoxy resin (EXA850CRP, Dainippon Ink Chemicals makes) of 320.2g, the methacrylic acid (Tokyo changes into company and makes) of 90.4g, the PS-PPh of 1.5g ₃The BHT of (BIOTAGE JAPAN LTD. manufacturing), 100mg mixes, and stirs 6 hours in 100 ℃.After reaction finishes, remove catalyzer by filtration, obtain part methyl acrylated epoxy resins (comparative compound 5c).

With the epoxy addition body that obtains in synthesis example 1～4, epoxy resin and part (methyl) acrylated epoxy resins, viscosity that uses E type viscometer (eastern machine industry company make RE105U) to get as mensuration viscosity under 2.5rpm at the rotating speed of bell-shaped rotor, the epoxy equivalent (weight) and the acryloyl rate that record according to JIS K 7236:2001 are shown in Table 1.Here, the acryloyl rate is calculated according to the equivalence ratio of the epoxy equivalent (weight) that uses and methacrylic acid equivalent.

[table 1]

Compound	1a	1b	1c	2a	2b	2c
							Viscosity (mPas)	Dope	27,600	209,400	Dope	94,800	240,000
Epoxy equivalent (weight) (g/eq.)	-	206	590	-	220	490
							Acryloyl rate (%)	-	-	50	-	-	50

Compound	3a	3b	3c	4a	4b	4c
							Viscosity (mPas)	Dope	15,000	121,200	Dope	212,400	559,200
Epoxy equivalent (weight) (g/eq.)	-	181	420	-	225	280
							Acryloyl rate (%)	-	-	50	-	-	25

for epoxy resin (the compound 1b that makes in synthesis example 1～4, 2b, 3b and 4b) and partial esterification epoxy resin (compound 1c, 2c, 3c and 4c) and synthesis example 1 in the bisphenol A type epoxy resin as starting compound (comparative compound 1a) that uses, the naphthalene type epoxy resin (comparative compound 3a) as starting compound that uses in synthesis example 3, (the TECHMORE VG3101L (PRINTEC CORPORATION manufacturing) of 3 functional-type epoxy resin as starting compound that uses in synthesis example 4, the various oligopolymer of the part methyl acrylated epoxy resins (comparative compound 5c) of the bisphenol A type epoxy resin of comparative compound 4a) and relatively making in synthesis example 1, carry out as follows the stripping property test.

[stripping property test]

The evaluation of the stripping property in liquid crystal is by as the variation of the Ni point (Nematic-Isotropic point) of the transformation temperature of liquid crystal with utilize the direct quantitative of the stripping quantity in liquid crystal of HPLC (high performance liquid chromatography) to carry out.The Ni point of liquid crystal is comprised of the mixing of the various compositions in liquid crystal and decides, and is intrinsic value under various cooperations.Generally speaking, known Ni point is sneaked into some impurity (other composition) and is reduced in liquid crystal because of these, can estimate impurity by the Ni point and sneak into situation.[measuring the making with sample]

The oligopolymer that adds 0.1g in ampoule adds liquid crystal (MLC-11900-080, the MERCK ﹠amp of 1g; CO., INC. makes).This bottle was dropped in 120 ℃ of baking ovens 1 hour, after this standing in room temperature, take out lcd segment after returning to room temperature (25 ℃), filter with 0.2 μ m strainer, make evaluation liquid crystal sample.

[mensuration that Ni is ordered]

The mensuration that Ni is ordered is used differential scanning calorimeter, and (DSC, PERKIN ELMER INC. makes, Pyris6).The evaluation of 10mg is sealing in the aluminium platter with the liquid crystal sample, is to measure under the condition of 5 ℃/minute at heat-up rate.

[calculating of stripping quantity]

The meltage of the oligopolymer in liquid crystal uses HPLC to measure.HPLC measure with sample use the liquid crystal that will take out with dilution in acetonitrile to 100 times and sample.In addition, stripping quantity quantitatively calculates according to the inspection amount line of the peak area of each compound.Will be for the viscosity of the compound of each test and each test the results are shown in table 2 and table 3.

[table 2]

[table 3]

Then, use the partial esterification epoxy resin (compound 1c and 2c) of making in synthesis example 1 and 2 and compare partial esterification epoxy resin (the comparative compound 5c that makes in synthesis example 1, the part methyl acrylated epoxy resins of bisphenol A type epoxy resin), recently make resin combination with cooperation as shown in table 4, carry out the evaluation of the liquid crystal aligning in test element.

[orientation evaluation]

With synthesis example 1 and 3 and the compound (compound 1c, 3c and 5c) that relatively obtains in synthesis example 1 respectively with EY resin KR-2 (KSM CO.; LTD. after manufacturing), SEAHOSTAR KE-C50HG (Japanese catalyst Co. manufacturing), adipic dihydrazide (tomb chemical company makes greatly) and KBM-403 (silane coupling agent: SHIN-ETSU HANTOTAI's chemical industry is made) press use level mixing as shown in table 4; use 3 rollers fully to carry out mixing, obtain various resin combinations (embodiment 9, embodiment 10 and comparative example 5).The resin combination that obtains is like this dripped device at 4000 μ m with sealing ²Sectional area in the (60mm * 70mm * 0.7mmt) that drips and be coated on ito glass substrate with the alignment films after milled processed (SUNEVERSE-7492, daily output chemical industrial company make).Then, the liquid crystal that drips on substrate (TN liquid crystal, MLC-11900-080, MERCK ﹠amp; CO., INC. makes), make upper and lower base plate bonding by liquid crystal dripping process (ODF technique), (UV irradiating unit: UVX-01224S1, USHIO INC. makes irradiation ultraviolet radiation, illumination and irradiation time: in the situation that 1000mJ 100mW/cm ²/ 365nm, 10 seconds are in the situation that 50mJ 50mW/cm ²/ 365nm, 1 second) make it to solidify, then carry out the thermofixation of 1 hour in the hot-air oven of 120 ℃, make the test element that is used for the orientation test.In addition, in the situation that illumination is 0mJ, at the bonding rear state that forms ultraviolet not irradiating liquid crystal and sealing agent with shadow mask, carry out the thermofixation of 1 hour in the hot-air oven of 120 ℃, make the test element that is used for the orientation test.

For the panel that obtains, the confirmation of the state of orientation of the liquid crystal when sealing.Confirmation is undertaken by opticmicroscope, and polaroid is clamped test element with the state of Nicol crossed (Network ロスニコ Le), observes by transmission.The microphotograph that shows the state of orientation of the corner part of the liquid crystal under 1000mJ, 50mJ and 0mJ illumination and line part is shown in Fig. 1～Fig. 6.It should be noted that, Fig. 1～Fig. 6 is the scale of vertical 900 μ m * horizontal 1200 μ m.The judgement criteria of the orientation of liquid crystal the time has or not orientation disorder to judge according to sealing.With when sealing orientation disorder be that situation below 50 μ m is counted " zero ", will have the situation of larger orientation disorder to count " * ".Show the result in table 4.It should be noted that, the content in table 4 is weight part.

[table 4]

Coordinate (weight part)	Embodiment 9	Embodiment 10	Comparative example 5
				Compound 1c	100
Compound 3c		100
				Comparative compound 5c			100
Initiator	2	2	2
				Solidifying agent	10	10	10
Weighting agent	10	10	10
				Coupling agent	1	1	1
Orientation (0mJ)	○	○	×
				Orientation (50mJ)	○	○	×
Orientation (1000mJ)	○	○	○
				Stripping property (Ni point)	○	○	×

Initiator: EY resin KR-2 (KSM CO., LTD. makes)

Solidifying agent: adipic dihydrazide (tomb chemical company makes greatly)

Weighting agent: the spherical particulate of silicon-dioxide, SEAHOSTAR KE-C50HG (Japanese catalyst Co. manufacturing)

Coupling agent: 3-glycidoxypropyltrime,hoxysilane, KBM-403 (manufacturing of chemical industrial company of SHIN-ETSU HANTOTAI)

Can confirm according to the result as shown in table 2 and table 4: epoxy resin of the present invention and the solvability of partial esterification epoxy resin in liquid crystal significantly reduce.In addition, according to the result as the orientation test of table 4 and Fig. 1～shown in Figure 6, even show the partial esterification epoxy resin that has used epoxy resin of the present invention in the situation that the UV irradiation dose is disorderly for low irradiation dose does not produce as the liquid crystal aligning that shows bad reason yet, high with the oligopolymer composition availability of liquid crystal sealing agent as the technique of dripping as can be known.On the other hand, in the situation that the composition of usage comparison example 5, produce the approximately liquid crystal aligning disorder of 200 μ m at corner part because of the stripping of solidification compound under the illumination of 50mJ, all produce the liquid crystal aligning disorder of 500～800 μ m because of the stripping of solidification compound at corner part and line part under the illumination of this external 0mJ.

Utilizability on industry

Epoxy resin of the present invention and partial esterification epoxy resin is because solvability, the stripping property to liquid crystal is low, thus can be used as by ultraviolet isoreactivity energy-ray and heat the two and all can keep the raw material of the sealing agent of high reliability.

Claims

1. epoxy resin, it is the epoxy resin by general formula (1), general formula (2) or general formula (3) expression,

In general formula (1), general formula (2) and general formula (3),

Y be carbonatoms 1～4 alkylene base-carbonatoms 6～20 arylidene-carbonatoms 1～4 alkylene base, carbonatoms 1～4 alkylene base-carbonatoms 6～20 arylidene or by-R ⁷-(O-R ⁷) _nThe group of-expression, described by-R ⁷-(O-R ⁷) _nIn the group of-expression, R ⁷Be the alkylene base of carbonatoms 1～4, n is 0 or 1～6 integer,

Each R ²¹Be hydrogen or methyl separately independently of each other,

2. partial esterification epoxy resin, it is the epoxy resin by general formula (4), general formula (5) or general formula (6) expression,

In general formula (4), general formula (5) and general formula (6),

X, Y and R ²¹As described in definition in claim 1,

R ¹¹, R ¹², R ¹³, R ¹⁴, R ¹⁵And R ¹⁶For hydrogen, glycidyl, methyl glycidyl or by-Z-R ⁸The group of expression, described by-Z-R ⁸In the group of expression, Z is 2-hydroxyl trimethylene base or 2-methyl-2-hydroxyl trimethylene base, R ⁸Be acryl or methacryloyl,

Glycidyl and methyl glycidyl, with the ratio of acryl and methacryloyl, that is, glycidyl+methyl glycidyl/acryl+methacryloyl is 10: 90～90: 10.

3. the manufacture method of an epoxy resin, it comprises operation (1A)～(1B),

4. the manufacture method of epoxy resin according to claim 3, it is for the manufacture of the method for the epoxy resin by general formula (1)～general formula (3) expression claimed in claim 1, comprises following operation (2A)～(2B),

Operation (2A): the epoxy compounds by general formula (7a), general formula (8a) or general formula (9a) expression is reacted with the dihydroxy compound that is represented by following general formula (10) under the existence of metal catalyst, thereby obtain the operation by the epoxy addition body of general formula (7b), general formula (8b) or general formula (9b) expression

In general formula (7a), general formula (8a) and general formula (9a), X and R ²¹As described in definition in claim 1,

HO-Y-OH (10)

In general formula (10), Y as in claim 1 definition as described in,

In general formula (7b), general formula (8b) and general formula (9b), X, Y and R ²¹As described in definition in claim 1;

5. the manufacture method of a partial esterification epoxy resin, it comprises operation (1C),

Operation (1C): the operation that the epoxy resin that makes by manufacture method claimed in claim 3 is reacted with (methyl) vinylformic acid under the existence of basic catalyst.

6. the manufacture method of partial esterification epoxy resin according to claim 5, it is for the manufacture of the method for the partial esterification epoxy resin by general formula (4)～general formula (6) expression claimed in claim 2, comprises operation (2C),

Operation (2C): the epoxy resin by general formula (1), general formula (2) or general formula (3) expression that makes by manufacture method claimed in claim 4 is reacted with (methyl) vinylformic acid under the existence of basic catalyst, obtain the operation by the partial esterification epoxy resin of general formula (4)～general formula (6) expression

In general formula (1), general formula (2) and general formula (3),

X, Y, R ¹, R ², R ³, R ⁴, R ⁵, R ⁶, R ²¹As described in definition in claim 1,

7. solidification compound, it contains and is selected from (a) epoxy resin by general formula (1), general formula (2) and general formula (3) expression claimed in claim 1, (b) the partial esterification epoxy resin by general formula (4), general formula (5) and general formula (6) expression claimed in claim 2, (c) epoxy resin that makes by manufacture method claimed in claim 3, and the resin more than a kind in the partial esterification epoxy resin that (d) makes by manufacture method claimed in claim 5.