WO2020171053A1

WO2020171053A1 - Curable resin composition, sealing agent for liquid crystal display element, vertical conductive material, and liquid crystal display element

Info

Publication number: WO2020171053A1
Application number: PCT/JP2020/006222
Authority: WO
Inventors: 駿介高橋
Original assignee: 積水化学工業株式会社
Priority date: 2019-02-18
Filing date: 2020-02-18
Publication date: 2020-08-27
Also published as: JPWO2020171053A1; JP7160907B2; TWI826652B; TW202104321A

Abstract

The objective of the present invention is to provide a curable resin composition having both excellent properties of adhering to an alignment film and moisture permeation preventive properties. In addition, the objective of the present invention is to provide a sealing agent for a liquid crystal display element, a vertical conductive material, and a liquid crystal display element, which are obtained by using the curable resin composition. The curable resin composition according to the present invention contains a curable resin and a polymerization initiator and/or a thermosetting agent, wherein the curable resin contains a compound represented by formula (1-1) and/or a compound represented by formula (1-2). In formulae (1-1) and (1-2), R^１ represents a hydrogen atom or a methyl group, and R^２ represents a group represented by formula (2-1), (2-2), or (2-3), R^３ represents a structure derived from an optionally substituted aliphatic dicarboxylic acid or an anhydride thereof, X represents a ring-opened structure of a cyclic lactone, n is 0-5, and Ep represents a structure derived from a bifunctional or higher functional epoxy compound. In formulae (2-1) to (2-3), * represents a binding position; in formula (2-2), a is an integer of 1-8; and in formula (2-3), b is an integer of 1-8, c is an integer of 1-3, and d is an integer of 1-8.

Description

Curable resin composition, sealant for liquid crystal display device, vertical conduction material, and liquid crystal display device

TECHNICAL FIELD The present invention relates to a curable resin composition which is excellent in both adhesiveness to an alignment film and moisture permeation preventive property. The present invention also relates to a liquid crystal display element sealant, a vertical conduction material, and a liquid crystal display element, which are obtained by using the curable resin composition.

In recent years, as a method for producing a liquid crystal display element such as a liquid crystal display cell, a curable resin composition as disclosed in Patent Document 1 and Patent Document 2 is used from the viewpoints of shortening tact time and optimizing the amount of liquid crystal used. A method called a dripping method in which is used as a sealant is used.
In the dropping method, first, a sealant is applied to one of the two substrates with electrodes to form a frame-shaped seal pattern. Then, a liquid crystal microdroplet is dropped in the sealing frame of the substrate while the sealant is uncured, the other substrate is superposed under vacuum, and the sealant is cured by light irradiation or heating to produce a liquid crystal display element. To do. At present, this dropping method is the mainstream method for manufacturing liquid crystal display elements.

By the way, downsizing of the device is the most demanded issue in the present age where mobile devices with various liquid crystal panels such as mobile phones and portable game machines are prevalent. As a method of miniaturization, there is a narrow frame of the liquid crystal display part, and for example, the position of the seal part is arranged under the black matrix (hereinafter, also referred to as a narrow frame design). With such a narrow frame design, the application position of the sealant is often on the alignment film such as polyimide.

JP 2001-133794 A International Publication No. 02/092718

With the spread of tablet terminals and mobile terminals, liquid crystal display elements are increasingly required to have moisture resistance reliability when driven in high temperature and high humidity environments, and the sealant has the ability to prevent water from entering from the outside. Is more sought after. In order to improve the moisture resistance reliability of the liquid crystal display element, the adhesion of the sealant to the substrate etc. is improved to prevent the infiltration of water from the interface between the sealant and the substrate etc., and the moisture permeation of the sealant is prevented. Needs to be improved. As a method of improving the moisture permeation preventive property of the sealant, a method of mixing a filler such as talc is considered, but when a strict humidity resistance reliability test is performed, display unevenness may occur in the liquid crystal display element. there were. In particular, when the application position of the sealant is on the alignment film such as polyimide, it is difficult to achieve both the adhesiveness to the alignment film and the moisture permeation preventive property.

An object of the present invention is to provide a curable resin composition which is excellent in both adhesiveness to an alignment film and moisture permeation preventive property. Another object of the present invention is to provide a liquid crystal display element sealant, a vertical conduction material, and a liquid crystal display element, which are obtained by using the curable resin composition.

The present invention contains a curable resin and a polymerization initiator and/or a thermosetting agent, wherein the curable resin is a compound represented by the following formula (1-1) and/or a formula (1-2) below. It is a curable resin composition containing the compound represented by.

In the formulas (1-1) and (1-2), R ¹ represents a hydrogen atom or a methyl group, and R ² represents the following formulas (2-1), (2-2), or (2-3 ), R ³ represents a structure derived from an optionally substituted aliphatic dicarboxylic acid or an anhydride thereof, X represents a ring-opening structure of a cyclic lactone, and n is 0 or more. It is 5 or less, and Ep represents a structure derived from a bifunctional or higher functional epoxy compound.

In formulas (2-1) to (2-3), * represents a bonding position, and in formula (2-2), a is an integer of 1 or more and 8 or less, and in formula (2-3), b is an integer of 1 or more and 8 or less, c is an integer of 1 or more and 3 or less, and d is an integer of 1 or more and 8 or less.
The present invention will be described in detail below.

The present inventors have found that by using a compound having a specific structure as the curable resin, it is possible to obtain a curable resin composition that is excellent in both the adhesiveness to the alignment film and the moisture permeation preventive property. It came to completion.

The curable resin composition of the present invention contains a curable resin.
The curable resin contains the compound represented by the formula (1-1) and/or the compound represented by the formula (1-2). By containing the compound represented by the above formula (1-1) and/or the compound represented by the above formula (1-2), the curable resin composition of the present invention has adhesiveness and transparency to an alignment film. Excellent both in moisture resistance. Further, both the compound represented by the above formula (1-1) and the compound represented by the above formula (1-2) are excellent from the viewpoint of low liquid crystal contamination when used as a sealant for a liquid crystal display element. Shows low liquid crystal contamination. The curable resin preferably contains the compound represented by the formula (1-1).

In the formulas (1-1) and (1-2), R ² represents a group represented by the formula (2-1), (2-2) or (2-3). Among them, R ² is preferably a group represented by the above formula (2-2) from the viewpoint of the adhesiveness of the obtained curable resin composition and the flexibility of the cured product, and the above formula (2 More preferably, a in 2) is 2 (ethylene group).
In the above formulas (2-1) and (2-3), among the bond positions shown by *, the bond position on the methylene group side is (meta) in the above formulas (1-1) and (1-2). ) It becomes the bonding position with the acryloyloxy group.
In addition, in this specification, the above-mentioned "(meth)acryloyl" means acryloyl or methacryloyl.

In the above formulas (1-1) and (1-2), R ³ represents a structure derived from an optionally substituted aliphatic dicarboxylic acid or an anhydride thereof. When R ³ has a structure derived from an optionally substituted aliphatic dicarboxylic acid or its anhydride, the resulting curable resin composition has excellent adhesiveness to the alignment film.

When the aliphatic dicarboxylic acid which may be substituted or the anhydride thereof is substituted, examples of the substituent include a carbon chain having 1 to 60 carbon atoms which may have an unsaturated bond or a branched structure. , A hydrocarbon skeleton including a cyclic structure, and the like. Among them, a hydrocarbon skeleton containing a cyclic structure is preferable from the viewpoint of enhancing the moisture permeation preventive property.

Examples of the above-mentioned optionally substituted aliphatic dicarboxylic acid or anhydride thereof include 1,2-cyclohexanedicarboxylic acid anhydride, 3-methylcyclohexane-1,2-dicarboxylic acid anhydride, and 4-methylcyclohexane-1,2-dicarboxylic acid anhydride. Methylcyclohexane-1,2-dicarboxylic acid anhydride, 4-cyclohexene-1,2-dicarboxylic acid, 3-methyl-4-cyclohexene-1,2-dicarboxylic acid anhydride, 3,4,5,6-tetrahydrophthal Acid anhydride, 4-methyl-4-cyclohexene-1,2-dicarboxylic acid anhydride, tetrapropenyl succinic anhydride, decyl succinic anhydride, tetradecyl succinic anhydride, tetradecenyl succinic anhydride, hexa Decyl succinic anhydride, isooctadecenyl succinic anhydride, butyl succinic anhydride, allyl succinic anhydride, 4-hexene-1,2-dicarboxylic acid anhydride, 2-dodecen-1-yl succinic anhydride, 2,2-Dimethylsuccinic anhydride, 2-hexen-1-ylsuccinic anhydride, 4-methyl-4-pentene-1,2-dicarboxylic anhydride, 2-octenylsuccinic anhydride, 4,9-decadiene -1,2-dicarboxylic acid anhydride, 5-norbornene-2,3-dicarboxylic acid anhydride, bicyclo[2.2.2]oct-5-ene-2,3-dicarboxylic acid anhydride, 2-(2 -Carboxyethyl)-3-methylmaleic anhydride, 7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid anhydride, and these dicarboxylic acids.

From the viewpoint of further improving the adhesion to the alignment film, R ³ preferably has a structure represented by the following formula (3-1), (3-2) or (3-3).

In formulas (3-1) to (3-3), * represents a bonding position, and in formula (3-1), R ⁴ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. In the formula (3-2), R ⁵ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and in the formula (3-3), R ⁶ and R ⁷ are each independently It represents a hydrogen atom or an organic group having 1 to 60 carbon atoms, or represents a structure in which R ⁶ and R ⁷ are bonded.

Examples of the structure represented by the above formula (3-1) include structures derived from 1,2-cyclohexanedicarboxylic acid anhydride, 3-methylcyclohexane-1,2-dicarboxylic acid anhydride and the like.
Examples of the structure represented by the above formula (3-2) include 4-cyclohexene-1,2-dicarboxylic acid, 3-methyl-4-cyclohexene-1,2-dicarboxylic acid anhydride, 3,4,5 , 6-tetrahydrophthalic anhydride, 4-methyl-4-cyclohexene-1,2-dicarboxylic acid anhydride and the like.
The structure represented by the above formula (3-3) may be a structure in which R ⁶ and R ⁷ are not bonded, or a structure in which R ⁶ and R ⁷ are bonded. From the viewpoint of enhancing the moisture permeation preventive property, a structure in which R ⁶ and R ⁷ are bonded is preferable.
Examples of the structure in which R ⁶ and R ⁷ are not bonded include, for example, tetrapropenyl succinic anhydride, decyl succinic anhydride, tetradecyl succinic anhydride, tetradecenyl succinic anhydride, and hexadecyl succinic anhydride. Compounds, isooctadecenyl succinic anhydride, butyl succinic anhydride, allyl succinic anhydride, 4-hexene-1,2-dicarboxylic acid anhydride, 2-dodecen-1-ylsuccinic anhydride, 2,2- Dimethylsuccinic anhydride, 2-hexen-1-ylsuccinic anhydride, 4-methyl-4-pentene-1,2-dicarboxylic acid anhydride, 2-octenylsuccinic anhydride, 4,9-decadiene-1,2 -A structure derived from a dicarboxylic acid anhydride or the like can be mentioned.
Examples of the structure in which R ⁶ and R ⁷ are bonded include 5-norbornene-2,3-dicarboxylic acid anhydride, bicyclo[2.2.2]oct-5-ene-2,3-dicarboxylic acid Structures derived from anhydride, 2-(2-carboxyethyl)-3-methylmaleic anhydride, 7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride, etc. Is mentioned.

In the above formulas (1-1) and (1-2), X represents a ring-opening structure of a cyclic lactone.
Examples of the cyclic lactone include γ-undecalactone, ε-caprolactone, γ-decalactone, σ-dodecalactone, γ-nonanolactone, γ-heptanolactone, γ-valerolactone, σ-valerolactone, β-butyrolactone. , Γ-butyrolactone, β-propiolactone, σ-hexanolactone, 7-butyl-2-oxepanone and the like. Above all, it is preferable that the number of carbon atoms in the straight chain portion of the main skeleton is 5 or more and 7 or less when the ring is opened.
In the formulas (1-1) and (1-2), even when n is 0, that is, even when there is no ring-opening structure of the cyclic lactone represented by X, the obtained curable resin composition has It has excellent adhesiveness to the alignment film and moisture-proof property of the cured product. When n is 1 or more and 5 or less, the resulting curable resin composition is more excellent in adhesiveness to the alignment film. In addition, the compound represented by the above formula (1-1) and the compound represented by the above formula (1-2) may be a mixture of compounds each having a different number of repetitions of X. Is the average value.

In the above formulas (1-1) and (1-2), Ep represents a structure derived from a bifunctional or higher functional epoxy compound.
Examples of the epoxy compound from which Ep is derived include bisphenol A type epoxy compound, bisphenol F type epoxy compound, bisphenol E type epoxy compound, bisphenol S type epoxy compound, resorcinol type epoxy compound, dicyclopentadiene type epoxy compound, naphthalene. Type epoxy compounds, rubber-modified epoxy compounds, glycidyl ester compounds and the like.
Above all, the Ep preferably has a structure derived from a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, or a bisphenol E type epoxy compound.

Examples of the method for producing the compound represented by the above formula (1-1) include the following methods. That is, a step of reacting the hydroxyalkyl (meth)acrylate with the optionally substituted aliphatic dicarboxylic acid or its anhydride by heating and stirring in the presence of a polymerization inhibitor, and the resulting reaction And the like, and a step of reacting a part of the epoxy groups by adding the above-mentioned bifunctional or higher functional epoxy compound and heating and stirring.
Further, examples of the method for producing the compound represented by the above formula (1-2) include the following methods. That is, a step of reacting the hydroxyalkyl (meth)acrylate with the optionally substituted aliphatic dicarboxylic acid or its anhydride by heating and stirring in the presence of a polymerization inhibitor, and the resulting reaction And a method of reacting all epoxy groups by adding the above-mentioned bifunctional or higher functional epoxy compound to the product and stirring with heating.
In addition, in this specification, the above-mentioned "(meth)acrylate" means an acrylate or a methacrylate.

Examples of the hydroxyalkyl (meth)acrylate include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate and 2-hydroxy-3-phenoxypropyl (meth). An acrylate etc. are mentioned.
The hydroxyalkyl (meth)acrylate may be reacted with the cyclic lactone before being reacted with the optionally substituted aliphatic dicarboxylic acid or its anhydride.

Examples of the polymerization inhibitor include hydroquinone and p-methoxyphenol.

The preferable lower limit of the content of the compound represented by the formula (1-1) and/or the compound represented by the formula (1-2) in 100 parts by weight of the curable resin is 5 parts by weight, and the preferable upper limit is 90 parts by weight. It is a department. When the content of the compound represented by the above formula (1-1) and/or the compound represented by the above formula (1-2) is within this range, the resulting curable resin composition has adhesiveness to an alignment film. It is more excellent due to the effect of achieving both the moisture permeation preventive property. The more preferable lower limit of the content of the compound represented by the formula (1-1) and/or the compound represented by the formula (1-2) is 10 parts by weight, and the more preferable upper limit thereof is 80 parts by weight.
The above “content of the compound represented by the formula (1-1) and/or the compound represented by the formula (1-2)” means that when only one of these compounds is contained, its content Means the content of one of the compounds, and when both are contained, it means the total content.

The curable resin composition of the present invention further comprises the compound represented by the formula (1-1) and the formula (1-2) as the curable resin as long as the object of the present invention is not impaired. You may contain other curable resins other than the compound.
Examples of the other curable resin include, for example, other epoxy compounds other than the compound represented by the formula (1-1) and other (meth)acryl other than the compound represented by the formula (1-2). A compound etc. are mentioned.
In the present specification, the “(meth)acryl” means acryl or methacryl, and the “(meth)acryl compound” means a compound having a (meth)acryloyl group.

Examples of the other epoxy compounds include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol S type epoxy compounds, 2,2′-diallyl bisphenol A type epoxy compounds, hydrogenated bisphenol type epoxy compounds, propylene oxide addition Bisphenol A type epoxy compound, resorcinol type epoxy compound, biphenyl type epoxy compound, sulfide type epoxy compound, diphenyl ether type epoxy compound, dicyclopentadiene type epoxy compound, naphthalene type epoxy compound, phenol novolac type epoxy compound, orthocresol novolak type epoxy compound , Dicyclopentadiene novolac type epoxy compounds, biphenyl novolac type epoxy compounds, naphthalene phenol novolac type epoxy compounds, glycidyl amine type epoxy compounds, alkyl polyol type epoxy compounds, rubber modified epoxy compounds, glycidyl ester compounds and the like.

Examples of commercially available bisphenol A type epoxy compounds include jER828EL, jER1004 (all manufactured by Mitsubishi Chemical Corporation), EPICLON EXA-850CRP (manufactured by DIC), and the like.
Examples of commercially available bisphenol F type epoxy compounds include jER806 and jER4004 (both manufactured by Mitsubishi Chemical Corporation).
Examples of commercially available bisphenol S-type epoxy compounds include EPICLON EXA1514 (manufactured by DIC) and the like.
Examples of commercially available 2,2′-diallyl bisphenol A type epoxy compounds include RE-810NM (manufactured by Nippon Kayaku Co., Ltd.) and the like.
Examples of commercially available hydrogenated bisphenol type epoxy compounds include EPICLON EXA7015 (manufactured by DIC).
Examples of commercially available propylene oxide-added bisphenol A type epoxy compounds include EP-4000S (manufactured by ADEKA).
Examples of commercially available resorcinol type epoxy compounds include EX-201 (manufactured by Nagase Chemtex) and the like.
Examples of commercially available biphenyl type epoxy compounds include jER YX-4000H (manufactured by Mitsubishi Chemical Corporation) and the like.
Examples of commercially available sulfide type epoxy compounds include YSLV-50TE (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) and the like.
Examples of commercially available diphenyl ether type epoxy compounds include YSLV-80DE (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) and the like.
Examples of commercially available dicyclopentadiene type epoxy compounds include EP-4088S (manufactured by ADEKA) and the like.
Commercially available naphthalene-type epoxy compounds include, for example, EPICLON HP4032 and EPICLON EXA-4700 (both manufactured by DIC).
Examples of commercially available phenol novolac type epoxy compounds include EPICLON N-770 (manufactured by DIC).
Examples of commercially available orthocresol novolac type epoxy compounds include EPICLON N-670-EXP-S (manufactured by DIC) and the like.
Examples of commercially available dicyclopentadiene novolac type epoxy compounds include EPICLON HP7200 (manufactured by DIC) and the like.
Examples of commercially available biphenyl novolac type epoxy compounds include NC-3000P (manufactured by Nippon Kayaku Co., Ltd.) and the like.
Examples of commercially available naphthalenephenol novolac type epoxy compounds include ESN-165S (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.).
Examples of commercially available glycidylamine type epoxy compounds include jER630 (manufactured by Mitsubishi Chemical Corporation), EPICLON 430 (manufactured by DIC Corporation), TETRAD-X (manufactured by Mitsubishi Gas Chemical Company) and the like.
Among the above-mentioned alkyl polyol type epoxy compounds, commercially available compounds include, for example, ZX-1542 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), EPICLON 726 (manufactured by DIC Co., Ltd.), Epolite 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.), and Denacol EX-611. (Manufactured by Nagase Chemtex) and the like.
Commercially available rubber-modified epoxy compounds include, for example, YR-450, YR-207 (all manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), and Epolide PB (manufactured by Daicel).
Examples of commercially available glycidyl ester compounds include Denacol EX-147 (manufactured by Nagase Chemtex) and the like.
Other commercially available epoxy compounds include, for example, YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), XAC4151 (manufactured by Asahi Kasei Co., Ltd.), jER1031, jER1032 (any one). And Mitsubishi Chemical Co., Ltd.), EXA-7120 (manufactured by DIC), TEPIC (manufactured by Nissan Chemical Co., Ltd.) and the like.

Further, the curable resin may contain a partial (meth)acryl-modified epoxy resin as the other epoxy compound.
In the present specification, the partial (meth)acryl-modified epoxy resin means, for example, reacting a part of epoxy groups of an epoxy compound having two or more epoxy groups in one molecule with (meth)acrylic acid. Means a compound having at least one epoxy group and at least one (meth)acryloyl group in one molecule.

Examples of the other (meth)acrylic compounds include (meth)acrylic acid ester compounds, epoxy (meth)acrylates, urethane (meth)acrylates, and the like. Of these, epoxy (meth)acrylate is preferable. The (meth)acrylic compound preferably has two or more (meth)acryloyl groups in one molecule from the viewpoint of reactivity.
In addition, in this specification, the said "epoxy (meth)acrylate" represents the compound which made all the epoxy groups in an epoxy compound react with (meth)acrylic acid.

Among the above-mentioned (meth)acrylic acid ester compounds, monofunctional ones include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate. , T-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, iso Myristyl (meth)acrylate, stearyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, cyclohexyl ( (Meth)acrylate, isobornyl (meth)acrylate, bicyclopentenyl (meth)acrylate, benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, methoxyethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, ethyl carbi Tol (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, 1H,1H,5H-octafluoropentyl (meth)acrylate, Imido (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, 2-(meth)acryloyloxyethylsuccinic acid, 2-(meth)acryloyloxyethylhexahydrophthalic acid, 2-( Examples thereof include (meth)acryloyloxyethyl 2-hydroxypropyl phthalate, 2-(meth)acryloyloxyethyl phosphate, and glycidyl (meth)acrylate.

Examples of the bifunctional compounds of the (meth)acrylic acid ester compound include, for example, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, and 1,6-hexane. Diol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di (Meth)acrylate, polyethylene glycol di(meth)acrylate, 2-n-butyl-2-ethyl-1,3-propanediol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth ) Acrylate, polypropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene oxide-added bisphenol A di(meth)acrylate, propylene oxide-added bisphenol A di(meth)acrylate, ethylene oxide-added bisphenol F di(meth)acrylate , Dimethyloldicyclopentadienyl di(meth)acrylate, ethylene oxide-modified isocyanuric acid di(meth)acrylate, 2-hydroxy-3-(meth)acryloyloxypropyl(meth)acrylate, carbonate diol di(meth)acrylate, Examples include polyether diol di(meth)acrylate, polyester diol di(meth)acrylate, polycaprolactone diol di(meth)acrylate, polybutadiene diol di(meth)acrylate, and the like.

Examples of the trifunctional or higher functional (meth)acrylic acid ester compound include, for example, trimethylolpropane tri(meth)acrylate, ethylene oxide-added trimethylolpropane tri(meth)acrylate, and propylene oxide-added trimethylolpropane tri( (Meth)acrylate, caprolactone-modified trimethylolpropane tri(meth)acrylate, ethylene oxide-added isocyanuric acid tri(meth)acrylate, glycerin tri(meth)acrylate, propylene oxide-added glycerin tri(meth)acrylate, pentaerythritol tri(meth)acrylate, Examples thereof include tris(meth)acryloyloxyethyl phosphate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate.

Examples of the epoxy (meth)acrylate include those obtained by reacting an epoxy compound and (meth)acrylic acid in the presence of a basic catalyst according to a conventional method.

As the epoxy compound which is a raw material for synthesizing the epoxy (meth)acrylate, the same epoxy compounds as those described above can be used.

Commercially available epoxy (meth)acrylates include, for example, epoxy (meth)acrylate manufactured by Daicel Ornex Co., epoxy (meth)acrylate manufactured by Shin-Nakamura Chemical Co., and epoxy (meth) manufactured by Kyoeisha Chemical Co., Ltd. Examples thereof include (meth)acrylate and epoxy (meth)acrylate manufactured by Nagase Chemtex.
The epoxy (meth) acrylate manufactured by the Daicel Orunekusu Inc., for example, EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRYL3703, EBECRYL3708, EBECRYL3800, EBECRYL6040, EBECRYL RDX63182, KRM8076, and the like.
Examples of the epoxy (meth)acrylate manufactured by Shin-Nakamura Chemical Co., Ltd. include EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, EMA-1020.
Examples of the epoxy (meth)acrylate manufactured by Kyoeisha Chemical Co., Ltd. include epoxy ester M-600A, epoxy ester 40EM, epoxy ester 70PA, epoxy ester 200PA, epoxy ester 80MFA, epoxy ester 3002M, epoxy ester 3002A, epoxy ester 1600A, Epoxy ester 3000M, epoxy ester 3000A, epoxy ester 200EA, epoxy ester 400EA, etc. are mentioned.
Examples of the epoxy (meth)acrylate manufactured by Nagase Chemtex include Denacol acrylate DA-141, Denacol acrylate DA-314, and Denacol acrylate DA-911.

The urethane (meth)acrylate can be obtained, for example, by reacting an isocyanate compound with a (meth)acrylic acid derivative having a hydroxyl group in the presence of a catalytic amount of a tin compound.

Examples of the above-mentioned isocyanate compound include isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4,4′-diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris (isocyanate phenyl) thiophosphate, tetramethyl xylylene diisocyanate Examples thereof include isocyanate and 1,6,11-undecane triisocyanate.

Further, as the above-mentioned isocyanate compound, a chain-extended isocyanate compound obtained by reacting a polyol with an excess isocyanate compound can also be used.
Examples of the polyol include ethylene glycol, propylene glycol, glycerin, sorbitol, trimethylolpropane, carbonate diol, polyether diol, polyester diol and polycaprolactone diol.

Examples of the (meth)acrylic acid derivative having a hydroxyl group include hydroxyalkyl mono(meth)acrylate, mono(meth)acrylate of divalent alcohol, mono(meth)acrylate of divalent alcohol or di(meth)acrylate. , Epoxy (meth) acrylate and the like.
Examples of the hydroxyalkyl mono(meth)acrylate include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. Can be mentioned.
Examples of the dihydric alcohol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, polyethylene glycol and the like.
Examples of the trihydric alcohol include trimethylolethane, trimethylolpropane, and glycerin.
Examples of the epoxy (meth)acrylate include bisphenol A type epoxy acrylate.

Examples of commercially available urethane (meth)acrylates include, for example, urethane (meth)acrylate manufactured by Toagosei Co., Ltd., urethane (meth)acrylate manufactured by Daicel Ornex Co., and urethane (meth) manufactured by Negami Kogyo Co., Ltd. Examples thereof include acrylate, urethane (meth)acrylate manufactured by Shin-Nakamura Chemical Co., Ltd., urethane (meth)acrylate manufactured by Kyoeisha Chemical Co., Ltd., and the like.
Examples of the urethane (meth)acrylate manufactured by Toagosei Co., Ltd. include M-1100, M-1200, M-1210, M-1600 and the like.
The urethane (meth) acrylate manufactured by the Daicel Orunekusu Inc., for example, EBECRYL210, EBECRYL220, EBECRYL230, EBECRYL270, EBECRYL1290, EBECRYL2220, EBECRYL4827, EBECRYL4842, EBECRYL4858, EBECRYL5129, EBECRYL6700, EBECRYL8402, EBECRYL8803, EBECRYL8804, EBECRYL8807, EBECRYL9260 etc. Can be mentioned.
Examples of the urethane (meth)acrylate manufactured by Negami Kogyo Co., Ltd. include Art Resin UN-330, Art Resin SH-500B, Art Resin UN-1200TPK, Art Resin UN-1255, Art Resin UN-3320HB, Art Resin UN-. 7100, Art Resin UN-9000A, Art Resin UN-9000H and the like.
Examples of the urethane (meth)acrylate manufactured by Shin Nakamura Chemical Co., Ltd. include U-2HA, U-2PHA, U-3HA, U-4HA, U-6H, U-6HA, U-6LPA, U-10H, U-15HA, U-108, U-108A, U-122A, U-122P, U-324A, U-340A, U-340P, U-1084A, U-2061BA, UA-340P, UA-4000, UA- 4100, UA-4200, UA-4400, UA-5201P, UA-7100, UA-7200, UA-W2A and the like.
Examples of the urethane (meth)acrylate manufactured by Kyoeisha Chemical Co., Ltd. include AH-600, AI-600, AT-600, UA-101I, UA-101T, UA-306H, UA-306I, UA-306T. To be

From the viewpoint of suppressing liquid crystal contamination, the above-mentioned other (meth)acrylic compounds are preferably those having a hydrogen-bonding unit such as —OH group, —NH— group, and —NH ₂ group.

The curable resin composition of the present invention contains a polymerization initiator and/or a thermosetting agent.
Examples of the polymerization initiator include radical polymerization initiators and cationic polymerization initiators.

Examples of the radical polymerization initiator include a photoradical polymerization initiator that generates a radical upon irradiation with light and a thermal radical polymerization initiator that generates a radical upon heating.

Examples of the photoradical polymerization initiator include benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, oxime ester compounds, benzoin ether compounds, thioxanthone compounds, and the like.
Specific examples of the photo-radical polymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone, 1,2-(dimethylamino) -2-((4-methylphenyl)methyl)-1-(4-(4-morpholinyl)phenyl)-1-butanone, 2,2-dimethoxy-1,2-diphenylethan-1-one, bis(2 , 4,6-Trimethylbenzoyl)phenylphosphine oxide, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 1-(4-(2-hydroxyethoxy)-phenyl)- 2-hydroxy-2-methyl-1-propan-1-one, 1-(4-(phenylthio)phenyl)-1,2-octanedione 2-(O-benzoyloxime), 2,4,6-trimethylbenzoyl Examples thereof include diphenylphosphine oxide, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and the like.

Examples of the thermal radical polymerization initiator include those composed of azo compounds, organic peroxides and the like. Among them, an initiator composed of a polymer azo compound (hereinafter, also referred to as “polymer azo initiator”) is preferable.
In the present specification, the polymeric azo compound means a compound having an azo group and having a number average molecular weight of 300 or more, which produces a radical capable of curing a (meth)acryloyl group by heat.

The preferable lower limit of the number average molecular weight of the high molecular weight azo compound is 1,000, and the preferable upper limit thereof is 300,000. When the number average molecular weight of the polymer azo compound is in this range, it can be easily mixed with the curable resin while suppressing liquid crystal contamination. The more preferable lower limit of the number average molecular weight of the high molecular weight azo compound is 5000, the more preferable upper limit is 100,000, the still more preferable lower limit is 10,000, and the still more preferable upper limit is 90,000.
In addition, in this specification, the said number average molecular weight is the value calculated|required by polystyrene conversion, using tetrahydrofuran as a solvent by gel permeation chromatography (GPC). Examples of columns for measuring the number average molecular weight in terms of polystyrene by GPC include Shodex LF-804 (Showa Denko KK).

Examples of the polymer azo compound include those having a structure in which a plurality of units such as polyalkylene oxide and polydimethylsiloxane are bonded via an azo group.
As the polymer azo compound having a structure in which a plurality of units such as polyalkylene oxide are bonded via the azo group, those having a polyethylene oxide structure are preferable.
Specific examples of the polymer azo compound include polycondensates of 4,4′-azobis(4-cyanopentanoic acid) and polyalkylene glycol, and 4,4′-azobis(4-cyanopentanoic acid). And a polycondensation product of polydimethylsiloxane having a terminal amino group.
Examples of commercially available high-molecular azo compounds include VPE-0201, VPE-0401, VPE-0601, VPS-0501, VPS-1001 (all manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.). To be
In addition, examples of commercially available azo compounds that are not polymers include V-65 and V-501 (both manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.).

Examples of the organic peroxide include ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, peroxy ester, diacyl peroxide, peroxydicarbonate and the like.

A photo-cationic polymerization initiator is preferably used as the above-mentioned cationic polymerization initiator.
The photocationic polymerization initiator is not particularly limited as long as it generates a protonic acid or a Lewis acid by light irradiation, and may be an ionic photoacid generating type or a nonionic photoacid generating type. May be

Examples of the photocationic polymerization initiator include onium salts such as aromatic diazonium salts, aromatic halonium salts and aromatic sulfonium salts, iron-arene complexes, titanocene complexes, arylsilanol-aluminum complexes and other organometallic complexes. Is mentioned.

Examples of commercially available photocationic polymerization initiators include ADEKA OPTOMER SP-150 and ADEKA OPTOMER SP-170 (both manufactured by ADEKA).

With respect to the content of the polymerization initiator, a preferable lower limit is 0.01 part by weight and a preferable upper limit is 10 parts by weight with respect to 100 parts by weight of the curable resin. When the content of the above-mentioned polymerization initiator is within this range, when the resulting curable resin composition is used as a sealant for liquid crystal display devices, while suppressing liquid crystal contamination, it is more excellent in storage stability and curability. Becomes The more preferable lower limit of the content of the polymerization initiator is 0.1 parts by weight, and the more preferable upper limit thereof is 5 parts by weight.

Examples of the thermosetting agent include organic acid hydrazides, imidazole derivatives, amine compounds, polyhydric phenol compounds, acid anhydrides, and the like. Among them, solid organic acid hydrazide is preferably used.

Examples of the solid organic acid hydrazide include 1,3-bis(hydrazinocarboethyl)-5-isopropylhydantoin, sebacic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide, malonic acid dihydrazide and the like.
Examples of commercially available solid organic acid hydrazides include organic acid hydrazides manufactured by Otsuka Chemical Co., Ltd., organic acid hydrazides manufactured by Nippon Finechem Co., Ltd., and organic acid hydrazides manufactured by Ajinomoto Fine Techno Co., Ltd., and the like.
Examples of the organic acid hydrazide manufactured by Otsuka Chemical Co., Ltd. include SDH and ADH.
Examples of the organic acid hydrazide manufactured by Nippon Finechem Co., Ltd. include MDH.
Examples of the organic acid hydrazides manufactured by Ajinomoto Fine-Techno Co., Inc. include Amicure VDH, Amicure VDH-J, Amicure UDH and the like.

The content of the thermosetting agent is preferably 1 part by weight and 50 parts by weight with respect to 100 parts by weight of the entire curable resin. When the content of the thermosetting agent is within this range, the curable resin composition obtained is more excellent in curability while maintaining excellent coatability and storage stability. A more preferable upper limit of the content of the thermosetting agent is 30 parts by weight.

The curable resin composition of the present invention contains a filler for the purpose of improving the viscosity, further improving the adhesiveness due to the stress dispersion effect, improving the linear expansion coefficient, further improving the moisture permeability of the cured product, and the like. Preferably.

An inorganic filler or an organic filler can be used as the filler.
Examples of the inorganic filler include silica, talc, glass beads, asbestos, gypsum, diatomaceous earth, smectite, bentonite, montmorillonite, sericite, activated clay, alumina, zinc oxide, iron oxide, magnesium oxide, tin oxide, titanium oxide. , Calcium carbonate, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, aluminum nitride, silicon nitride, barium sulfate, calcium silicate and the like.
Examples of the organic filler include polyester fine particles, polyurethane fine particles, vinyl polymer fine particles, acrylic polymer fine particles, and the like.

The preferred lower limit of the content of the filler in 100 parts by weight of the curable resin composition of the present invention is 10 parts by weight, and the preferred upper limit is 70 parts by weight. When the content of the filler is within this range, it is possible to further exhibit the effect of improving the adhesiveness while suppressing the deterioration of the coating property and the like. The more preferable lower limit of the content of the filler is 20 parts by weight, and the more preferable upper limit thereof is 60 parts by weight.

The curable resin composition of the present invention preferably contains a silane coupling agent for the purpose of further improving the adhesiveness. The above-mentioned silane coupling agent mainly has a role as an adhesion aid for favorably adhering the curable resin composition to the substrate and the like.
As the silane coupling agent, for example, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane and the like are preferably used.

The preferred lower limit of the content of the silane coupling agent in 100 parts by weight of the curable resin composition of the present invention is 0.1 part by weight, and the preferred upper limit is 10 parts by weight. The content of the silane coupling agent is within this range, the effect of improving the adhesiveness while suppressing the occurrence of liquid crystal contamination when the resulting curable resin composition is used as a sealant for liquid crystal display elements Can be more exerted. The more preferable lower limit of the content of the silane coupling agent is 0.3 parts by weight, and the more preferable upper limit thereof is 5 parts by weight.

The curable resin composition of the present invention may contain a light shielding agent. By containing the above light-shielding agent, the curable resin composition of the present invention can be suitably used as a light-shielding sealant.

Examples of the light-shielding agent include iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, resin-coated carbon black, and the like. Of these, titanium black is preferable.

The titanium black is a substance having a higher transmittance in the vicinity of the ultraviolet region, particularly in the light having a wavelength of 370 nm to 450 nm, as compared with the average transmittance of light having a wavelength of 300 nm to 800 nm. That is, the titanium black has a property of imparting a light-shielding property to the curable resin composition of the present invention by sufficiently shielding light having a wavelength in the visible light region, while transmitting light having a wavelength near the ultraviolet region. It is a light-shielding agent. The light-shielding agent contained in the curable resin composition of the present invention is preferably a substance having a high insulating property, and titanium black is also suitable as a light-shielding agent having a high insulating property.

The titanium black has sufficient effects even if it is not surface-treated, but the surface is treated with an organic component such as a coupling agent, silicon oxide, titanium oxide, germanium oxide, aluminum oxide, or oxide. It is also possible to use surface-treated titanium black such as one coated with an inorganic component such as zirconium or magnesium oxide. Among them, those treated with an organic component are preferable because the insulating property can be further improved.
Further, a liquid crystal display device produced by using the curable resin composition of the present invention containing the above-mentioned titanium black as a light shielding agent as a sealing agent for liquid crystal display devices has sufficient light shielding properties, and thus does not leak light. It is possible to realize a liquid crystal display element having high contrast and excellent image display quality.

Examples of commercially available titanium blacks include titanium black manufactured by Mitsubishi Materials and titanium black manufactured by Ako Kasei.
Examples of the titanium black manufactured by Mitsubishi Materials include 12S, 13M, 13M-C, 13R-N and 14M-C.
Examples of titanium black manufactured by Ako Kasei Co., Ltd. include Tilak D.

The preferred lower limit of the specific surface area of the titanium black is 13 m ² /g, the preferred upper limit is 30 m ² /g, the more preferred lower limit is 15 m ² /g, and the more preferred upper limit is 25 m ² /g.
The preferred lower limit of the volume resistance of the titanium black is 0.5 Ω·cm, the preferred upper limit is 3 Ω·cm, the more preferred lower limit is 1 Ω·cm, and the more preferred upper limit is 2.5 Ω·cm.

The preferable lower limit of the primary particle diameter of the light-shielding agent is 1 nm, and the preferable upper limit thereof is 5 μm. When the primary particle size of the light-shielding agent is in this range, the viscosity and thixotropy of the resulting curable resin composition are not significantly increased, and the coating property is more excellent. The more preferable lower limit of the primary particle size of the light shielding agent is 5 nm, the more preferable upper limit thereof is 200 nm, the still more preferable lower limit thereof is 10 nm, and the still more preferable upper limit thereof is 100 nm.
The primary particle size of the light-shielding agent can be measured using a particle size distribution meter (for example, "NICOMP 380ZLS" manufactured by PARTICLE SIZING SYSTEMS).

The preferable lower limit of the content of the light-shielding agent in 100 parts by weight of the curable resin composition of the present invention is 5 parts by weight, and the preferable upper limit is 80 parts by weight. When the content of the light-shielding agent is within this range, the effect of improving the light-shielding property can be more exerted while maintaining the adhesiveness, the strength after curing, and the drawing property of the curable resin composition obtained. The more preferable lower limit of the content of the light-shielding agent is 10 parts by weight, the more preferable upper limit thereof is 70 parts by weight, the further preferable lower limit thereof is 30 parts by weight, and the further preferable upper limit thereof is 60 parts by weight.

The curable resin composition of the present invention further contains additives such as a stress relaxation agent, a reactive diluent, a thixotropic agent, a spacer, a curing accelerator, an antifoaming agent, a leveling agent, and a polymerization inhibitor, if necessary. May be included.

As a method for producing the curable resin composition of the present invention, for example, a curable resin, a polymerization initiator and/or a thermosetting agent, and a silane coupling agent to be added if necessary, using a mixer. And the like.
Examples of the mixer include a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, and a three-roll mill.

The curable resin composition of the present invention can be used as an adhesive, and can be particularly preferably used as a sealant for liquid crystal display elements. A sealant for liquid crystal display devices, which comprises the curable resin composition of the present invention, is also one aspect of the present invention.
In addition, a vertical conduction material can be manufactured by blending conductive fine particles with the liquid crystal display element sealing agent of the present invention. A vertical conduction material containing the liquid crystal display element sealant of the present invention and conductive fine particles is also one aspect of the present invention.

As the conductive fine particles, metal balls, resin fine particles having a conductive metal layer formed on the surface thereof, or the like can be used. Above all, a resin fine particle having a conductive metal layer formed on the surface thereof is preferable because the conductive connection can be made without damaging the transparent substrate or the like due to the excellent elasticity of the resin fine particle.

A liquid crystal display device having the cured product of the sealant for a liquid crystal display device of the present invention or the cured product of the vertically conductive material of the present invention is also one aspect of the present invention.

The sealant for a liquid crystal display element of the present invention can be suitably used for manufacturing a liquid crystal display element by a liquid crystal dropping method.
As a method for producing the liquid crystal display element of the present invention using the sealant for a liquid crystal display element of the present invention, a liquid crystal dropping method is preferably used, and specific examples thereof include a method having the following steps. To be
First, a step of forming a frame-shaped seal pattern by applying the liquid crystal display element sealant of the present invention to one of two transparent substrates having electrodes such as ITO thin films by screen printing, dispenser application, or the like. Then, a step of applying minute droplets of liquid crystal to the entire surface of the frame of the seal pattern and applying the other transparent substrate under vacuum is performed. After that, a liquid crystal display element can be obtained by a method of performing a step of irradiating the seal pattern portion with light such as ultraviolet rays to temporarily cure the sealing agent, and a step of heating the temporarily cured sealing agent to perform a final curing. it can.

According to the present invention, it is possible to provide a curable resin composition which is excellent in both the adhesiveness to an alignment film and the moisture permeation preventive property. Further, according to the present invention, it is possible to provide a sealant for liquid crystal display elements, a vertical conduction material, and a liquid crystal display element, which are obtained by using the curable resin composition.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

(Preparation of curable resin A)
232 parts by weight of 2-hydroxyethyl acrylate, 336 parts by weight of 4-methylcyclohexane-1,2-dicarboxylic acid anhydride, and 0.1 part by weight of hydroquinone as a polymerization inhibitor were added to a reaction flask, and a mantle heater was used. And stirred at 90° C. for 5 hours. Next, 340 parts by weight of bisphenol A diglycidyl ether was added to the obtained reaction product, 0.5 parts by weight of triphenylphosphine was further added, and the mixture was stirred at 110° C. for 5 hours to obtain a curable resin A.
^{By 1} H-NMR and ¹³ C-NMR, the curable resin A shows that in the above formula (1-2), R ¹ is a hydrogen atom, R ² is an ethylene group, and R ³ is the above formula (3-1). It was confirmed that the compound has a structure (R ⁴ is a methyl group), n is 0, and Ep is a structure derived from bisphenol A diglycidyl ether.

(Preparation of curable resin B)
A curable resin B was obtained in the same manner as in “(Preparation of curable resin A)” above except that 232 parts by weight of 2-hydroxyethyl acrylate was changed to 256 parts by weight of 2-hydroxypropyl acrylate.
^{By 1} H-NMR and ¹³ C-NMR, the curable resin B shows that in the above formula (1-2), R ¹ is a hydrogen atom, R ² is a methylethylene group, and R ³ is the above formula (3-1). It was confirmed that the compound has a structure represented (R ⁴ is a methyl group), n is 0, and Ep is a structure derived from bisphenol A diglycidyl ether.

(Preparation of curable resin C)
A curable resin C was obtained in the same manner as in “(Preparation of curable resin A)” above except that 232 parts by weight of 2-hydroxyethyl acrylate was changed to 256 parts by weight of 2-hydroxyethyl methacrylate.
^{By 1} H-NMR and ¹³ C-NMR, the curable resin C shows that in the above formula (1-2), R ¹ is a methyl group, R ² is an ethylene group, and R ³ is a group represented by the above formula (3-1). It was confirmed that the compound has a structure (R ⁴ is a methyl group), n is 0, and Ep is a structure derived from bisphenol A diglycidyl ether.

(Preparation of curable resin D)
A curable resin D was obtained in the same manner as in "(Preparation of curable resin A)" above except that 340 parts by weight of bisphenol A diglycidyl ether was changed to 268 parts by weight of dicyclopentadiene diglycidyl ether.
^{According to 1} H-NMR and ¹³ C-NMR, the curable resin D shows that in the above formula (1-2), R ¹ is a hydrogen atom, R ² is an ethylene group, and R ³ is the above formula (3-1). It was confirmed that the compound had a structure (R ⁴ is a methyl group), n was 0, and Ep was a structure derived from dicyclopentadiene diglycidyl ether.

(Preparation of curable resin E)
232 parts by weight of 2-hydroxyethyl acrylate, 228 parts by weight of ε-caprolactone and 0.1 part by weight of hydroquinone as a polymerization inhibitor were added to the reaction flask, and the mixture was stirred at 90° C. for 5 hours using a mantle heater. Then, 336 parts by weight of 4-methylcyclohexane-1,2-dicarboxylic acid anhydride was added, and the mixture was further stirred for 5 hours. Then, 340 parts by weight of bisphenol A diglycidyl ether was added to the obtained reaction product, 0.5 parts by weight of triphenylphosphine was further added, and the mixture was stirred at 110° C. for 5 hours to obtain a curable resin E.
^{By 1} H-NMR and ¹³ C-NMR, the curable resin E shows that in the above formula (1-2), R ¹ is a hydrogen atom, R ² is an ethylene group, and R ³ is the above formula (3-1). (R ⁴ is a methyl group), X is a ring-opening structure of ε-caprolactone, n is 2.0 (average value), and Ep is a compound derived from bisphenol A diglycidyl ether. ..

(Preparation of curable resin F)
The above "(Preparation of curable resin A)" except that 336 parts by weight of 4-methylcyclohexane-1,2-dicarboxylic acid anhydride is changed to 332 parts by weight of 4-cyclohexene-1,2-dicarboxylic acid anhydride A curable resin F was obtained in the same manner as in.
^{According to 1} H-NMR and ¹³ C-NMR, the curable resin F shows that in the above formula (1-2), R ¹ is a hydrogen atom, R ² is an ethylene group, and R ³ is the above formula (3-2). It was confirmed that the compound has the structure (R ⁵ is a hydrogen atom), n is 0, and Ep is a structure derived from bisphenol A diglycidyl ether.

(Production of curable resin G)
Curable resin in the same manner as in "(Preparation of Curable Resin A)" above except that 336 parts by weight of 4-methylcyclohexane-1,2-dicarboxylic acid anhydride was changed to 536 parts by weight of tetrapropenyl succinic anhydride. Got G.
^{By 1} H-NMR and ¹³ C-NMR, the curable resin G shows that in the formula (1-2), R ¹ is a hydrogen atom, R ² is an ethylene group, and R ³ is a group represented by the formula (3-3). It was confirmed that the compound has a structure (R ⁶ is a hydrogen atom, R ⁷ is a dodecyl group), n is 0, and Ep is a structure derived from bisphenol A diglycidyl ether.

(Preparation of curable resin H)
To the reaction flask, 116 parts by weight of 2-hydroxyethyl acrylate, 168 parts by weight of 4-methylcyclohexane-1,2-dicarboxylic acid anhydride, and 0.05 parts by weight of hydroquinone as a polymerization inhibitor were added, and a mantle heater was used. And stirred at 90° C. for 5 hours. Then, 340 parts by weight of bisphenol A diglycidyl ether was added to the obtained reaction product, 0.5 parts by weight of triphenylphosphine was further added, and the mixture was stirred at 110° C. for 5 hours to obtain a curable resin H.
^{By 1} H-NMR and ¹³ C-NMR, the curable resin H indicates that the compound represented by the above formula (1-1), the compound represented by the above formula (1-2), and bisphenol A diglycidyl ether. It was confirmed that the content ratio of the compound represented by the formula (1-1) was 57% by weight and the content ratio of the compound represented by the formula (1-2) was 23% by weight. Further, in the compound represented by the formula (1-1) contained in the curable resin H, R ¹ is a hydrogen atom, R ² is an ethylene group, and R ³ is a structure represented by the formula (3-1). (R ⁴ is a methyl group), n was 0, and Ep was confirmed to be a structure derived from bisphenol A diglycidyl ether. Further, in the compound represented by the above formula (1-2) contained in the curable resin H, R ¹ is a hydrogen atom, R ² is an ethylene group, and R ³ is a structure represented by the above formula (3-1). (R ⁴ is a methyl group), n was 0, and Ep was confirmed to be a structure derived from bisphenol A diglycidyl ether.

(Preparation of curable resin I)
Curable resin in the same manner as in “(Preparation of Curable Resin H)” above, except that 168 parts by weight of 4-methylcyclohexane-1,2-dicarboxylic acid anhydride was changed to 268 parts by weight of tetrapropenyl succinic anhydride. Got I.
^{By 1} H-NMR and ¹³ C-NMR, the curable resin I shows that the curable resin I is a compound represented by the above formula (1-1), a compound represented by the above formula (1-2), and bisphenol A diglycidyl ether. It was confirmed that the content ratio of the compound represented by the formula (1-1) was 60% by weight, and the content ratio of the compound represented by the formula (1-2) was 22% by weight. The compound represented by the above formula (1-1) contained in the curable resin I has a structure in which R ¹ is a hydrogen atom, R ² is an ethylene group, and R ³ is a structure represented by the above formula (3-3). It was confirmed that (R ⁶ is a hydrogen atom, R ⁷ is a dodecyl group), n is 0, and Ep is a structure derived from bisphenol A diglycidyl ether. Furthermore, in the compound represented by the above formula (1-2) contained in the curable resin I, R ¹ is a hydrogen atom, R ² is an ethylene group, and R ³ is a structure represented by the above formula (3-3). It was confirmed that (R ⁶ is a hydrogen atom, R ⁷ is a dodecyl group), n is 0, and Ep is a structure derived from bisphenol A diglycidyl ether.

(Preparation of curable resin J)
To the reaction flask were added 116 parts by weight of 2-hydroxyethyl acrylate, 114 parts by weight of ε-caprolactone, and 0.5 parts by weight of hydroquinone as a polymerization inhibitor, and the mixture was stirred at 90° C. for 5 hours using a mantle heater. Then, 168 parts by weight of 4-methylcyclohexane-1,2-dicarboxylic acid anhydride was added, and the mixture was further stirred for 5 hours. Next, 340 parts by weight of bisphenol A diglycidyl ether was added to the obtained reaction product, 0.5 parts by weight of triphenylphosphine was further added, and the mixture was stirred at 110° C. for 5 hours to obtain a curable resin J.
^{By 1} H-NMR and ¹³ C-NMR, the curable resin J shows that the compound represented by the above formula (1-1), the compound represented by the above formula (1-2), and bisphenol A diglycidyl ether. It was confirmed that the content of the compound represented by the formula (1-1) was 57% by weight and the content of the compound represented by the formula (1-2) was 21% by weight. In the compound represented by the above formula (1-1) contained in the curable resin J, R ¹ is a hydrogen atom, R ² is an ethylene group, and R ³ is a structure represented by the above formula (3-1). It was confirmed that (R ⁴ is a methyl group), X is a ring-opening structure of ε-caprolactone, n is 1.0 (average value), and Ep is a structure derived from bisphenol A diglycidyl ether. Further, in the compound represented by the above formula (1-2) contained in the curable resin J, R ¹ is a hydrogen atom, R ² is an ethylene group, and R ³ is a structure represented by the above formula (3-1). It was confirmed that (R ⁴ is a methyl group), X is a ring-opening structure of ε-caprolactone, n is 1.8 (average value), and Ep is a structure derived from bisphenol A diglycidyl ether.

(Preparation of curable resin K)
A curable resin K was prepared in the same manner as in “(Preparation of curable resin H)” above except that 168 parts by weight of 4-methylcyclohexane-1,2-dicarboxylic acid anhydride was changed to 148 parts by weight of phthalic anhydride. Obtained.
^{According to 1} H-NMR and ¹³ C-NMR, the curable resin K shows that in the above formula (1-1), a portion corresponding to R ¹ is a hydrogen atom, a portion corresponding to R ² is an ethylene group, and R ³ corresponds to R ³ . It was confirmed that the portion containing 1,2-phenylene group, the value corresponding to n was 0, and the portion corresponding to Ep contained 55% by weight of a compound derived from bisphenol A diglycidyl ether. In the curable resin K, in the above formula (1-2), a portion corresponding to R ¹ is a hydrogen atom, a portion corresponding to R ² is an ethylene group, and a portion corresponding to R ³ is a 1,2-phenylene group. , N was 0, and the portion corresponding to Ep contained 24% by weight of a compound having a structure derived from bisphenol A diglycidyl ether. Further, it was confirmed that the curable resin K contained 21% by weight of bisphenol A diglycidyl ether.

(Preparation of curable resin L)
A curable resin L was prepared in the same manner as in “(Preparation of curable resin A)” above, except that 336 parts by weight of 4-methylcyclohexane-1,2-dicarboxylic acid anhydride was changed to 296 parts by weight of phthalic anhydride. Obtained.
^{According to 1} H-NMR and ¹³ C-NMR, the curable resin L shows that in the above formula (1-2), the portion corresponding to R ¹ is a hydrogen atom, the portion corresponding to R ² is an ethylene group, and R ³ is equivalent to R ³ . It was confirmed that the portion corresponding to 1,2-phenylene group, the value corresponding to n was 0, and the portion corresponding to Ep had a structure derived from bisphenol A diglycidyl ether.

(Production of curable resin M)
To the reaction flask, 116 parts by weight of acrylic acid, 340 parts by weight of bisphenol A diglycidyl ether, 0.5 parts by weight of hydroquinone as a polymerization inhibitor, and 0.5 parts by weight of triphenylphosphine were added, and a mantle heater was used. And a curable resin M was obtained by stirring at 110° C. for 5 hours.
^{By 1} H-NMR and ¹³ C-NMR, the curable resin M contains 53% by weight of the compound represented by the following formula (4-1), and the curable resin M contains the compound represented by the following formula (4-2). It was confirmed that the content ratio was 22% by weight.

(Examples 1 to 12, Comparative Examples 1 to 4)
According to the compounding ratios shown in Tables 1 and 2, each material was stirred by a planetary stirring device and then uniformly mixed by a three-roll ceramic roll to cure Examples 1 to 12 and Comparative Examples 1 to 4. A resin composition was obtained. As a planetary stirrer, Awatori Rentaro (manufactured by Shinky Co.) was used.

<Evaluation>
The following evaluations were performed for each curable resin composition obtained in the examples and comparative examples. The results are shown in Tables 1 and 2.

(Adhesiveness to alignment film)
A glass substrate with an ITO thin film was applied with an imide resin by spin coating, prebaked at 80° C., and then baked at 230° C. to prepare a substrate with an alignment film. SE 7492 (manufactured by Nissan Kagaku) was used as the imide resin.
To 100 parts by weight of each curable resin composition obtained in Examples and Comparative Examples, 1 part by weight of a silica spacer was uniformly dispersed by a planetary stirring device. SI-H055 (manufactured by Sekisui Chemical Co., Ltd.) was used as the silica spacer. Then, the curable resin composition in which the silica spacer was dispersed was minutely dropped on the alignment film of the substrate with the alignment film. After the curable resin composition was dropped onto the substrate with an alignment film, another substrate with an alignment film was laminated in a cross shape with the curable resin composition interposed therebetween, and after irradiating with ultraviolet rays of 3000 mJ/cm ² with a metal halide lamp, An adhesive test piece was obtained by heating at 120° C. for 60 minutes. The strength when the panel peeled off was measured when the edge of the substrate in the produced adhesive test piece was pushed at a speed of 5 mm/min using a metal cylinder having a radius of 5 mm. When the value obtained by dividing the obtained measured value (kgf) by the seal diameter (cm) was 3.0 kgf/cm or more, it was “⊚”, and it was 2.5 kgf/cm or more and less than 3.0 kgf/cm. The adhesiveness to the alignment film was evaluated as "○" when the case was 2.0 kgf/cm or more and less than 2.5 kgf/cm and "x" when it was less than 2.0 kgf/cm. ..

(Moisture-proof property)
Each curable resin composition obtained in Examples and Comparative Examples was applied on a smooth release film by using a coater so that the thickness was 200 μm or more and 300 μm or less. Then, after irradiating with ultraviolet rays of 3000 mJ/cm ² using a metal halide lamp, the film for moisture permeability measurement was obtained by heating at 120° C. for 60 minutes. A moisture permeability test cup was prepared by a method according to the moisture permeability test method (cup method) for moisture-proof packaging materials of JIS Z 0208, and the obtained moisture permeability measurement film was attached to the cup at a temperature of 80° C. and a humidity of 90% RH. It was placed in a constant temperature and constant humidity oven and the water vapor permeability was measured. When the obtained water vapor transmission rate was less than 50 g/m ² ·24 hr, “⊚”, and when it was 50 g/m ² ·24 hr or more and less than 60 g/m ² ·24 hr, “◯”, 60 g/ m ² · 24 hr or more ^{70 g} / m where the a was less than 2 · 24 hr or "△", was evaluated anti-moisture permeability as "×" the case was ^70g / m 2 · 24hr or more.

(Display performance of liquid crystal display element)
A glass substrate with an ITO thin film was applied with an imide resin by spin coating, prebaked at 80° C., and then baked at 230° C. to prepare a substrate with an alignment film. SE 7492 (manufactured by Nissan Kagaku) was used as the imide resin.
To 100 parts by weight of each curable resin composition obtained in Examples and Comparative Examples, 1 part by weight of a silica spacer was uniformly dispersed by a planetary stirrer, and defoaming treatment was performed to obtain a curable resin composition. After removing the bubbles, the syringe for filling was filled, and the defoaming treatment was performed again. SI-H055 (manufactured by Sekisui Chemical Co., Ltd.) was used as the silica spacer, and PSY-10E (manufactured by Musashi Engineering Co., Ltd.) was used as the syringe for dispensing. Then, using a dispenser, the curable resin composition was applied onto the alignment film of the substrate with the alignment film so as to draw a frame. As the dispenser, SHOTMASTER 300 (manufactured by Musashi Engineering Co., Ltd.) was used. Then, fine droplets of TN liquid crystal were dropped and applied in the frame of the curable resin composition by a liquid crystal dropping device. Another substrate with an alignment film is overlaid on the substrate with an alignment film onto which TN liquid crystal has been dropped and applied via a curable resin composition, and the two substrates are bonded together under a reduced pressure of 5 Pa with a vacuum bonding device to form a cell. Got JC-5001LA (manufactured by Chisso Corporation) was used as the TN liquid crystal. After irradiating the obtained cell with ultraviolet rays of 3000 mJ/cm ² with a metal halide lamp, the curable resin composition was cured by heating at 120° C. for 60 minutes to prepare a liquid crystal display element. The obtained liquid crystal display element was stored under an environment of a temperature of 80° C. and a humidity of 90% RH for 144 hours, then driven at a voltage of AC 3.5 V, and the presence or absence of display unevenness (color unevenness) was visually observed. When there is no display unevenness at the periphery of the liquid crystal display element, it is indicated as "◎", when a slightly light display unevenness is seen, it is indicated as "○", and when there is a clear dark display unevenness, it is indicated as "△". The display performance of the liquid crystal display device was evaluated as "x" when the dark display unevenness spreads not only to the peripheral portion but also to the central portion.
In addition, the liquid crystal display elements with the evaluations of “⊚” and “∘” have practically no problems.

Claims

A curable resin and a polymerization initiator and/or a thermosetting agent are contained, and the curable resin is a compound represented by the following formula (1-1) and/or a compound represented by the following formula (1-2). A curable resin composition comprising a compound.

In the formulas (1-1) and (1-2), R 1 represents a hydrogen atom or a methyl group, and R 2 represents the following formulas (2-1), (2-2), or (2-3 ), R 3 represents a structure derived from an optionally substituted aliphatic dicarboxylic acid or an anhydride thereof, X represents a ring-opening structure of a cyclic lactone, and n is 0 or more. It is 5 or less, and Ep represents a structure derived from a bifunctional or higher functional epoxy compound.

In formulas (2-1) to (2-3), * represents a bonding position, and in formula (2-2), a is an integer of 1 or more and 8 or less, and in formula (2-3), b is an integer of 1 or more and 8 or less, c is an integer of 1 or more and 3 or less, and d is an integer of 1 or more and 8 or less.
R 3 in the formulas (1-1) and (1-2) is a structure represented by the following formula (3-1), (3-2) or (3-3): The curable resin composition described.

In formulas (3-1) to (3-3), * represents a bonding position, and in formula (3-1), R 4 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. In the formula (3-2), R 5 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and in the formula (3-3), R 6 and R 7 are each independently It represents a hydrogen atom or an organic group having 1 to 60 carbon atoms, or represents a structure in which R 6 and R 7 are bonded.
The curable resin composition according to claim 1, wherein the curable resin contains a compound represented by the formula (1-1).
A sealant for a liquid crystal display device, which comprises the curable resin composition according to claim 1.
A vertical conduction material containing the sealant for liquid crystal display device according to claim 4 and conductive fine particles.
A liquid crystal display device comprising the cured product of the sealant for a liquid crystal display device according to claim 4 or the cured product of the vertical conduction material according to claim 5.