JP2017203122A - Resin composition and adhesive for electronic components - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition, wherein, since a cured product thereof has a high glass transition temperature and high heat resistance, use of the resin composition for an adhesive can yield a cured product having excellent heat-resistance reliability; and the resin composition also has high adhesive strength and is, therefore, particularly suitable as an adhesive for electronic components.SOLUTION: A resin composition contains a compound (A) having at least one acryloyl group, at least one methacryloyl group, and at least one skeleton represented by the following formula (1), in one molecule (where, Rand Rindependently represent a hydrocarbon group. Rand Rmay be bonded together to form a ring structure).SELECTED DRAWING: Figure 1

Description

  The present invention relates to a resin composition used for an adhesive for electronic components. More specifically, the present invention relates to a resin composition containing a compound having at least one acryloyl group, methacryloyl group, and one or more epoxy groups having a specific structure in one molecule. This resin composition has high reactivity and extremely high heat resistance. Therefore, it is particularly suitable as an adhesive for electronic parts such as semiconductors.

Since the epoxy compound gives a cured product having excellent mechanical properties, water resistance, chemical resistance, heat resistance, electrical properties, etc., as a main raw material of a thermosetting or photocurable resin composition, an adhesive, It is used in a wide range of fields such as paints, laminates, molding materials, casting materials, and resists. The reaction proceeds by a nucleophilic or electrophilic addition reaction with a thermosetting agent, photoacid or base generator, and since the reaction rate is relatively slow, the shrinkage of curing is small, and it is widely applied to adhesives, etc. Has been.
On the other hand, acrylic compounds are often used mainly as radically reactive compounds by light. In this case, there is a problem that the reaction rate is very fast, but the curing shrinkage is large and stress is stored in the structure.
In order to realize a resin composition having both of these characteristics, various compounds having both an epoxy group and an acryloyl group in a molecule such as a partially (meth) acrylated epoxy compound have been proposed (Patent Document 1).
In addition, the acrylic compound has a feature that the reaction is very fast as compared with the methacrylic compound, and has a disadvantage that the glass transition temperature (Tg) is low and the heat resistance is inferior. In order to solve this problem, a resin composition using a compound in which an acryloyl group, a methacryloyl group, and a glycidyl group coexist in one molecule has been proposed (Patent Document 3).

However, these compounds still have a problem that heat resistance is not sufficient, and improvement is demanded.
Moreover, generally improving heat resistance also means raising the crosslink density, and there is a problem that the adhesive strength is lowered.

JP-A 61-197622 Japanese Patent Publication No. 6-89109 JP 2008-88167 A

In view of the above situation, the present invention proposes a resin composition using a compound in which an epoxy group, an acryloyl group, and a methacryloyl group having a specific structure in one molecule coexist.
Since this resin composition has both properties such as reactivity and adhesive strength and has a very high heat resistance, it is suitable for use as an adhesive for electronic parts.

As a result of intensive studies, the present inventors have found that a cured product containing a compound having a specific structure has extremely high heat resistance and can achieve both adhesive strength and can provide an extremely excellent resin composition. It was discovered that the present invention was achieved.
That is, the present invention relates to the following 1) to 11). In the present specification, “(meth) acryl” means “acryl” and / or “methacryl”, and similarly, “(meth) acryloyl” means “acryloyl” and / or “methacryloyl”.
In this specification, the superscript RTM means a registered trademark.

（式（１）中、Ｒ^１及びＲ^２は、それぞれ独立に、炭化水素基を表す。また、Ｒ^１とＲ^２は、結合することで環構造を形成していても良い。）
２）
上記（Ａ）が、分子内に、さらにヒドロキシ基を１つ以上有する化合物である上記１）に記載の樹脂組成物、
３）
上記（Ａ）が、分子内に、さらにエステル結合を４つ以上有する化合物である上記１）又は２）に記載の樹脂組成物、
４）
さらに、（ｂ）ラジカル重合開始剤を含有する上記１）乃至３）のいずれか一項に記載の樹脂組成物、
５）
さらに、（ｃ）無機フィラーを含有する上記１）乃至４）のいずれか一項に記載の樹脂組成物、
６）
さらに、（ｄ）シランカップリング剤を含有する上記１）乃至５）のいずれか一項に記載の樹脂組成物、
７）
上記１）乃至６）のいずれか一項に記載の樹脂組成物を用いた電子部品用接着剤、
８）
上記７）に記載の電子部品用接着剤を硬化して得られる硬化物で接着された電子部品、
９）
上記１）乃至６）のいずれか一項に記載の樹脂組成物を用いた液晶表示セル用接着剤、
１０）
上記１）乃至６）のいずれか一項に記載の樹脂組成物を用いた液晶シール剤、
１１）
上記９）又は１０）に記載の液晶表示セル用接着剤又は液晶シール剤を用いて接着された液晶表示セル、に関する。 That is, the present invention
1)
(A) A resin composition containing a compound having one or more acryloyl groups, methacryloyl groups, and a skeleton represented by the following formula (1) in one molecule,

(In Formula (1), R ¹ and R ² each independently represents a hydrocarbon group. R ¹ and R ² may be bonded to form a ring structure.)
2)
The resin composition according to 1) above, wherein (A) is a compound further having one or more hydroxy groups in the molecule,
3)
The resin composition according to 1) or 2) above, wherein (A) is a compound further having four or more ester bonds in the molecule;
4)
Furthermore, (b) the resin composition according to any one of 1) to 3) above containing a radical polymerization initiator,
5)
Furthermore, (c) the resin composition according to any one of 1) to 4) above, which contains an inorganic filler,
6)
Furthermore, (d) the resin composition according to any one of 1) to 5) containing a silane coupling agent,
7)
An adhesive for electronic parts using the resin composition according to any one of 1) to 6) above,
8)
An electronic component bonded with a cured product obtained by curing the adhesive for electronic components according to 7),
9)
An adhesive for liquid crystal display cells using the resin composition according to any one of 1) to 6) above;
10)
A liquid crystal sealing agent using the resin composition according to any one of 1) to 6) above;
11)
The present invention relates to a liquid crystal display cell bonded using the liquid crystal display cell adhesive or liquid crystal sealant described in 9) or 10) above.

  Since the cured composition has a high glass transition temperature and high heat resistance, the resin composition of the present invention can realize a cured product having excellent heat reliability when used as an adhesive. In general, the improvement in heat resistance is also an increase in the crosslink density, and there is concern about a decrease in the adhesive strength, but the resin composition of the present invention can also realize a high adhesive strength.

These are the figures shown about the measuring method of adhesive strength. A liquid crystal sealant to which a gap agent is added is drawn on a glass base piece coated with an alignment film of about 20 mm × 30 mm using a dispenser. At this time, the coating amount is set so that the line width is 0.7 mm, and drawing is performed in the form as shown in FIG. Thereafter, a glass substrate coated with an alignment film of about 10 mm × 25 mm is bonded as a counter substrate, photocured by UV irradiation of 3000 mJ / cm ² , and further cured by heating in a 120 ° C. oven for 1 hour. Make a piece. The test piece obtained is peeled off from below with a bond tester (SS-30WD: manufactured by Seishin Shoji Co., Ltd.).

[(A) Compound having one or more acryloyl group, methacryloyl group, and skeleton represented by the following formula (1) in one molecule]
The present invention contains (meth) acrylic compounds each having one or more acryloyl group, methacryloyl group, and skeleton represented by the above formula (1) in one molecule.

In said formula (1), R < ¹ > and R < ² > represents a hydrocarbon group each independently.
The hydrocarbon group may be a saturated or unsaturated aliphatic group, an aromatic group, a chain group, or a cyclic group. Further, it may contain a hetero atom.
Moreover, you may have a substituent further on the said hydrocarbon group. Examples of the substituent that may be present include a halogen atom; a cyano group; a hydroxy group; a carboxy group; a sulfo group; a sulfamoyl group; a (C1-C4) alkoxy group; a hydroxy group, a (C1-C4) alkoxy group, and a sulfo group. And (C1-C4) alkoxy group substituted with at least one group selected from the group consisting of carboxy group; N-alkylaminosulfonyl group; N-phenylaminosulfonyl group; phospho group; nitro group; A ureido group; an (C1-C6) alkyl group substituted with an acylamino group substituted with at least one group selected from the group consisting of an acylamino group, a (C1-C4) alkoxy group, a sulfo group, and a carboxy group; Etc.

R ¹ and R ² may be bonded to form a ring structure, and include, for example, structures such as those shown by the following formulas (2), (3), and (4).

The R ¹ and ^{R 2,} preferably a hydrocarbon group having 1 to 20 carbon atoms, more preferably a hydrocarbon group having 1 to 10 carbon atoms.
A case where R ¹ and R ² are bonded to form a cyclic structure is a particularly preferable embodiment.

  The component (A) preferably has one or more hydroxy groups in the molecule. Further, it is particularly preferable to have 4 or more ester bonds.

The compound can be obtained, for example, through the steps [1] to [3] below.
[1] A step of reacting a corresponding carbon-carbon double bond-containing carboxylic anhydride compound (a-1) with a (meth) acryloyl group-containing alcohol (a-2) to convert it into an ester.
[2] A step of reacting the compound obtained in [1] with a (meth) acryloyl group-containing epoxy compound (a-3).
[3] A step of oxidizing a carbon-carbon double bond to convert it into an epoxy group.

（式（５）中、Ｒ^３乃至Ｒ^７はそれぞれ独立に水素原子また炭素数１〜３の炭化水素基を表す。ｎ及びｍは、０〜６の整数を表す。） Each process will be described in the following order.
[1]
In this step, first, the corresponding carbon-carbon double bond-containing carboxylic acid anhydride (a-1) and (meth) acryloyl group-containing alcohol (a-2) are stirred at a temperature of about 50 to 120 ° C. for 5 to 10 hours. To obtain an ester of the corresponding carboxylic acid compound.
(A-1) The carbon-carbon double bond-containing carboxylic anhydride compound is not particularly limited as long as it is a carboxylic anhydride containing a carbon-carbon double bond, but itaconic anhydride, maleic acid. Anhydride, tetrahydrophthalic anhydride, 3-methyl-4-cyclohexene-1,2-dicarboxylic acid anhydride, 4-methyl-4-cyclohexene-1,2-dicarboxylic acid anhydride, nadic acid anhydride, bicyclo [2. 2.2] Oct-5-ene-2,3-dicarboxylic anhydride, bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, alkenyl succinic anhydride represented by the following formula (5), and the like. Among these, tetrahydrophthalic anhydride, 3-methyl-4-cyclohexene-1,2-dicarboxylic anhydride, 4-methyl-4-cyclohexene-1,2-dicarboxylic acid are used because of the ease of oxidation of the carbon-carbon double bond. Acid anhydride, nadic acid anhydride, bicyclo [2.2.2] oct-5-ene-2,3-dicarboxylic acid anhydride, bicyclo [2.2.2] oct-7-ene-2,3 5,6-tetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, an alkenyl succinic acid represented by the following formula (2) Of the acid anhydrides, those in which n and m are 1 to 6 are preferable. From the reactivity of the epoxy group obtained by oxidation, tetrahydrophthalic anhydride, 3-methyl-4-cyclohexene-1,2-di Carboxylic anhydride, 4-methyl-4-cyclohexene-1,2-dicarboxylic anhydride, bicyclo [2.2.2] oct-5-ene-2,3-dicarboxylic anhydride, bicyclo [2.2. 2] Oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid Among the alkenyl succinic anhydrides represented by the following formula (5), those in which R ⁴ and R ⁶ are hydrogen atoms and n and m are 1 to 6 are particularly preferable. From the viewpoint of availability, tetrahydrophthalic acid An anhydride, octenyl succinic anhydride, is most preferred.

(In Formula (5), R ^{3 to} R ⁷ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms. N and m represent an integer of 0 to 6)

  (A-2) The (meth) acryloyl group-containing alcohol is not particularly limited as long as it is a linear or branched aliphatic alcohol having 4 to 16 carbon atoms and containing a (meth) acryloyl group. Considering the ease, hydroxyethyl (meth) acrylate or 2-hydroxypropyl (meth) acrylate is preferable, and hydroxyethyl (meth) acrylate is particularly preferable because of high reactivity. The amount of the (meth) acryloyl group-containing alcohol used is preferably 0.8 to 1.2 mol, more preferably 0.9 to 1.1, based on 1 mol of the carboxylic anhydride compound. In the case of mol, the case of 0.95 to 1.05 mol is most preferable.

  In this step, a catalyst may be used. The catalyst to be used is not particularly limited as long as it accelerates the reaction, but an ammonium salt, an amine compound or a phosphine compound is preferable, and an ammonium salt or an amine compound is particularly preferable because of easy removal.

  The reaction temperature is 50 to 120 ° C., and the reaction time is preferably about 5 to 20 hours. The reaction can be followed by gel permeation chromatography (GPC) or the like. The reaction solution containing the target ester may be used as it is for the subsequent reaction with the (meth) acryloyl group-containing epoxy compound, and may be separated from the reaction solution by separation operations such as extraction, concentration, and crystallization. It may be separated and purified and used for the next reaction.

（式（３）中、Ｒ^８及びＲ^９は、それぞれ独立に水素原子又は炭素数１〜３の炭化水素基を表し、Ｒ^１０及びＲ^１１はそれぞれ独立に水素原子又は炭素数１〜２０の炭化水素基を表し、Ｒ^８及びＲ^９の少なくともどちらかは炭素−炭素二重結合を必ず含有する。また、Ｒ^１０とＲ^１１は結合して環構造を形成してもよい。ｌは０〜６の整数を表す。）
上記式（６）において、Ｒ^１０、Ｒ^１１が結合して環構造を形成している場合とは、例えば下記式（７）〜（９）で表される構造を意味する。

The compound obtained by this step is a compound represented by the following formula (6).

(In Formula (3), R ⁸ and R ⁹ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, and R ¹⁰ and R ¹¹ each independently represent a hydrogen atom or a carbon atom having 1 to 20 carbon atoms. Represents a hydrocarbon group, and at least one of R ⁸ and R ⁹ necessarily contains a carbon-carbon double bond, and R ¹⁰ and R ¹¹ may combine to form a ring structure. Represents an integer of ~ 6)
In the above formula (6), the case where R ¹⁰ and R ¹¹ are combined to form a ring structure means, for example, a structure represented by the following formulas (7) to (9).

[2]
In this step, following the step of synthesizing the ester of the carboxylic anhydride compound, after mixing the (meth) acryloyl group-containing epoxy compound (a-3) at 0 to 80 ° C. with the carboxy group of the carboxylic acid compound, The reaction is carried out at 50 to 120 ° C. for 1 to 20 hours.

  This step does not necessarily require a solvent, but may be performed using an organic solvent. Specific examples of the organic solvent that can be used include alkanes such as hexane, cyclohexane and heptane, and aromatic hydrocarbon compounds such as toluene and xylene. In some cases, ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone and anone, ethers such as diethyl ether, tetrahydrofuran and dioxane, ester compounds such as ethyl acetate, butyl acetate and methyl formate, and nitriles such as acetonitrile Compounds and the like can also be used.

（式（１０）及び（１１）中、Ｒ^１２は水素原子又はメチル基を表す。） This step is performed by, for example, dissolving the compound represented by the formula (6) in the organic solvent and adding a (meth) acryloyl group-containing epoxy compound at 0 ° C. to 80 ° C. After the addition, the compound represented by the following formula (10) or (11) can be obtained by heating from 50 ° C. to 120 ° C. and reacting for 1 to 20 hours. In formulas (10) and (11), R ^{8 to} R ¹¹ and l have the same meaning as in formula (6).

(In the formulas (10) and (11), R ¹² represents a hydrogen atom or a methyl group.)

  (A-3) The (meth) acryloyl group-containing epoxy compound is not particularly limited as long as it is an epoxy compound having 6 to 18 carbon atoms and containing a (meth) acryloyl group. Considering this, glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, and 3,4-epoxycyclohexylmethyl (meth) acrylate are preferable, and glycidyl (meth) acrylate is most preferable because of easy control of the reaction. The amount of the (meth) acryloyl group-containing epoxy compound used is preferably 0.8 to 1.2 mol, more preferably 0.9 to 1.1 mol, based on 1 mol of the ester of the carboxylic anhydride compound. .95 to 1.05 mole is most preferred.

  In this step, a catalyst may be used. The catalyst to be used is not particularly limited as long as it accelerates the reaction, but an ammonium salt, an amine compound or a phosphine compound is preferable, and an ammonium salt or an amine compound is particularly preferable because of easy removal. The same catalyst as in the previous step may be used, or a different catalyst may be used.

  The end point of the reaction can be confirmed by gel permeation chromatography (GPC), epoxy equivalent measurement or the like. The reaction solution containing the compound represented by the above formula (10) or (11) may be used as it is in the next reaction, which is an oxidation reaction of a carbon-carbon double bond, and extraction, concentration, crystallization, etc. In this separation operation, it may be isolated and purified from the reaction solution and used in the next reaction.

[3]
It can be set as the acrylic compound of this invention by oxidizing the compound represented by the said Formula (10) or (11). Examples of the oxidation method include, but are not limited to, a method of oxidizing with a peracid such as peracetic acid, a method of oxidizing with a hydrogen peroxide solution, and a method of oxidizing with air (oxygen).
Specific examples of the epoxidation method using peracid include the method described in Japanese Patent Application Laid-Open No. 2006-52187. Examples of peracids that can be used include formic acid, acetic acid, propionic acid, maleic acid, benzoic acid, m-chlorobenzoic acid, organic acids such as phthalic acid, and acid anhydrides thereof. Among these, it is preferable to use formic acid, acetic acid, and phthalic anhydride from the viewpoint of the efficiency of reacting with hydrogen peroxide to produce an organic peracid, the reaction temperature, the ease of operation, and the economy. Formic acid or acetic acid is more preferably used from the viewpoint of simplicity of reaction operation.
Various methods can be applied to the method of epoxidation with hydrogen peroxide solution. Specifically, Japanese Patent Application Laid-Open No. 59-108793, Japanese Patent Application Laid-Open No. 62-234550, Japanese Patent Application Laid-Open No. No. 5-291919, Japanese Patent Application Laid-Open No. 11-349579, Japanese Patent Publication No. 1-33341, Japanese Patent Publication No. 2001-17864, Japanese Patent Publication No. 3-57102, etc. Various methods can be applied.
In addition, Non-Patent Document 1 (James V. Crivello and Ramesh Narayan, Novel Epoxynorbornane Monomers. 1. Synthesis and Characterization, Macromolecules 1996, 29, pp. 433-438) can also be described. . Specifically, the olefin group can be obtained by epoxidation using oxone.

Hereinafter, a particularly preferable method is exemplified as the step [3].
First, the compound represented by the above formula (10) or (11), which is a precursor of the acrylic compound of the present invention, a polyacid, and a quaternary ammonium salt are reacted in two layers of an organic solvent and hydrogen peroxide solution. .

The polyacid used in the present invention is not particularly limited as long as it is a compound having a polyacid structure, but polyacids containing tungsten or molybdenum are preferred, polyacids containing tungsten are more preferred, and tungstates are particularly preferred.
Specific polyacids and polyacid salts included in the polyacids include tungsten acids selected from tungstic acid, 12-tungstophosphoric acid, 12-tungstoboric acid, 18-tungstophosphoric acid, 12-tungstosilicic acid, and the like. Examples thereof include molybdenum-based acids selected from molybdic acid and phosphomolybdic acid, and salts thereof.
Examples of the counter cation of these salts include ammonium ions, alkaline earth metal ions, and alkali metal ions.
Specific examples include alkaline earth metal ions such as calcium ions and magnesium ions, alkali metal ions such as sodium, potassium and cesium, but are not limited thereto. Particularly preferred counter cations are sodium ion, potassium ion, calcium ion and ammonium ion.

  Polyacids are used in terms of metal elements (tungstenic acid) with respect to 1 mol (functional group equivalent) of a carbon-carbon double bond other than the (meth) acryloyl group in the compound represented by the above formula (10) or (11). In the case of tungsten atom, the number of moles of molybdenum atom in the case of molybdic acid is 1.0 to 20 mmol, preferably 2.0 to 20 mmol, more preferably 2.5 to 10 mmol.

As the quaternary ammonium salt, a quaternary ammonium salt having a total carbon number of 10 or more, preferably 25 to 100, more preferably 25 to 55 can be preferably used, and in particular, the alkyl chain is preferably an aliphatic chain. .
Specifically, tridecanylmethylammonium salt, dilauryldimethylammonium salt, trioctylmethylammonium salt, trialkylmethyl (a mixed type of a compound in which the alkyl group is an octyl group and a compound in which the decanyl group is a compound) ammonium salt, trihexa Examples include decylmethylammonium salt, trimethylstearylammonium salt, tetrapentylammonium salt, cetyltrimethylammonium salt, benzyltributylammonium salt, dicetyldimethylammonium salt, tricetylmethylammonium salt, and di-cured tallow alkyldimethylammonium salt. It is not limited to.
The anion species of these salts use carboxylate ions. As the carboxylate ion, acetate ion, carbonate ion and formate ion are preferable. In particular, acetate ion is preferred.
If the quaternary ammonium salt has more than 100 carbon atoms, the hydrophobicity may become too strong and the solubility in the organic layer may deteriorate. On the other hand, when the carbon number of the quaternary ammonium salt is less than 10, the hydrophilicity becomes strong, and the compatibility with the organic layer may be similarly deteriorated.
In general, halogen remains in the quaternary ammonium salt. Especially in this invention, it is 1 mass% or less, More preferably, it is 1000 ppm or less, More preferably, it is 700 ppm or less. When the total halogen amount exceeds 1% by mass, a large amount of halogen remains in the product, which is not preferable.
The amount of tungstic acid and quaternary ammonium carboxylate used is preferably 0.01 to 0.8 times equivalent, or 1.1 to 10 times equivalent to the valence of the tungstic acid used. More preferably, it is 0.05 to 0.7 times equivalent, or 1.2 to 6.0 times equivalent, and more preferably 0.05 to 0.5 times equivalent, or 1.3 to 4.5 times equivalent. is there.
For example, since tungstic acid is divalent with H2WO4, the quaternary ammonium carboxylate is preferably in the range of 0.02 to 1.6 mol or 2.2 to 20 mol with respect to 1 mol of tungstic acid. . In addition, since it is trivalent in the case of tungstophosphoric acid, it is similarly 0.03 to 2.4 mol, or 3.3 to 30 mol, and in the case of silicotungstic acid, it is tetravalent, so 0.04 to 3.2. Mole or 4.4 to 40 mol is preferred.
When the amount of the quaternary ammonium carboxylate is lower than 1.1 times equivalent of the valence of tungstic acids, the epoxidation reaction is difficult to proceed (in some cases, the reaction proceeds faster), and a by-product is produced. The problem is that things are easy to make. When the amount is more than 10 times the equivalent, not only is the treatment of the excess quaternary ammonium carboxylate difficult, but it also serves to suppress the reaction, which is not preferable.

  A commercially available product may be used as the quaternary ammonium salt having a carboxylate ion as an anion. For example, the raw material quaternary ammonium salt is treated with a metal hydroxide or an ion exchange resin to be converted into a quaternary ammonium hydroxide. Further, it may be produced by a method of reacting with various carboxylic acids. Examples of the raw material quaternary ammonium salt include quaternary ammonium halides and various metal salts. If there is a suitable quaternary ammonium hydroxide, it may be used.

Any buffer can be used, but it is preferable to use an aqueous phosphate solution in this reaction. The pH is preferably adjusted between pH 4 and 10, more preferably pH 5-9. When the pH is less than 4, the hydrolysis reaction and polymerization reaction of the epoxy group easily proceed. Moreover, when pH10 is exceeded, reaction will become extremely slow and the problem that reaction time is too long will arise.
In particular, in the present invention, when the tungstic acid as a catalyst is dissolved, the pH is preferably adjusted to be between 5 and 9.
For example, in the case of a phosphoric acid-phosphate aqueous solution which is a preferable buffer solution, a buffer solution is used in an amount of 0.1 to 10 mol% of phosphoric acid (or phosphorous such as sodium dihydrogen phosphate) with respect to hydrogen peroxide. Acid salt) and adjusting the pH with a basic compound (for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, etc.). Here, it is preferable that the pH is added so that the above-mentioned pH is obtained when hydrogen peroxide is added. Moreover, it is also possible to adjust using sodium dihydrogen phosphate or disodium hydrogen phosphate. The preferred phosphate concentration is 0.1 to 60% by weight, preferably 5 to 45% by weight.
In this reaction, a buffer such as disodium hydrogen phosphate, sodium dihydrogen phosphate, sodium phosphate or sodium tripolyphosphate (or its hydrate) is not used without adjusting the pH. It may be added directly. In the sense of simplifying the process, there is no troublesome pH adjustment, and direct addition is particularly preferred. The amount of phosphate used in this case is usually 0.1 to 5 mol% equivalent, preferably 0.2 to 4 mol% equivalent, more preferably 0.3 to 3 mol% equivalent to hydrogen peroxide. It is. In this case, if the amount exceeds 5 mol% equivalent to hydrogen peroxide, pH adjustment is required. If the amount is less than 0.1 mol% equivalent, the resulting epoxy resin hydrolyzate tends to proceed or the reaction is slow. The bad effect of becoming.

  This reaction is epoxidized using hydrogen peroxide. As the hydrogen peroxide used in this reaction, an aqueous solution having a hydrogen peroxide concentration of 10 to 40% by weight is preferable because of easy handling. When the concentration exceeds 40% by weight, handling becomes difficult and the decomposition reaction of the produced epoxy resin also tends to proceed.

  This reaction may use an organic solvent. The amount of the organic solvent to be used is 0.3 to 10 by mass ratio, preferably 0.3 to 5, with respect to the compound 1 represented by the above formula (10) or (11) as the reaction substrate. More preferably, it is 0.5-2.5. When the mass ratio exceeds 10, it is not preferable because the progress of the reaction becomes extremely slow. Specific examples of organic solvents that can be used include alkanes such as hexane, cyclohexane and heptane, aromatic hydrocarbon compounds such as toluene and xylene, and alcohols such as methanol, ethanol, isopropanol, butanol, hexanol and cyclohexanol. It is done. In some cases, ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone and anone, ethers such as diethyl ether, tetrahydrofuran and dioxane, ester compounds such as ethyl acetate, butyl acetate and methyl formate, and nitriles such as acetonitrile Compounds and the like can also be used.

  As a specific reaction operation method, for example, when the reaction is performed in a batch-type reaction kettle, the compound represented by the above formula (10) or (11), hydrogen peroxide (aqueous solution), polyacids (catalyst), Add buffer, quaternary ammonium salt and organic solvent and stir in two layers. There is no specific designation for the stirring speed. Since heat is often generated when hydrogen peroxide is added, a method of gradually adding hydrogen peroxide after each component may be added.

  Although reaction temperature is not specifically limited, 0-90 degreeC is preferable, More preferably, it is 0-75 degreeC, Especially 15 to 60 degreeC is preferable. When the reaction temperature is too high, the hydrolysis reaction tends to proceed, and when the reaction temperature is low, the reaction rate becomes extremely slow.

  Although the reaction time depends on the reaction temperature, the amount of catalyst, etc., from the viewpoint of industrial production, a long-time reaction is not preferable because it consumes a large amount of energy. A preferred range is 1 to 48 hours, preferably 3 to 36 hours.

  After completion of the reaction, quenching of excess hydrogen peroxide is performed. The quenching treatment is preferably performed using a basic compound. It is also preferable to use a reducing agent and a basic compound in combination. As a preferred treatment method, there is a method of quenching the remaining hydrogen peroxide using a reducing agent after neutralization adjustment to pH 6 to 12 with a basic compound. If the pH is less than 6, the heat generated during the reduction of excess hydrogen peroxide is large, which may cause decomposition products.

  Examples of the reducing agent include sodium sulfite, sodium thiosulfate, hydrazine, oxalic acid, vitamin C and the like. As the amount of the reducing agent used, excess hydrogen peroxide is usually 0.01 to 20 times mol, more preferably 0.05 to 10 times mol, still more preferably 0.05 to 3 times mol, based on the number of moles. is there.

Basic compounds include metal hydroxides such as sodium hydroxide, potassium hydroxide, magnesium hydroxide and calcium hydroxide, metal carbonates such as sodium carbonate and potassium carbonate, phosphorus such as sodium phosphate and sodium hydrogen phosphate. Examples thereof include basic solids such as acid salts, ion exchange resins, and alumina.
The amount used is water or organic solvents (for example, aromatic hydrocarbons such as toluene and xylene, ketones such as methyl isobutyl ketone and methyl ethyl ketone, hydrocarbons such as cyclohexane, heptane and octane, methanol, ethanol, isopropyl alcohol, etc. The amount used is usually 0.01 to 20 times mol, more preferably 0.05 to 10 times the number of moles of excess hydrogen peroxide. Mol, more preferably 0.05 to 3 times mol. These may be added as water or a solution of the above-mentioned organic solvent, or may be added alone.
When a solid base that does not dissolve in water or an organic solvent is used, it is preferable to use an amount of 1 to 1000 times in terms of mass ratio with respect to the amount of hydrogen peroxide remaining in the system. More preferably, it is 10-500 times, More preferably, it is 10-300 times. In the case of using a solid base that does not dissolve in water or an organic solvent, the treatment may be carried out after separation of an aqueous layer and an organic layer described later.

After the hydrogen peroxide quench (or before quenching), if the organic layer and the aqueous layer are not separated, or if no organic solvent is used, the above-mentioned organic solvent is added and the operation is performed. The reaction product is extracted from the layer. The organic solvent used in this case is 0.5 to 10 times, preferably 0.5 to 5 times in weight ratio to the compound represented by the above formula (10) or (11) as a raw material. This operation is repeated several times as necessary, and then the organic layer is separated. If necessary, the organic layer is washed with water and purified.
The obtained organic layer may be an ion exchange resin or a metal oxide (especially silica gel or alumina is preferred), activated carbon (especially a chemical activated carbon is particularly preferred), or a composite metal salt (especially a basic composite metal salt). Are preferably removed), a mineral with a viscosity (especially, a layered viscosity mineral such as montmorillonite is preferred), and after washing with water and filtration, the solvent is distilled off to obtain the desired epoxy compound. In some cases, it may be further purified by column chromatography or distillation.

The resin composition of the present invention may contain a curable compound in addition to the component (A). Examples of the curable compound include epoxy compounds, (meth) acrylated epoxy compounds, (meth) acrylate monomers, (meth) acrylate oligomers, and partial (meth) acrylated epoxy compounds. . In addition, in the case of adhesive use, in addition to the acrylic compound of the present invention, among the above, one or two selected from an epoxy compound, a (meth) acrylated epoxy compound and a partial (meth) acrylated epoxy compound The case containing more than seeds is particularly preferred. Examples thereof include an epoxy compound, a mixture of an epoxy compound and a (meth) acrylated epoxy compound, a (meth) acrylated epoxy compound, and a partial (meth) acrylated epoxy compound. In particular, when used as an adhesive for liquid crystal display cells, when used in a portion in direct contact with liquid crystal, those having low contamination and solubility in liquid crystal are preferred. Examples of suitable epoxy compounds include bisphenol A Type epoxy compound, bisphenol F type epoxy compound, bisphenol S type epoxy compound, phenol novolac type epoxy compound, cresol novolac type epoxy compound, bisphenol A novolak type epoxy compound, bisphenol F novolak type epoxy compound, alicyclic epoxy compound, aliphatic Chain epoxy compound, glycidyl ester type epoxy compound, glycidyl amine type epoxy compound, hydantoin type epoxy compound, isocyanurate type epoxy compound, phenol novo having triphenolmethane skeleton -Type epoxy compounds, diglycidyl etherified products of bifunctional phenols, diglycidyl etherified products of bifunctional alcohols, and their halides, hydrogenated products, etc., but are not limited thereto. Absent. The (meth) acryloylated epoxy compound and the partially (meth) acryloylated epoxy compound can be obtained by a known reaction of an epoxy compound and (meth) acrylic acid. For example, a predetermined equivalent ratio of (meth) acrylic acid to a catalyst (for example, benzyldimethylamine, triethylamine, benzyltrimethylammonium chloride, triphenylphosphine, triphenylstibine, etc.) and a polymerization inhibitor (for example, methoquinone, Hydroquinone, methylhydroquinone, phenothiazine, dibutylhydroxytoluene, etc.) are added, and the esterification reaction is performed at 80 to 110 ° C., for example. Although it does not specifically limit as an epoxy compound used as a raw material, A bifunctional or more epoxy compound is preferable, for example, a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a bisphenol S type epoxy compound, a phenol novolac type epoxy compound , Cresol novolac type epoxy compound, bisphenol A novolak type epoxy compound, bisphenol F novolak type epoxy compound, alicyclic epoxy compound, aliphatic chain epoxy compound, glycidyl ester type epoxy compound, glycidyl amine type epoxy compound, hydantoin type epoxy compound , Isocyanurate type epoxy compounds, phenol novolac type epoxy compounds having a triphenolmethane skeleton, and other difunctional phenolic diglycidyl Ether compound, bi-functional alcohol diglycidyl ethers of, and their halides, and the like hydrogenated product. Of these, bisphenol type epoxy resin and novolac type epoxy resin are more preferable from the viewpoint of liquid crystal contamination. Further, the ratio of the epoxy group to the (meth) acryloyl group is not limited, and is appropriately selected from the viewpoint of process compatibility and liquid crystal contamination.

  In the resin composition of the present invention, a monomer and / or oligomer of (meth) acrylic acid ester may be used as necessary. Examples of such a monomer or oligomer include a reaction product of dipentaerythritol and (meth) acrylic acid, a reaction product of dipentaerythritol / caprolactone and (meth) acrylic acid, and the like. Absent.

  The resin composition of the present invention is suitable for use as an adhesive. In this case, the content of the component (A) is preferably 1 to 100 parts by mass in 100 parts by mass of the curable compound. Further, it is more preferably 10 to 90 parts by mass, and particularly preferably 20 to 80 parts by mass.

[(B) Radical polymerization initiator]
The resin composition of the present invention may contain (b) a radical polymerization initiator.
The radical polymerization initiator (b) that may be contained in the resin composition of the present invention is not particularly limited as long as it is a compound that generates a radical and initiates a chain polymerization reaction, but is a photo radical polymerization initiator or a thermal radical polymerization. Initiators are preferred, and either one may be used or both may be used together.

  The photo-radical polymerization initiator that may be contained in the resin composition of the present invention is not particularly limited as long as it is a compound that generates radicals by irradiation of energy rays such as ultraviolet rays and visible light and initiates a chain polymerization reaction. For example, benzyldimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, diethylthioxanthone, benzophenone, 2-ethylanthraquinone, 2-hydroxy-2-methylpropiophenone, 2-methyl- [4- (methylthio) phenyl] -2 -Morpholino-1-propane, 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like. In addition, when used as an adhesive for liquid crystal display cells as described below, and when used in a portion that is in direct contact with the liquid crystal, the one having a (meth) acryl group in the molecule should be used from the viewpoint of liquid crystal contamination. For example, a reaction product of 2-methacryloyloxyethyl isocyanate and 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2methyl-1-propan-1-one is preferably used. . This compound can be obtained by the method described in International Publication WO2006 / 027982. Content of this photoinitiator is 0.1-20 mass% normally, when the whole resin composition of this invention is 100 mass%, Preferably it is 1-15 mass%.

  The thermal radical polymerization initiator that may be contained in the resin composition of the present invention is not particularly limited as long as it is a compound that generates radicals by heating and initiates a chain polymerization reaction, but is not limited to organic peroxides, azo compounds, and benzoin. Compound, benzoin ether compound, acetophenone compound, benzopinacol and the like can be mentioned, and benzopinacol is preferably used. For example, examples of the organic peroxide include Kayamek A, Kayamek M, Kayamek R, Kayamek L, Kayamek LH, Kayamek SP-30C, Perdox CH-50L, Perdox BC-FF, Kadox B-40ES, Perdox 14, Trigonox 22- 70E, Trigonox 23-C70, Trigonox 121, Trigonox 121-50E, Trigonox 121-LS50E, Trigonox 21-LS50E, Trigonox 42, Trigonox 42LS, Kayaester P-70, Kayaester TMPO-70, Kayaester CND-C70, Kaya Ester O, Kaya Este O-50E, Kaya Este AN, Kaya Butyl B, Perdox 16, Kaya Carbon BIC-75, Kaya Caro AIC-75 (Kayaku Akzo Corporation Made by company), Permec N, Permec H, Permec S, Permec F, Permec D, Permec G, Perhexa H, Perhexa HC, Perhexa TMH, Perhexa C, Perhexa V, Perhexa 22, Perhexa MC, Percure AH, Percure AL, Percure HB, perbutyl H, perbutyl C, perbutyl ND, perbutyl L, park mill H, park mill D, parroyl IB, parroyl IPP, perocta ND (manufactured by NOF Corporation) and the like are commercially available. Moreover, as an azo compound, VA-044, V-070, VPE-0201, VSP-1001, etc. (made by Wako Pure Chemical Industries Ltd.) etc. are available as a commercial item. The content of the thermal radical polymerization initiator is preferably 0.0001 to 10 parts by mass, more preferably 0.0005 to 7 parts by mass, when the total amount of the resin composition of the present invention is 100 parts by mass. Part, and 0.001 to 3 parts by mass is particularly preferable.

[(C) Inorganic filler]
The resin composition of the present invention may contain (c) an inorganic filler.
Examples of the inorganic filler (component (c)) that may be contained in the resin composition of the present invention include fused silica, crystalline silica, silicon carbide, silicon nitride, boron nitride, calcium carbonate, magnesium carbonate, barium sulfate, calcium sulfate, Mica, talc, clay, alumina, magnesium oxide, zirconium oxide, aluminum hydroxide, magnesium hydroxide, calcium silicate, aluminum silicate, lithium aluminum silicate, zirconium silicate, barium titanate, glass fiber, carbon fiber, molybdenum disulfide, asbestos Preferably fused silica, crystalline silica, silicon nitride, boron nitride, calcium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, alumina, aluminum hydroxide, calcium silicate, aluminum silicate, Preferably fused silica, crystalline silica, alumina, talc. These inorganic fillers may be used in combination of two or more. In particular, when used as an adhesive for the following liquid crystal display cell, if the average particle size is too large, it becomes a cause of defects such as inability to form a gap when the upper and lower glass substrates are bonded together when manufacturing a narrow gap liquid crystal display cell. Therefore, 3 μm or less is appropriate, and preferably 2 μm or less. The particle size was measured with a laser diffraction / scattering type particle size distribution analyzer (dry type) (manufactured by Seishin Enterprise Co., Ltd .; LMS-30).

  Content in the resin composition of the said inorganic filler is 1-60 mass parts normally, when the whole resin composition of this invention is 100 mass parts, Preferably it is 5-50 mass parts. When there is too little content of an inorganic filler, since adhesive strength falls and moisture resistance reliability is also inferior, the fall of the adhesive strength after moisture absorption may also become large. Moreover, when there is too much content of an inorganic filler, since there is too much filler content, when it uses as an adhesive agent for liquid crystal display cells, it may become impossible to form the gap of a cell.

[(D) Silane coupling agent]
The resin composition of the present invention may contain (d) a silane coupling agent.
Examples of the silane coupling agent (component (d)) that the resin composition of the present invention may contain include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 3-glycidoxy. Propylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, N- (2- (vinylbenzylamino) ethyl) 3- Aminopropyltrimethoxysilane hydrochloride, 3-methyl Methacryloxy propyl trimethoxy silane, 3-chloropropyl methyl dimethoxy silane, 3-chloropropyl trimethoxy silane, and the like. The content of the silane coupling agent in the resin composition is preferably 0.01 to 3 parts by mass when the entire resin composition of the present invention is 100 parts by mass.

[(E) Thermosetting agent]
The resin composition of the present invention may contain (e) a thermosetting agent.
The thermosetting agent (e) that may be contained in the resin composition of the present invention is not particularly limited (however, the thermal radical polymerization initiator is not included), polyvalent amines, polyhydric phenols. Hydrazide compounds and the like can be mentioned, and hydrazide compounds are particularly preferably used. For example, the aromatic hydrazide salicylic acid hydrazide, terephthalic acid dihydrazide, isophthalic acid dihydrazide, 2,6-naphthoic acid dihydrazide, 2,6-pyridinedihydrazide, 1,2,4-benzenetrihydrazide, 1,4,5,8 -Naphthoic acid tetrahydrazide, pyromellitic acid tetrahydrazide, etc. can be mentioned. Examples of the aliphatic hydrazide compounds include form hydrazide, acetohydrazide, propionic acid hydrazide, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, pimelic acid dihydrazide, 1,4- Cyclohexane dihydrazide, tartaric acid dihydrazide, malic acid dihydrazide, iminodiacetic acid dihydrazide, N, N'-hexamethylenebissemicarbazide, citric acid trihydrazide, nitriloacetic acid trihydrazide, cyclohexanetricarboxylic acid trihydrazide, 1,3-bis (hydrazinocarbono) Ethyl) -5-isopropylhydantoin and other hydantoin skeletons, preferably valine hydantoin skeletons (bones in which the carbon atoms of the hydantoin ring are substituted with isopropyl groups) A dihydrazide compound having a case), tris (1-hydrazinocarbonylmethyl) isocyanurate, tris (2-hydrazinocarbonylethyl) isocyanurate, tris (2-hydrazinocarbonylethyl) isocyanurate, tris (3-hydrazinocarbonyl) Propyl) isocyanurate, bis (2-hydrazinocarbonylethyl) isocyanurate, and the like. Preferably, from the balance of curing reactivity and latency, isophthalic acid dihydrazide, malonic acid dihydrazide, adipic acid dihydrazide, tris (1-hydrazinocarbonylmethyl) isocyanurate, tris (2-hydrazinocarbonylethyl) isocyanurate, tris (2-hydrazinocarbonylethyl) isocyanurate and tris (3-hydrazinocarbonylpropyl) isocyanurate, particularly preferably tris (2-hydrazinocarbonylethyl) isocyanurate. The amount of the thermosetting agent used is preferably 0.1 parts by mass to 20 parts by mass, more preferably 1 part by mass when the total resin composition of the present invention is 100 parts by mass. Part-10 parts by mass, and two or more kinds may be mixed and used.

[Other ingredients]
If necessary, the resin composition of the present invention may further contain additives such as curing accelerators such as organic acids, radical polymerization inhibitors, pigments, leveling agents, antifoaming agents, and solvents.
Examples of the curing accelerator include organic acids.
Examples of the organic acid include organic carboxylic acids and organic phosphoric acids, but organic carboxylic acids are preferred. Specifically, aromatic carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, benzophenone tetracarboxylic acid, furandicarboxylic acid, succinic acid, adipic acid, dodecanedioic acid, sebacic acid, thiodipropionic acid , Cyclohexanedicarboxylic acid, tris (2-carboxymethyl) isocyanurate, tris (2-carboxyethyl) isocyanurate, tris (2-carboxypropyl) isocyanurate, bis (2-carboxyethyl) isocyanurate and the like. .
In the liquid crystal sealant of the present invention, when a curing accelerator is used, it is usually 0.1 to 10% by mass, preferably 1 to 5% by mass, based on the total amount of the liquid crystal sealant.

The radical polymerization inhibitor is not particularly limited as long as it is a compound that traps radicals generated from a photopolymerization initiator, a thermal radical polymerization initiator, etc., and prevents polymerization, and is not limited to quinone, piperidine, hinders. Dophenol type, nitroso type, etc. can be used. Specifically, naphthoquinone, 2-hydroxynaphthoquinone, 2-methylnaphthoquinone, 2-methoxynaphthoquinone, 2,2,6,6, -tetramethylpiperidine-1-oxyl, 2,2,6,6, -tetramethyl -4-hydroxypiperidine-1-oxyl, 2,2,6,6, -tetramethyl-4-methoxypiperidine-1-oxyl, 2,2,6,6, -tetramethyl-4-phenoxypiperidine-1- Oxyl, hydroquinone, 2-methylhydroquinone, 2-methoxyhydroquinone, parabenzoquinone, butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylphenol, 2,6-di-t-butylcresol, stearyl β -(3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,2'-methylene (4-ethyl-6-tert-butylphenol), 4,4′-thiobis-3-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 3 , 9-bis [1,1-dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl], 2,4,8,10-tetraoxaspiro [ 5,5] undecane, tetrakis- [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenylpropionate) methane, 1,3,5-tris (3 ′, 5′- Di-t-butyl-4′-hydroxybenzyl) -sec-triazine-2,4,6- (1H, 3H, 5H) trione, paramethoxyphenol, 4-methoxy-1-naphthol, thiodiphenylamine, N-nitroso Examples include, but are not limited to, an aluminum salt of phenylhydroxyamine, trade name ADK STAB LA-81, trade name ADK STAB LA-82 (manufactured by Adeka Corporation), and the like. Of these, naphthoquinone, hydroquinone, and nitroso piperazine radical polymerization inhibitors are preferred, and naphthoquinone, 2-hydroxynaphthoquinone, hydroquinone, 2,6-di-tert-butyl-P-cresol, Polystop 7300P (Hakuto Co., Ltd.) Company-made) is more preferred, and Polystop 7300P (made by Hakuto Co., Ltd.) is most preferred.
The content of the radical polymerization inhibitor is preferably 0.0001 to 1% by mass, more preferably 0.001 to 0.5% by mass, and 0.01 to 0.2% by mass in the total amount of the liquid crystal sealant of the present invention. Is particularly preferred.

  An example of a method for obtaining the resin composition of the present invention is the following method. First, the radical photopolymerization initiator (b) is heated and dissolved in a curable compound (component (A) or other curable compound), cooled to room temperature, and then inorganic filler (component (c)), silane coupling agent. (Component (d)), thermal radical polymerization initiator (b), thermosetting agent (e) and the like are mixed, and then uniformly mixed by a known mixing device such as a three roll, sand mill, ball mill, etc. The resin composition of the present invention can be produced by filtration at

  An example of a method for obtaining the resin composition of the present invention is the following method. First, the photoradical polymerization initiator (b) is heated and dissolved in the curable resin (component (a)) of the present invention, cooled to room temperature, and then inorganic filler (component (c)), silane coupling agent (component ( d)), a thermal radical polymerization initiator (b), a thermosetting agent (e), etc. are mixed, and then uniformly mixed by a known mixing device such as a three roll, sand mill, ball mill, etc., and filtered through a metal mesh. By doing so, the resin composition of the present invention can be produced.

  The resin composition of the present invention is very useful as an adhesive for electronic parts. Examples of the adhesive for electronic components include, but are not limited to, an adhesive for flexible printed wiring boards, an adhesive for TAB, an adhesive for semiconductors, and various display adhesives.

  The resin composition of the present invention is very useful as an adhesive for liquid crystal display cells, particularly as a liquid crystal sealant. An example is shown below about the liquid crystal display cell at the time of using the resin composition of this invention as a liquid-crystal sealing compound.

A liquid crystal display cell manufactured using the liquid crystal display cell adhesive according to the present invention has a pair of substrates on which predetermined electrodes are formed facing each other at a predetermined interval, and the periphery is sealed with the liquid crystal sealant of the present invention. Liquid crystal is sealed in the gap. The kind of liquid crystal to be sealed is not particularly limited. Here, the substrate is composed of a combination of substrates made of at least one of glass, quartz, plastic, silicon, etc. and having light transmission properties. As a manufacturing method thereof, after adding a spacer (gap control material) such as glass fiber to the liquid crystal sealant of the present invention, the liquid crystal sealant is applied to one of the pair of substrates using a dispenser or a screen printing device. Then, if necessary, temporary curing is performed at 80 to 120 ° C. Thereafter, a liquid crystal is dropped inside the weir of the liquid crystal sealant, and the other glass substrate is overlaid in a vacuum to create a gap. After the gap is formed, the liquid crystal sealant is irradiated with ultraviolet rays by an ultraviolet irradiator and photocured. UV irradiation dose is preferably 500~6000mJ / cm ^2, more preferably the dose of 1000~4000mJ / cm ² is preferred. Then, if necessary, the liquid crystal display cell of the present invention can be obtained by curing at 90 to 130 ° C. for 1 to 2 hours. The liquid crystal display cell of the present invention thus obtained has a high glass transition temperature and is excellent in heat resistance reliability. Examples of the spacer include glass fiber, silica beads, polymer beads and the like. The diameter varies depending on the purpose, but is usually 2 to 8 μm, preferably 4 to 7 μm. The amount used is usually 0.1 to 4% by mass, preferably 0.5 to 2% by mass, and more preferably about 0.9 to 1.5% by mass with respect to 100% by mass of the liquid crystal sealant of the present invention. is there.

  The resin composition of the present invention is very suitable for use in adhesive applications. That is, since the cured product has a high glass transition temperature and excellent heat resistance, it has a remarkable effect on the heat resistance reliability of the cured product. Moreover, the resin composition using the acrylic compound of the present invention is very useful as an adhesive for electronic parts and an adhesive for liquid crystal display cells.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to an Example. Unless otherwise specified, “part” and “%” in the text are based on mass.

  Each physical property value in Synthesis Examples and Examples was measured by the following method. Here, the part represents part by weight unless otherwise specified.

○ ¹ H-NMR: Measured with deuterated chloroform solvent using JNM-ECS400 manufactured by JEOL Ltd.

○ LC / MS: LC / MS was measured under the following conditions.
Various LC / MS condition equipment: Ultimate 3000 / Q-Executive (Thermo)
Detector: PDA (190-800 nm), FT-MS (m / z = 150-2000)
Column: YMC-Triart C18 2.1 × 150 mm, 1.9 μm (YMC)
Column temperature: 40 ° C
Flow rate: 0.3 mL / min Fluidized bed: (A) 5 mM ammonium acetate aqueous solution / (B) Acetonitrile gradient (B%): 50% -15 min-95% (10 min)
Injection: 0.2μL
[Synthesis Example 1]
[Synthesis of 4,5-epoxy-1,2,3,6-tetrahydrophthalic acid (acryloylethyl) (methacryloyl-2-hydroxypropyl)]
(Process 1)
Dissolve 55.6 g of 1,2,3,6-tetrahydrophthalic anhydride and 43.3 g of hydroxyethyl acrylate in 42 g of toluene, add 0.5 g of dibutylhydroxytoluene as a polymerization inhibitor, and raise the temperature to 95 ° C. . After stirring at 95 ° C. for 6 hours, the mixture was allowed to cool to 60 ° C. To this reaction solution, 59 g of toluene, 53.0 g of glycidyl methacrylate, and 0.8 g of tetrapropylammonium hydroxide 40% aqueous solution were added, and the temperature was raised to 98 ° C. After stirring at 98 ° C. for 18 hours, the mixture was allowed to cool to room temperature, and 150 g of toluene and 300 g of methyl isobutyl ketone were added and washed with water. The organic solvent was removed from the evaporator to obtain 1,2,3,6-tetrahydrophthalic acid (acryloylethyl) (methacryloyl leu-2-hydroxypropyl). ( ¹ H-NMR data: 6.4 (1H), 6.1 (2H) 5.9 (1H), 5.7 (2H), 5.6 (1H), 4.0 to 4.5 (8H ), 3.8 (1H), 3.1 (2H), 2.5 (2H), 2.3 (2H), 1.9 (3H), LC-MS data: m / z = 428.19 [ M + NH4 ⁺ ]), m / z = 469.17 [M + CH3COO ⁻ ])
(Process 2)
1,2,3,6-tetrahydrophthalic acid (acryloylethyl) (methacryloyl 2-hydroxypropyl) synthesized in step 1 28.9 g, toluene 29 g, trioctylmethylammonium acetate 0.3 g (manufactured by Lion Akzo 50% Xylene solution, TOMAA-50), 2 g of water, 0.5 g of 12-tungstophosphoric acid, 0.2 g of sodium tungstate, and 2.9 g of sodium dihydrogen phosphate. 8.9 g of a weight% hydrogen peroxide solution was added, and the mixture was stirred as it was at 50 ± 3 ° C. for 30 hours. When the progress of the reaction was confirmed by 1H-NMR, the conversion rate from the carbon-carbon double bond to the epoxy after completion of the reaction was> 99%, and the carbon-carbon double bond peak of the raw material disappeared (1% The following).
Next, the pH was adjusted to 9 with a 30% aqueous sodium hydroxide solution, 25 parts of a 20% aqueous sodium thiosulfate solution was added, and the mixture was stirred for 30 minutes and allowed to stand. The organic layer separated into two layers was taken out, 6 g of activated carbon (SD produced by Ajinomoto Fine Techno) and 3 g of montmorillonite (Kunipia F manufactured by Kumiai Chemical Co., Ltd.) were added thereto, and the mixture was stirred at room temperature for 4 hours and filtered. By distilling off the organic solvent of the obtained filtrate, 25.3 g of the desired 4,5-epoxy-1,2,3,6-tetrahydrophthalic acid (acryloylethyl) (methacryloyl 2-hydroxypropyl) was obtained. Got. ( ¹ H-NMR data: 6.4 (1H), 6.1 (2H) 5.9 (1H), 5.6 (1H), 4.0 to 4.5 (8H), 3.8 (1H ), 3.2 (2H), 3.0 (2H), 2.2-2.3 (4H), 1.9 (3H), LC-MS data: m / z = 444.19 [M + NH4 ^<+ >]. ), M / z = 485.17 [M + CH 3 COO ⁻ ])
[Reference Synthesis Example 1]
[Synthesis of Acrylated Resorcin Diglycidyl Ether]
Resorcin diglycidyl ether 181.2 g (Nagase ChemteX Corporation) was dissolved in 266.8 g of toluene, and 0.8 g of dibutylhydroxytoluene was added thereto as a polymerization inhibitor, and the temperature was raised to 60 ° C. Thereafter, 117.5 g of acrylic acid with 100% equivalent of epoxy group was added and the temperature was further raised to 80 ° C., 0.6 g of trimethylammonium chloride as a reaction catalyst was added thereto, and the mixture was stirred at 98 ° C. for about 30 hours, A reaction solution was obtained. This reaction solution was washed with water, and toluene was distilled off to obtain 253 g of a desired resorcin diglycidyl ether epoxy acrylate (acrylated resorcin diglycidyl ether).
[Reference Synthesis Example 2]
[Synthesis of 1,2-bis (trimethylsiloxy) -1,1,2,2-tetraphenylethane]
100 parts (0.28 mol) of commercially available benzopinacol (manufactured by Tokyo Chemical Industry) was dissolved in 350 parts of dimethylformaldehyde. To this was added 32 parts (0.4 mol) of pyridine as a base catalyst and 150 parts (0.58 mol) of BSTFA (manufactured by Shin-Etsu Chemical Co., Ltd.) as a silylating agent, and the mixture was heated to 70 ° C. and stirred for 2 hours. The obtained reaction solution was cooled and stirred while adding 200 parts of water to precipitate the product and deactivate the unreacted silylating agent. The precipitated product was separated by filtration and thoroughly washed with water. Subsequently, the obtained product was dissolved in acetone, recrystallized by adding water and purified. 105.6 parts (yield 88.3%) of the target 1,2-bis (trimethylsiloxy) -1,1,2,2-tetraphenylethane were obtained.
As a result of analysis by HPLC (high performance liquid chromatography), the purity was 99.0% (area percentage).

(Adjustment of liquid crystal sealant)
[Example 1, Comparative Example 1]
(Meth) acrylic compounds (component (A)), (meth) having one or more skeletons represented by the acryloyl group, methacryloyl group and the following formula (1) in one molecule at the ratio shown in Table 1 below. ) Acrylic resin, epoxy resin, radical photopolymerization initiator (component (b)) are heated and dissolved at 90 ° C., and then cooled to room temperature, silane coupling agent (component (d)), inorganic filler (component ( c)), an organic filler, a thermal radical polymerization initiator (component (b)) and a curing agent are added and stirred, then dispersed with a three roll mill, filtered through a metal mesh (635 mesh), and a liquid crystal dropping method. Sealant Example 1 and Comparative Example 1 were prepared.

The evaluation test was carried out by the following method.

(Glass transition temperature measurement)
A liquid crystal sealant produced in Examples and Comparative Examples was sandwiched between polyethylene terephthalate (PET) films to form a thin film having a thickness of 100 μm, and irradiated with 3000 mJ / cm ² of ultraviolet rays using a UV irradiator, and then placed in an oven. C. for 1 hour. After curing, the PET film was peeled to obtain a cured sealant film, which was then cut into 5 mm × 5 mm strips to obtain sample pieces. This sample piece was measured in a tensile mode of a dynamic viscoelasticity measuring apparatus (DMS-6100: manufactured by SII Nano Technology) under the conditions of a frequency of 10 Hz and a temperature rising temperature of 3 ° C./min, and the obtained loss factor The maximum temperature in the Tan δ curve was defined as the glass transition temperature. The results are shown in Table 1.

(Adhesive strength)
To 1 g of the obtained liquid crystal sealant, 0.01 g of 3 μm glass fiber was added as a spacer and mixed and stirred. The liquid crystal sealant was placed on a glass base piece coated with an alignment film of about 20 mm × 30 mm using a dispenser. Drawn. At this time, the coating amount was set so that the line width was 0.7 mm, and drawing was performed in the form as shown in FIG. Thereafter, a glass substrate coated with an alignment film of about 10 mm × 25 mm is bonded as a counter substrate, photocured by UV irradiation of 3000 mJ / cm ² , put into a 120 ° C. oven for 1 hour, further thermally cured, and a test piece is obtained. Created. The test piece was peeled from the bottom to the top with a bond tester (SS-30WD: manufactured by Seishin Shoji Co., Ltd.), and the peel adhesive strength was measured.

  From the results of Table 1, it was confirmed that the cured product of the resin composition of the present invention had a high glass transition temperature and excellent heat resistance. It was also confirmed that the adhesive strength was high.

  The resin composition of the present invention is very useful as an adhesive for electronic parts, particularly as a liquid crystal sealant.

Claims (11)

(A) A resin composition containing a compound having at least one acryloyl group, methacryloyl group, and skeleton represented by the following formula (1) in one molecule.

(In Formula (1), R ¹ and R ² each independently represents a hydrocarbon group. R ¹ and R ² may be bonded to form a ring structure.)   The resin composition according to claim 1, wherein (A) is a compound further having one or more hydroxy groups in the molecule.   The resin composition according to claim 1 or 2, wherein (A) is a compound further having four or more ester bonds in the molecule.   Furthermore, the resin composition as described in any one of Claims 1 thru | or 3 containing (b) radical polymerization initiator.   Furthermore, (c) The resin composition as described in any one of Claims 1 thru | or 4 containing an inorganic filler.   Furthermore, (d) The resin composition as described in any one of the Claims 1 thru | or 5 containing a silane coupling agent.   The adhesive for electronic components using the resin composition as described in any one of Claims 1 thru | or 6.   The electronic component adhere | attached with the hardened | cured material obtained by hardening | curing the adhesive agent for electronic components of Claim 7.   The adhesive for liquid crystal display cells using the resin composition as described in any one of Claims 1 thru | or 6.   The liquid-crystal sealing compound using the resin composition as described in any one of Claims 1 thru | or 6.   The liquid crystal display cell adhere | attached using the adhesive agent for liquid crystal display cells or liquid crystal sealing agent of Claim 9 or 10.

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