WO2020204029A1 - Curable resin composition, sealing agent for liquid crystal display element, vertical conductive material, and liquid crystal display element - Google Patents

Abstract

The purpose of the present invention is to provide a curable resin composition excelling both in adhesion to an alignment film and in moisture permeation preventive properties. The purpose of the present invention is also to provide a sealing agent for a liquid crystal display element, obtained by using the curable resin composition, and a vertical conductive material and a liquid crystal display element. The present invention contains a curable resin and a polymerization initiator and/or a thermosetting agent, the curable resin being a curable resin composition including a compound represented by formula (1). In formula (1), m is an integer from 2 to 4, R¹ represents an m-valent polyol-derived structure, R² represents a structure derived from a dicarboxylic acid or an anhydride thereof which may be substituted, R³ represents a group represented by formula (2-1) or (2-2), X represents a cyclic lactone open-ring structure, n is 0 to 5 (average value), and Ep represents a structure derived from a bifunctional or higher epoxy compound. In formulas (2-1) and (2-2), * represents a bond position, and in formula (2-2), R⁴ represents a hydrogen atom or a methyl group.

Description

Curable resin composition, sealant for liquid crystal display element, vertical conductive material, and liquid crystal display element

The present invention relates to a curable resin composition having both excellent adhesiveness to an alignment film and moisture permeation prevention property. The present invention also relates to a sealant for a liquid crystal display element, a vertical conductive material, and a liquid crystal display element, which are made of the curable resin composition.

In recent years, as a method for manufacturing 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 from the viewpoint of shortening the tact time and optimizing the amount of liquid crystal used. Is used as a sealing agent, which is called a dropping method.
In the dropping method, first, a sealant is applied to one of the two electrode-equipped substrates to form a frame-shaped seal pattern. Next, in a state where the sealant is uncured, fine droplets of liquid crystal are dropped into the seal frame of the substrate, the other substrate is overlapped under vacuum, and the sealant is cured by light irradiation or heating to produce a liquid crystal display element. To do. Currently, this dropping method is the mainstream method for manufacturing liquid crystal display elements.

Japanese Unexamined Patent Publication No. 2001-133794 International Publication No. 02/092718

By the way, in the present age when various mobile devices with liquid crystal panels such as mobile phones and portable game machines are widespread, miniaturization of devices is the most sought after issue. As a method of miniaturization, a narrowing of the frame of the liquid crystal display unit can be mentioned. For example, the position of the seal portion is arranged under the black matrix (hereinafter, also referred to as a narrow frame design). With such a narrow frame design, the coating position of the sealant is often on an alignment film such as polyimide.

In addition, with the spread of tablet terminals and mobile terminals, liquid crystal display elements are increasingly required to have moisture resistance and reliability when driven in a high temperature and high humidity environment, and the sealant prevents water from entering from the outside. Performance is further required. In order to improve the moisture resistance and reliability of the liquid crystal display element, the adhesiveness of the sealant to the substrate, etc. is improved in order to prevent water from entering from the interface between the sealant and the substrate, and the moisture permeation of the sealant is prevented. It is necessary to improve the sex. As a method of improving the moisture permeation prevention property of the sealant, a method of blending a filler such as talc can be considered, but when a strict moisture resistance reliability test is performed, display unevenness may occur on the liquid crystal display element. there were. In particular, when the coating position of the sealant is on an alignment film such as polyimide, it is difficult to achieve both adhesiveness to the alignment film and moisture permeation prevention property.

An object of the present invention is to provide a curable resin composition having excellent adhesiveness to an alignment film and moisture permeation prevention property. Another object of the present invention is to provide a sealant for a liquid crystal display element, a vertical conductive material, and a liquid crystal display element using the curable resin composition.

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

In formula (1), m is an integer of 2 or more and 4 or less, R ¹ represents a structure derived from an m-valent polyol, and R ² is derived from a optionally substituted dicarboxylic acid or an anhydride thereof. Represents the structure, R ³ represents the group represented by the following formula (2-1) or (2-2), X represents the ring-opening structure of the cyclic lactone, and n is 0 or more and 5 or less (mean). Value), and Ep represents a structure derived from a bifunctional or higher functional epoxy compound.

In formulas (2-1) and (2-2), * represents a bond position, and in formula (2-2), R ⁴ represents a hydrogen atom or a methyl group.
The present invention will be described in detail below.

The present inventor has found that by using a compound having a specific structure as a curable resin, a curable resin composition excellent in both adhesiveness to an alignment film and moisture permeation prevention property can be obtained, and the present invention has been developed. It came to be completed.

The curable resin composition of the present invention contains a curable resin.
The curable resin contains a compound represented by the above formula (1). By containing the compound represented by the above formula (1) as the curable resin, the curable resin composition of the present invention is excellent in both adhesiveness to the alignment film and moisture permeation prevention property.

In the above equation (1), m is an integer of 2 or more and 4 or less. The above m is preferably 2.

In the above formula (1), R ¹ represents a structure derived from an m-valent polyol.
The preferable upper limit of the molecular weight of the polyol from which R ¹ is derived is 500. When the molecular weight of the polyol is 500 or less, the obtained curable resin composition becomes more excellent in moisture permeation prevention property. A more preferable upper limit of the molecular weight of the polyol is 400.
In the present specification, the above-mentioned "molecular weight" is the molecular weight obtained from the structural formula for a compound whose molecular structure is specified, but for a compound having a wide distribution of degree of polymerization and a compound having an unspecified modification site. It may be expressed using a number average molecular weight. Further, in the present specification, the number average molecular weight is a value obtained by measuring by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent and converting it into polystyrene. Examples of the column for measuring the number average molecular weight in terms of polystyrene by GPC include Shodex LF-804 (manufactured by Showa Denko KK).

Specific examples of the polyol from which R ¹ is derived include an aliphatic diol having 2 to 60 carbon atoms which may have a branched structure and 2 to 60 carbon atoms which may have a branched structure. Examples thereof include an aliphatic triol of the above, an aliphatic tetraol having 2 to 60 carbon atoms which may have a branched structure, and a diol containing an aromatic ring. Of these, an aliphatic diol having 2 to 60 carbon atoms, which may have a branched structure, is preferable from the viewpoint of adhesiveness.
Examples of the aliphatic diol having 2 to 60 carbon atoms include ethanediol, propanediol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, undecanediol, dodecanediol, and tridecandi. All, tetradecanediol, pentadecanediol, hexadecanediol, heptadecanediol, octadecanediol, nonanediol, 2-butene-1,4-diol, 1,4-cyclohexanedimethanol, 1,2-cyclohexanediol, 1,3 -Cyclohexanediol, 1,4-cyclohexanediol, 1,3-cyclopentanediol, 1,2-cyclopentanediol, 1,3-adamantandiol, 3,9-bis (1,1-dimethyl-2-hydroxyethyl) ) -2,4,8,10-Tetraoxaspiro [5.5] undecane, 4,4'-bicyclohexanol, 4- (2-hydroxyethyl) hexanol, hydrogenated bisphenol A and the like.
Examples of the diol containing the aromatic ring include bisphenol A, bisphenol F, bisphenol B, bisphenol E, bisphenol S, naphthalene diol, resorcinol, catechol, 4,4'-bis (hydroxymethyl) biphenyl, and 9,9-bis. (4-Hydroxyphenyl) fluorene, 1,4-bis (3-hydroxyphenoxy) benzene, 4,4'-dihydroxybiphenyl, 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene, glycerol-2 -Benzyl ether, 2,2'-oxydi (benzyl alcohol), 4,4'-cyclohexylidenebisphenol and the like can be mentioned.

In the above formula (1), R ² represents a structure derived from a dicarboxylic acid or an anhydride thereof which may be substituted. Since the R ² has a structure derived from a dicarboxylic acid or an anhydride thereof which may be substituted, the obtained curable resin composition has excellent moisture permeation prevention properties.

When the substituted dicarboxylic acid or its anhydride is substituted, for example, an unsaturated bond containing an aromatic ring or a branched structure may have 1 to 60 carbon atoms. Examples thereof include a carbon chain and a hydrocarbon skeleton containing a cyclic structure.

Specific examples of the dicarboxylic acid or its anhydride which may be substituted include phthalic anhydride, 3-methylphthalic anhydride, 4-methylphthalic anhydride, 1,2-naphthalenedicarboxylic acid anhydride, and the like. 2,3-naphthalenedicarboxylic acid anhydride, 1,8-naphthalenedicarboxylic acid anhydride, 4-tert-butylphthalic acid anhydride, phenylmaleic acid anhydride, phenylsuccinic anhydride, 1,2-cyclohexanedicarboxylic acid anhydride , 3-Methylcyclohexane-1,2-dicarboxylic acid anhydride, 4-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-tetrahydrophthalic anhydride, 4-methyl-4-cyclohexene-1,2-dicarboxylic acid anhydride, tetrapropenylsuccinic anhydride, decylsuccinic anhydride, Tetradecyl succinic anhydride, tetradecenyl succinic anhydride, hexadecyl succinic acid anhydride, allyl succinic acid anhydride, isooctadecenyl succinic acid anhydride, butyl succinic acid anhydride, 4-hexene-1,2 -Dicarboxylic acid anhydride, 2-dodecene-1-ylsuccinate anhydride, 2,2-dimethylsuccinic anhydride, 2-hexene-1-ylsuccinic anhydride, 4-methyl-4-pentene-1,2- Dicarboxylic Acid Anhydride, 2-octenyl succinic anhydride, 4,9-decadien-1,2-dicarboxylic acid anhydride, 5-norbornene-2,3-dicarboxylic acid anhydride, bicyclo [2.2.2] octo- 5-En-2,3-dicarboxylic acid anhydride, 2- (2-carboxyethyl) -3-methylmaleic acid anhydride, 7-oxabicyclo [2.2.1] hepta-5-en-2,3 -Dicarboxylic acid anhydrides, these dicarboxylic acids and the like can be mentioned.

From the viewpoint of further improving the adhesiveness of the obtained curable resin composition to the alignment film, it is preferable that R ² has a structure represented by the following formula (3).

In the formula (3), * represents a bond position, and R ⁵ and R ⁶ each independently represent a hydrogen atom or an organic group having 1 or more and 60 or less carbon atoms, or R ⁵ and R. Represents a structure in which ⁶ is bonded.

The structure represented by the above formula (3) may be a structure in which R ⁵ and R ⁶ are not bonded, or a structure in which R ⁵ and R ⁶ are bonded, but it is transparent. From the viewpoint of enhancing moisture resistance, a structure in which R ⁵ and R ⁶ are bonded is preferable, and a structure represented by the following formula (4-1) or (4-2) is more preferable.

In formula (4-1), * represents a bond position, and in formula (4-1), R ⁷ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and formula (4-2). ), R ⁸ represents a hydrogen atom or an alkyl group having 1 or more and 10 or less carbon atoms.

Examples of the structure represented by the above formula (4-1) 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 (4-2) 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.
Among the structures represented by the above formula (3), as the structural above formula (4-1) or the above ^R 5, ^{R 6} other than the structure represented by (4-2) are attached, for example, 5-Norbornene-2,3-dicarboxylic acid anhydride, bicyclo [2.2.2] octo-5-ene-2,3-dicarboxylic acid anhydride, 2- (2-carboxyethyl) -3-methylmaleic acid Examples thereof include structures derived from anhydrides, 7-oxabicyclo [2.2.1] hepta-5-ene-2,3-dicarboxylic acid anhydrides and the like.

Among the structures represented by the above formula (3), the structures to which the above R ⁵ and R ⁶ are not bound include, for example, tetrapropenyl succinic anhydride, decyl succinic anhydride, tetradecyl succinic anhydride, and tetra. Decenyl succinic anhydride, hexadecyl succinic anhydride, isooctadecenyl succinic anhydride, butyl succinic anhydride, allyl succinic anhydride, 4-hexene-1,2-dicarboxylic acid anhydride, 2- Dodecene-1-yl succinic anhydride, 2,2-dimethylsuccinic anhydride, 2-hexene-1-yl succinic anhydride, 4-methyl-4-penten-1,2-dicarboxylic acid anhydride, 2-octenyl succinic anhydride Examples thereof include structures derived from acid anhydrides, 4,9-decadien-1,2-dicarboxylic acid anhydrides and the like.

In the above formula (1), R ³ represents a group represented by the above formula (2-1) or (2-2). From the viewpoint of excellent low liquid crystal contamination when the curable resin composition of the present invention is used as a sealant for a liquid crystal display element, at least one R ³ is a group represented by the above formula (2-2). Is preferable.

In the above formula (1), X represents the ring-opening structure of the cyclic lactone.
Examples of the cyclic lactone include γ-undecalactone, ε-caprolactone, γ-decalactone, σ-dodecalactone, γ-nonanolactone, γ-heptanolactone, γ-valerolactone, σ-valerolactone, and β-butyrolactone. , Γ-Butyrolactone, β-propiolactone, σ-hexanolactone, 7-butyl-2-oxepanone and the like. Among them, those having 5 or more and 7 or less carbon atoms in the linear portion of the main skeleton when the ring is opened are preferable.
In the above formula (1), 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 excellent adhesiveness to the alignment film and It has the moisture permeation prevention property of the cured product. When the above n is 1 or more and 5 or less, the obtained curable resin composition is more excellent in adhesiveness to the alignment film.

In the above formula (1), Ep represents a structure derived from a bifunctional or higher functional epoxy compound.
Examples of the epoxy compound from which the above Ep is derived include bisphenol A type epoxy compound, bisphenol F type epoxy compound, bisphenol E type epoxy compound, bisphenol S type epoxy compound, hydrogenated bisphenol A type epoxy compound, and hydrogenated bisphenol F type. Epoxy compound, hydrogenated bisphenol E type epoxy compound, hydrogenated bisphenol S type epoxy compound, resorcinol type epoxy compound, dicyclopentadiene type epoxy compound, naphthalene type epoxy compound, fluorene type epoxy compound, rubber modified type epoxy compound, glycidyl ester compound And so on.
Among them, the above 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.

The preferable upper limit of the molecular weight of the epoxy compound from which the Ep is derived is 1000. When the molecular weight of the epoxy compound is 1000 or less, the obtained curable resin composition has a low viscosity and is excellent in handleability. A more preferable upper limit of the molecular weight of the epoxy compound is 500.

Examples of the method for producing the compound represented by the above formula (1) include the following methods.
That is, first, the above-mentioned polyol and the above-mentioned optionally substituted dicarboxylic acid or its anhydride are heated and stirred in the presence of a polymerization inhibitor to obtain the reaction product 1. Next, the above-mentioned bifunctional or higher functional epoxy compound is added to the obtained reaction product 1 and heated and stirred to obtain the reaction product 2. Then, by a method having a step of reacting a part or all of the epoxy groups with (meth) acrylic acid by adding (meth) acrylic acid to the obtained reaction product 2 and heating and stirring, the above formula (1) is used. The compound represented can be obtained.
The polyol may be reacted with the cyclic lactone before being reacted with the optionally substituted dicarboxylic acid or its anhydride.
In addition, in this specification, the said "(meth) acrylic" means acrylic or methacrylic.

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

The preferable lower limit of the content of the compound represented by the above formula (1) in 100 parts by weight of the curable resin is 5 parts by weight, and the preferable upper limit is 95 parts by weight. When the content of the compound represented by the above formula (1) is in this range, the obtained curable resin composition is more excellent in the effect of achieving both adhesiveness to the alignment film and moisture permeation prevention property. The more preferable lower limit of the content of the compound represented by the above formula (1) is 10 parts by weight, and the more preferable upper limit is 90 parts by weight.

The curable resin composition of the present invention may further contain other curable resin other than the compound represented by the above formula (1) as the curable resin as long as the object of the present invention is not impaired. Good.
Examples of the other curable resin include other epoxy compounds and other (meth) acrylic compounds other than the compound represented by the above formula (1).
In the present specification, the above-mentioned "(meth) acrylic" means acrylic or methacrylic, and the above-mentioned "(meth) acrylic compound" means a compound having a (meth) acryloyl group.

Examples of the other epoxy compounds include bisphenol A type epoxy compound, bisphenol F type epoxy compound, bisphenol S type epoxy compound, 2,2'-diallyl bisphenol A type epoxy compound, hydrogenated bisphenol type epoxy compound, and propylene oxide addition. Bisphenol A type epoxy compound, resorsinol 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 novolac type epoxy compound , Dicyclopentadiene novolac type epoxy compound, biphenyl novolac type epoxy compound, naphthalenephenol novolac type epoxy compound, glycidylamine type epoxy compound, alkyl polyol type epoxy compound, rubber modified epoxy compound, glycidyl ester compound 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 Corporation), 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 Corporation) and the like.
Among the above 2,2'-diallyl bisphenol A type epoxy compounds, commercially available ones include, for example, RE-810NM (manufactured by Nippon Kayaku Co., Ltd.).
Examples of commercially available hydrogenated bisphenol type epoxy compounds include EPICLON EXA7015 (manufactured by DIC Corporation) and the like.
Examples of commercially available propylene oxide-added bisphenol A type epoxy compounds include EP-4000S (manufactured by ADEKA Corporation) and the like.
Examples of commercially available resorcinol-type epoxy compounds include EX-201 (manufactured by Nagase ChemteX Corporation) 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 Corporation) and the like.
Examples of commercially available naphthalene-type epoxy compounds include EPICLON HP4032 and EPICLON EXA-4700 (both manufactured by DIC Corporation).
Examples of commercially available phenol novolac type epoxy compounds include EPICLON N-770 (manufactured by DIC Corporation) and the like.
Examples of commercially available orthocresol novolac type epoxy compounds include EPICLON N-670-EXP-S (manufactured by DIC Corporation) and the like.
Examples of commercially available dicyclopentadiene novolac type epoxy compounds include EPICLON HP7200 (manufactured by DIC Corporation) 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 naphthalene phenol 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, Inc.) and the like.
Commercially available alkyl polyol type epoxy compounds include, for example, ZX-1542 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), EPICLON 726 (manufactured by DIC Corporation), Epolite 80MFA (manufactured by Kyoei Co., Ltd.), and Denacol EX-611. (Manufactured by Nagase ChemteX Corporation) and the like.
Examples of commercially available rubber-modified epoxy compounds include YR-450, YR-207 (all manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), Epolide PB (manufactured by Daicel Co., Ltd.), and the like.
Examples of commercially available glycidyl ester compounds include Denacol EX-147 (manufactured by Nagase ChemteX Corporation) 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 Corporation), jER1031 and jER1032 (all of which are manufactured by Asahi Kasei Corporation). Mitsubishi Chemical Corporation), EXA-7120 (DIC Corporation), TEPIC (Nissan Chemical Industries, Ltd.) and the like.

Further, the curable resin may contain a partially (meth) acrylic-modified epoxy resin as the other epoxy compound.
In the present specification, the above-mentioned partial (meth) acrylic-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. It means a compound having one or more epoxy groups and one or more (meth) acryloyl groups in one molecule.

Examples of the other (meth) acrylic compound include (meth) acrylic acid ester compounds, epoxy (meth) acrylates, urethane (meth) acrylates, and the like. Of these, epoxy (meth) acrylate is preferable. Further, the (meth) acrylic compound preferably has two or more (meth) acryloyl groups in one molecule from the viewpoint of reactivity.
In the present specification, the above-mentioned "(meth) acrylate" means acrylate or methacrylate, and the above-mentioned "epoxy (meth) acrylate" means that all epoxy groups in the epoxy compound are referred to as (meth) acrylic acid. Represents a reacted compound.

Among the above (meth) acrylic acid ester compounds, monofunctional ones include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, and 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 ( Meta) 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, ethylcarbi Thor (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, Iimide (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2-( Examples thereof include 2- (meth) acryloyloxyethyl 2-hydroxypropylphthalate, 2- (meth) acryloyloxyethyl phosphate, and glycidyl (meth) acrylate.

Among the above (meth) acrylic acid ester compounds, bifunctional ones 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-nonane diol di (meth) acrylate, 1,10-decane diol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (Meta) 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) ) Acrylic, 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 , Dimethylol dicyclopentadienyldi (meth) acrylate, ethylene oxide-modified isocyanurate di (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, carbonatediol di (meth) acrylate, Examples thereof include polyether diol di (meth) acrylate, polyester diol di (meth) acrylate, polycaprolactone diol di (meth) acrylate, and polybutadiene diol di (meth) acrylate.

Among the above (meth) acrylic acid ester compounds, those having trifunctionality or higher include, for example, trimetyl propanetri (meth) acrylate, ethylene oxide-added trimethyl propanetri (meth) acrylate, and propylene oxide-added trimethyl propanetri (meth) acrylate. Meta) acrylate, caprolactone-modified trimethylol propantri (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, ditrimethylolpropantetra (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 used as a raw material for synthesizing the epoxy (meth) acrylate, the same epoxy compound as the other epoxy compounds described above can be used.

Among the above-mentioned epoxy (meth) acrylates, commercially available ones include, for example, epoxy (meth) acrylate manufactured by Daicel Ornex, epoxy (meth) acrylate manufactured by Shin-Nakamura Chemical Industry Co., Ltd., and epoxy (meth) acrylate manufactured by Kyoei Co., Ltd. Examples thereof include meta) acrylate and epoxy (meth) acrylate manufactured by Nagase ChemteX Corporation.
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 Industry Co., Ltd. include EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, and 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, and epoxy ester 1600A. Examples thereof include epoxy ester 3000M, epoxy ester 3000A, epoxy ester 200EA, and epoxy ester 400EA.
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 a (meth) acrylic acid derivative having a hydroxyl group with respect to an isocyanate compound in the presence of a catalytic amount of a tin compound.

Examples of the isocyanate compound include isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4,4'-diisocyanate (MDI), and hydrogenation. MDI, Polymeric MDI, 1,5-naphthalenediocyanate, Norbornan diisocyanate, Trizine diisocyanate, Xylylene diisocyanate (XDI), Hydrogenated XDI, Lysine diisocyanate, Triphenylmethane triisocyanate, Tris (isocyanatephenyl) thiophosphate, Tetramethylxylylene diisocyanate Examples thereof include isocyanates and 1,6,11-undecantry isocyanates.

Further, as the 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 dihydric alcohol, mono (meth) acrylate of trihydric alcohol, and 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 divalent 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 and the like.

Among the above urethane (meth) acrylates, commercially available ones include, for example, urethane (meth) acrylate manufactured by Toa Synthetic Co., Ltd., urethane (meth) acrylate manufactured by Daicel Ornex, and urethane (meth) manufactured by Negami Kogyo Co., Ltd. Examples thereof include acrylate, urethane (meth) acrylate manufactured by Shin-Nakamura Chemical Industry Co., Ltd., and urethane (meth) acrylate manufactured by Kyoeisha Chemical Co., Ltd.
Examples of the urethane (meth) acrylate manufactured by Toagosei Co., Ltd. include M-1100, M-1200, M-1210, and M-1600.
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, and Art Resin UN-. 7100, Art Resin UN-9000A, Art Resin UN-9000H and the like can be mentioned.
Examples of the urethane (meth) acrylate manufactured by Shin-Nakamura Chemical Industry Co., Ltd. include U-2HA, U-2PHA, U-3HA, U-4HA, U-6H, U-6HA, U-6LPA, U-10H, and the like. 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- Examples thereof include 4100, UA-4200, UA-4400, UA-5201P, UA-7100, UA-7200, and UA-W2A.
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, and UA-306T. Be done.

The other (meth) acrylic compound preferably has a hydrogen-bonding unit such as an -OH group, an -NH- group, or an -NH ₂ group from the viewpoint of suppressing liquid crystal contamination.

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.
The above-mentioned "polymerization initiator and / or thermosetting agent" means either one or both of the polymerization initiator and the thermosetting agent.

Examples of the radical polymerization initiator include a photoradical polymerization initiator that generates radicals by light irradiation, a thermal radical polymerization initiator that generates radicals by heating, and the like.

Examples of the photoradical polymerization initiator include benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanosen compounds, oxime ester compounds, benzoin ether compounds, thioxanthone compounds and the like.
Specific examples of the photoradical polymerization initiator include 1-hydroxycyclohexylphenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone, and 1,2- (dimethylamino). -2-((4-Methylphenyl) methyl) -1- (4- (4-morpholinyl) phenyl) -1-butanone, 2,2-dimethoxy-1,2-diphenylethane-1-one, bis (2) , 4,6-trimethylbenzoyl) Phenylphosphenyl oxide, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, 1- (4- (2-hydroxyethoxy) -phenyl)- 2-Hydroxy-2-methyl-1-propane-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 made of an azo compound, an organic peroxide and the like. Of these, an initiator composed of a polymer azo compound (hereinafter, also referred to as “polymer azo initiator”) is preferable.
In the present specification, the polymer azo compound means a compound having an azo group and having a number average molecular weight of 300 or more, which generates a radical capable of curing the (meth) acryloyl group by heat.

The preferable lower limit of the number average molecular weight of the polymer azo compound is 1000, and the preferable upper limit 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 polymer azo compound is 5000, the more preferable upper limit is 100,000, the further preferable lower limit is 10,000, and the further preferable upper limit is 90,000.

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 a polycondensate of 4,4'-azobis (4-cyanopentanoic acid) and polyalkylene glycol, and 4,4'-azobis (4-cyanopentanoic acid). And a polycondensate of polydimethylsiloxane having a terminal amino group and the like.
Examples of commercially available polymer azo compounds include VPE-0201, VPE-0401, VPE-0601, VPS-0501, and VPS-1001 (all manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.). Be done.
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 peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, peroxyesters, diacyl peroxides, peroxydicarbonates and the like.

As the cationic polymerization initiator, a photocationic polymerization initiator is preferably used.
The photocationic polymerization initiator is not particularly limited as long as it generates protonic acid or Lewis acid by light irradiation, and may be an ionic photoacid generation type or a nonionic photoacid generation type. It may be.

Examples of the photocationic polymerization initiator include onium salts such as aromatic diazonium salt, aromatic halonium salt and aromatic sulfonium salt, and organic metal complexes such as iron-allene complex, titanosen complex and arylsilanol-aluminum complex. Can be mentioned.

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

The content of the polymerization initiator is preferably 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 obtained curable resin composition is used as a sealant for a liquid crystal display element, it is excellent in storage stability and curability while suppressing liquid crystal contamination. It 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 is 5 parts by weight.

Examples of the heat-curing agent include organic acid hydrazide, imidazole derivatives, amine compounds, polyhydric phenolic compounds, acid anhydrides and the like. Of these, solid organic acid hydrazide is preferably used.

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

The content of the thermosetting agent is preferably 1 part by weight and a preferable upper limit of 50 parts by weight with respect to 100 parts by weight of the entire curable resin. When the content of the thermosetting agent is in this range, the obtained curable resin composition becomes 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 by the stress dispersion effect, improving the coefficient of linear expansion, further improving the moisture permeation prevention property of the cured product, and the like. It is preferable to do so.

As the filler, an inorganic filler or an organic filler can be used.
Examples of the inorganic filler include silica, talc, glass beads, asbestos, gypsum, diatomaceous earth, smectite, bentonite, montmorillonite, sericite, active white clay, alumina, zinc oxide, iron oxide, magnesium oxide, tin oxide and 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 preferable 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 preferable upper limit is 70 parts by weight. When the content of the filler is in this range, it is possible to further exert the effect of improving the adhesiveness while suppressing the deterioration of the coatability 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 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 silane coupling agent mainly has a role as an adhesive auxiliary for satisfactorily adhering the curable resin composition to a substrate or the like.
As the silane coupling agent, for example, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane and the like are preferably used.

The preferable 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 parts by weight, and the preferable upper limit is 10 parts by weight. When 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 obtained curable resin composition is used as a sealant for a liquid crystal display element. Can be demonstrated more. 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 is 5 parts by weight.

The curable resin composition of the present invention may contain a light-shielding agent. By containing the above-mentioned 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 for light in the ultraviolet region, particularly for light having a wavelength of 370 nm or more and 450 nm or less, as compared with the average transmittance for light having a wavelength of 300 nm or more and 800 nm or less. That is, the titanium black has a property of imparting 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. As the light-shielding agent contained in the curable resin composition of the present invention, a substance having high insulating properties is preferable, and titanium black is also preferable as the light-shielding agent having high insulating properties.

The above titanium black exerts a sufficient effect 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 oxidation. Surface-treated titanium black, such as those coated with an inorganic component such as zirconium or magnesium oxide, can also be used. Among them, those treated with an organic component are preferable in that the insulating property can be further improved.
Further, the liquid crystal display element manufactured by using the curable resin composition of the present invention containing the titanium black as a light-shielding agent as a sealant for a liquid crystal display element has sufficient light-shielding properties, so that light does not leak out. 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, titanium black manufactured by Ako Kasei Co., Ltd., and the like.
Examples of the titanium black manufactured by Mitsubishi Materials Corporation include 12S, 13M, 13M-C, 13RN, 14MC and the like.
Examples of the titanium black manufactured by Ako Kasei Co., Ltd. include Tilak D and the like.

The preferable lower limit of the specific surface area of the titanium black is 13 m ² / g, the preferable upper limit is 30 m ² / g, the more preferable lower limit is 15 m ² / g, and the more preferable upper limit is 25 m ² / g.
The preferable 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 preferable lower limit is 1 Ω · cm, and the more preferable 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 is 5 μm. When the primary particle size of the light-shielding agent is in this range, the viscosity and thixotropy of the obtained curable resin composition are not significantly increased, and the coatability is improved. The more preferable lower limit of the primary particle diameter of the light shielding agent is 5 nm, the more preferable upper limit is 200 nm, the further preferable lower limit is 10 nm, and the further preferable upper limit 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 further exhibited while maintaining the adhesiveness, the strength after curing, and the drawability of the obtained curable resin composition. The more preferable lower limit of the content of the light-shielding agent is 10 parts by weight, the more preferable upper limit is 70 parts by weight, the more preferable lower limit is 30 parts by weight, and the further preferable upper limit is 60 parts by weight.

The curable resin composition of the present invention further comprises additives such as stress relaxation agents, reactive diluents, rocking agents, spacers, curing accelerators, defoamers, leveling agents, and polymerization inhibitors, if necessary. May be contained.

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, a silane coupling agent to be added as needed, and the like using a mixer are used. Examples thereof include a method of mixing with the additive of.
Examples of the mixer include a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, and three rolls.

The curable resin composition of the present invention can be used as an adhesive, and can be particularly preferably used as a sealant for a liquid crystal display element. A sealant for a liquid crystal display element using the curable resin composition of the present invention is also one of the present inventions.
Further, by blending the conductive fine particles with the sealant for a liquid crystal display element of the present invention, a vertically conductive material can be produced. A vertically conductive material containing the sealant for a liquid crystal display element of the present invention and conductive fine particles is also one of the present inventions.

As the conductive fine particles, metal balls, those having a conductive metal layer formed on the surface of the resin fine particles, and the like can be used. Among them, the one in which the conductive metal layer is formed on the surface of the resin fine particles is preferable because the excellent elasticity of the resin fine particles enables conductive connection without damaging the transparent substrate or the like.

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

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 manufacturing the liquid crystal display element of the present invention using the sealant for the liquid crystal display element of the present invention, the liquid crystal dropping method is preferably used, and specific examples thereof include a method having the following steps. Be done.
First, a step of applying the sealant for a liquid crystal display element of the present invention to one of two transparent substrates having electrodes such as an ITO thin film by screen printing, dispenser application, or the like to form a frame-shaped seal pattern is performed. Next, a step of dropping and applying fine droplets of liquid crystal on the entire surface of the frame of the seal pattern and superimposing the other transparent substrate under vacuum is performed. After that, the liquid crystal display element can be obtained by a method of irradiating the seal pattern portion with light such as ultraviolet rays to temporarily cure the sealant and a step of heating the temporarily cured sealant to perform main curing. it can.

According to the present invention, it is possible to provide a curable resin composition having both excellent adhesiveness to an alignment film and moisture permeation prevention property. Further, according to the present invention, it is possible to provide a sealant for a liquid crystal display element, a vertical conductive material, and a liquid crystal display element 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)
To a reaction flask, 118 parts by weight of 1,6-hexanediol, 296 parts by weight of phthalic anhydride, and 0.1 parts by weight of hydroquinone as a polymerization inhibitor were added, and the mixture was stirred at 90 ° C. for 5 hours using a mantle heater. 760 parts by weight of bisphenol A diglycidyl ether was added to the obtained reaction product, 0.5 part by weight of triphenylphosphine was further added, and the mixture was stirred at 110 ° C. for 5 hours. Then, 144 parts by weight of acrylic acid was added to the obtained reaction product, and the mixture was stirred at 110 ° C. for 5 hours to obtain a curable resin A.
The structure of the curable resin A was analyzed by ¹ H-NMR and ¹³ C-NMR. As a result, in the curable resin A, in the formula (1), m is 2, R ¹ is a structure derived from 1,6-hexanediol, R ² is a structure derived from phthalic anhydride, and R ³ is a formula (2-2). ) group represented by (R ⁴ is a hydrogen atom), n is 0, Ep was confirmed to be the compound 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 the above "(Preparation of curable resin A)" except that 118 parts by weight of 1,6-hexanediol was changed to 258 parts by weight of 1,16-hexadecanediol.
The structure of the curable resin B was analyzed by ¹ H-NMR and ¹³ C-NMR. As a result, in the curable resin B, in the formula (1), m is 2, R ¹ is a structure derived from 1,16-hexadecanediol, R ² is a structure derived from phthalic anhydride, and R ³ is a formula (2-2). ) group represented by (R ⁴ is a hydrogen atom), n is 0, Ep was confirmed to be the compound is a structure derived from bisphenol a diglycidyl ether.

(Preparation of curable resin C)
Except that 118 parts by weight of 1,6-hexanediol was changed to 234 parts by weight of bisphenol A and 760 parts by weight of bisphenol A diglycidyl ether was changed to 536 parts by weight of dicyclopentadiene diglycidyl ether, the above "(curable resin A) was changed. The curable resin C was obtained in the same manner as in the above procedure.
The structure of the curable resin C was analyzed by ¹ H-NMR and ¹³ C-NMR. As a result, the curable resin C is represented by the formula (1), in which m is 2, R ¹ is a structure derived from bisphenol A, R ² is a structure derived from phthalic anhydride, and R ³ is a formula (2-2). that group (R ⁴ is a hydrogen atom), n is 0, Ep was confirmed to be the compound is a structure derived from dicyclopentadiene diglycidyl ether.

(Preparation of curable resin D)
A curable resin D was obtained in the same manner as in the above "(Preparation of curable resin A)" except that 760 parts by weight of bisphenol A diglycidyl ether was changed to 720 parts by weight of bisphenol F diglycidyl ether.
The structure of the curable resin D was analyzed by ¹ H-NMR and ¹³ C-NMR. As a result, in the curable resin D, in the formula (1), m is 2, R ¹ is a structure derived from 1,6-hexanediol, R ² is a structure derived from phthalic anhydride, and R ³ is a formula (2-2). ) group represented by (R ⁴ is a hydrogen atom), n is 0, Ep was confirmed to be the compound is a structure derived from bisphenol F diglycidyl ether.

(Preparation of curable resin E)
Except that 296 parts by weight of phthalic anhydride was changed to 536 parts by weight of tetrapropenyl succinic anhydride and 760 parts by weight of bisphenol A diglycidyl ether was changed to 720 parts by weight of bisphenol F diglycidyl ether, the above "(curable resin A) The curable resin E was obtained in the same manner as in the above procedure.
The structure of the curable resin E was analyzed by ¹ H-NMR and ¹³ C-NMR. As a result, in the curable resin E, in the formula (1), m is 2, R ¹ is a structure derived from 1,6-hexanediol, R ² is a structure derived from tetrapropenyl succinic anhydride, and R ³ is a formula (2). groups represented by -2) (R ⁴ is a hydrogen atom), n is 0, Ep was confirmed to be the compound is a structure derived from bisphenol F diglycidyl ether.

(Preparation of curable resin F)
Except that 296 parts by weight of phthalic anhydride was changed to 336 parts by weight of 4-methylcyclohexane-1,2-dicarboxylic acid anhydride, and 760 parts by weight of bisphenol A diglycidyl ether was changed to 720 parts by weight of bisphenol F diglycidyl ether. , The curable resin F was obtained in the same manner as in the above "(Preparation of curable resin A)".
The structure of the curable resin F was analyzed by ¹ H-NMR and ¹³ C-NMR. As a result, the curable resin F has a structure in the formula (1) in which m is 2 and R ¹ is derived from 1,6-hexanediol, and R ² is derived from 4-methylcyclohexane-1,2-dicarboxylic acid anhydride. It was confirmed that the structure, R ³ is a group represented by the formula (2-2) (R ⁴ is a hydrogen atom), n is 0, and Ep is a compound derived from bisphenol F diglycidyl ether.

(Preparation of curable resin G)
A curable resin G was obtained in the same manner as in the above "(Preparation of curable resin F)" except that 144 parts by weight of acrylic acid was changed to 168 parts by weight of methacrylic acid.
The structure of the curable resin G was analyzed by ¹ H-NMR and ¹³ C-NMR. As a result, the curable resin G has a structure in the formula (1) in which m is 2 and R ¹ is derived from 1,6-hexanediol, and R ² is derived from 4-methylcyclohexane-1,2-dicarboxylic acid anhydride. It was confirmed that the structure, R ³ is a group represented by the formula (2-2) (R ⁴ is a methyl group), n is 0, and Ep is a compound derived from bisphenol F diglycidyl ether.

(Preparation of curable resin H)
To a reaction flask, 118 parts by weight of 1,6-hexanediol, 228 parts by weight of ε-caprolactone, and 0.1 parts by weight of hydroquinone as a polymerization inhibitor were added, and the mixture was stirred at 90 ° C. for 5 hours using a mantle heater. Then, 296 parts by weight of phthalic anhydride was added, and the mixture was further stirred for 5 hours. 760 parts by weight of bisphenol A diglycidyl ether was added to the obtained reaction product, 0.5 part by weight of triphenylphosphine was further added, and the mixture was stirred at 110 ° C. for 5 hours. Then, 144 parts by weight of acrylic acid was added to the obtained reaction product, and the mixture was stirred at 110 ° C. for 5 hours to obtain a curable resin H.
The structure of the curable resin H was analyzed by ¹ H-NMR and ¹³ C-NMR. As a result, in the curable resin H, in the formula (1), m is 2, R ¹ is a structure derived from 1,6-hexanediol, R ² is a structure derived from phthalic anhydride, and R ³ is a formula (2-2). ) Is a group (R ⁴ is a hydrogen atom), X is a ring-opening structure of ε-caprolactone, n is 1.9 (average value), and Ep is a compound derived from bisphenol A diglycidyl ether. It was confirmed.

(Preparation of curable resin I)
A curable resin I was obtained in the same manner as in the above "(Preparation of curable resin A)" except that the blending amount of acrylic acid was changed to 72 parts by weight.
The structure of the curable resin I was analyzed by ¹ H-NMR and ¹³ C-NMR. As a result, the curable resin I contained 52% by weight of the compound I-1 represented by the formula (1), 23% by weight of the compound I-2 represented by the formula (1), and 23% of the bisphenol A diglycidyl ether. It was confirmed that it contained% by weight.
Compound I-1 has a structure in the formula (1) in which m is 2, R ¹ is derived from 1,6-hexanediol, R ² is a structure derived from phthalic anhydride, and one of R ³ is the formula (2-1). group a group represented by the other is represented by formula (2-2) is (R ⁴ is a hydrogen atom), compounds wherein n 0, Ep is a structure derived from bisphenol a diglycidyl ether.
Compound I-2 is represented by the formula (1), in which m is 2, R ¹ is a structure derived from 1,6-hexanediol, R ² is a structure derived from phthalic anhydride, and R ³ is a structure derived from formula (2-2). it is the group (R ⁴ is a hydrogen atom), n is 0, Ep is a compound a structure derived from bisphenol a diglycidyl ether.

(Preparation of curable resin J)
To the reaction flask, 118 parts by weight of 1,6-hexanediol, 336 parts by weight of 4-methylcyclohexane-1,2-dicarboxylic acid anhydride, and 0.1 parts by weight of hydroquinone as a polymerization inhibitor were added, and a mantle heater was added. It was stirred at 90 ° C. for 5 hours. 720 parts by weight of bisphenol F diglycidyl ether was added to the obtained reaction product, 0.5 part by weight of triphenylphosphine was further added, and the mixture was stirred at 110 ° C. for 5 hours to obtain a curable resin J.
The structure of the curable resin J was analyzed by ¹ H-NMR and ¹³ C-NMR. As a result, the curable resin J has a structure in the formula (1) in which m is 2 and R ¹ is derived from 1,6-hexanediol, and R ² is derived from 4-methylcyclohexane-1,2-dicarboxylic acid anhydride. It was confirmed that the structure, R ³ is a group represented by the formula (2-1), n is 0, and Ep is a compound derived from bisphenol F diglycidyl ether.

(Preparation of curable resin K)
Except that 760 parts by weight of bisphenol A diglycidyl ether was changed to 924 parts by weight of 9,9-bis (4-glycidyloxy-3-phenyl) full orange glycidyl ether, the above "(preparation of curable resin A)" was applied. A curable resin K was obtained in the same manner.
The structure of the curable resin K was analyzed by ¹ H-NMR and ¹³ C-NMR. As a result, in the curable resin K, in the formula (1), m is 2, R ¹ is a structure derived from 1,6-hexanediol, R ² is a structure derived from phthalic anhydride, and R ³ is a formula (2-2). ) group represented by ^{(R 4} is a hydrogen atom), verify that n is 0, Ep is the 9,9-bis (4-glycidyloxy-3-phenyl) compound is a structure derived from diglycidyl ether did.

(Preparation of curable resin L)
Except for changing 760 parts by weight of bisphenol A diglycidyl ether to 544 parts by weight of 1,6-bis (2,3-epoxypropane-1-yloxy) naphthalene diglycidyl ether, the above "(Preparation of curable resin A)" A curable resin L was obtained in the same manner as above.
The structure of the curable resin L was analyzed by ¹ H-NMR and ¹³ C-NMR. As a result, in the curable resin L, in the formula (1), m is 2, R ¹ is a structure derived from 1,6-hexanediol, R ² is a structure derived from phthalic anhydride, and R ³ is a formula (2-2). ) (R ⁴ is a hydrogen atom), n is 0, Ep is 1,6-bis (2,3-epoxypropane-1-yloxy), and the compound has a structure derived from naphthalenediglycidyl ether. It was confirmed.

(Preparation of curable resin M)
A curable resin M was obtained in the same manner as in the above "(Preparation of curable resin A)" except that 760 parts by weight of bisphenol A diglycidyl ether was changed to 444 parts by weight of resorcinol diglycidyl ether.
The structure of the curable resin M was analyzed by ¹ H-NMR and ¹³ C-NMR. As a result, in the curable resin M, in the formula (1), m is 2, R ¹ is a structure derived from 1,6-hexanediol, R ² is a structure derived from phthalic anhydride, and R ³ is a formula (2-2). ) group represented by (R ⁴ is a hydrogen atom), n is 0, Ep was confirmed to be the compound is a structure derived from resorcinol diglycidyl ether.

(Preparation of curable resin N)
A curable resin N was obtained in the same manner as in the above "(Preparation of curable resin A)" except that 760 parts by weight of bisphenol A diglycidyl ether was changed to 706 parts by weight of hydrogenated bisphenol A diglycidyl ether.
Structural analysis of the curable resin N was performed by ¹ H-NMR and ¹³ C-NMR. As a result, in the curable resin N, in the formula (1), m is 2, R ¹ is a structure derived from 1,6-hexanediol, R ² is a structure derived from phthalic anhydride, and R ³ is a formula (2-2). ) group represented by (R ⁴ is a hydrogen atom), n is 0, Ep was confirmed to be the compound is a structure derived from hydrogenated bisphenol a diglycidyl ether.

(Preparation of curable resin O)
To the reaction flask, 298 parts by weight of 1,6-hexanediol diglycidyl ether and 456 parts by weight of bisphenol A were added, the temperature was raised to 150 ° C. using a mantle heater, and 1 part by weight of a 4% NaOH aqueous solution was added to 150 ° C. Was stirred for 3 hours. After confirming that the liquid temperature had dropped to 60 ° C., 500 parts by weight of chloroform was added, and the mixture was washed 5 times with 500 parts by weight of a 1% NaOH aqueous solution and 3 times with 1000 parts by weight of water. Then, the reaction product was dried over magnesium sulfate, filtered, and the solvent was flushed off under reduced pressure. 295 parts by weight of epichlorohydrin was added to the reaction product, and the mixture was stirred at 80 ° C. for 2 hours. Then, 144 parts by weight of acrylic acid was added to the obtained reaction product, and the mixture was stirred at 110 ° C. for 5 hours to obtain a curable resin O.
The structure of the curable resin O was analyzed by ¹ H-NMR and ¹³ C-NMR. As a result, it was confirmed that the curable resin O was a compound represented by the following formula (5).

(Preparation of curable resin P)
To the reaction flask, 298 parts by weight of 1,6-hexanediol diglycidyl ether and 456 parts by weight of bisphenol A were added, the temperature was raised to 150 ° C. using a mantle heater, and 1 part by weight of a 4% NaOH aqueous solution was added to 150 ° C. Was stirred for 3 hours. After confirming that the liquid temperature had dropped to 60 ° C., 500 parts by weight of chloroform was added, and the mixture was washed 5 times with 500 parts by weight of a 1% NaOH aqueous solution and 3 times with 1000 parts by weight of water. Then, 295 parts by weight of epichlorohydrin was added to the reaction product obtained by drying and filtering with magnesium sulfate and flowing off the solvent under reduced pressure, and the mixture was stirred at 80 ° C. for 2 hours to obtain a curable resin P. It was.
The structure of the curable resin P was analyzed by ¹ H-NMR and ¹³ C-NMR. As a result, it was confirmed that the curable resin P was a compound represented by the following formula (6).

(Examples 1 to 16, Comparative Examples 1 to 4)
According to the compounding ratios shown in Tables 1 and 2, each material was stirred with a planetary stirrer, then uniformly mixed with three ceramic rolls, and cured of Examples 1 to 16 and Comparative Examples 1 to 4. A sex resin composition was obtained. As the planetary agitator, Awatori Rentaro (manufactured by Shinky Co., Ltd.) was used.

<Evaluation>
The following evaluations were performed on each of the curable resin compositions obtained in Examples and Comparative Examples. The results are shown in Tables 1 and 2.

(Adhesion to alignment film)
An imide resin was applied to a glass substrate with an ITO thin film by spin coating, prebaked at 80 ° C., and then fired at 230 ° C. to prepare a substrate with an alignment film. SE7492 (manufactured by Nissan Chemical Industries, Ltd.) was used as the imide resin.
With respect 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. SI-H055 (manufactured by Sekisui Chemical Co., Ltd.) was used as the silica spacer. Next, a curable resin composition in which silica spacers were dispersed was added dropwise onto the alignment film of the substrate with the alignment film. Another substrate with an alignment film is attached to the substrate with an alignment film on which the curable resin composition is dropped in a cross shape via the curable resin composition, and after irradiating with an ultraviolet ray of 3000 mJ / cm ² with a metal halide lamp, Adhesion test pieces were obtained by heating at 120 ° C. for 60 minutes. When the edge of the substrate in the produced adhesive test piece was pushed in at a speed of 5 mm / min using a metal cylinder having a radius of 5 mm, the strength at which the panel peeled off was measured. The value obtained by dividing the obtained measured value (kgf) by the seal diameter (cm) was "◎" when it was 3.0 kgf / cm or more, and it was 2.5 kgf / cm or more and less than 3.0 kgf / cm. The case was evaluated as "○", the case of 2.0 kgf / cm or more and less than 2.5 kgf / cm was evaluated as "Δ", and the case of less than 2.0 kgf / cm was evaluated as "x" to evaluate the adhesiveness to the alignment film. ..

(Moisture prevention)
Each of the curable resin compositions obtained in Examples and Comparative Examples was applied onto a smooth release film using a coater so as to have a thickness of 200 μm or more and 300 μm or less. Next, a film for measuring moisture permeability was obtained by irradiating with an ultraviolet ray of 3000 mJ / cm ² using a metal halide lamp and then heating at 120 ° C. for 60 minutes. A cup for moisture permeability test is prepared by a method according to the moisture permeability test method (cup method) of the moisture-proof packaging material of JIS Z 0208, the obtained film for moisture permeability measurement is attached, and a constant temperature of 80 ° C. and 90% humidity RH is attached. It was put into a constant humidity oven and the moisture permeability was measured. The obtained value of the moisture permeability, the case was less than ^50g / m 2 · 24hr "◎", the case was less than ^50g / m 2 · 24hr or more ^60g / m 2 · 24hr "○", 60g / 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)
An imide resin was applied to a glass substrate with an ITO thin film by spin coating, prebaked at 80 ° C., and then fired at 230 ° C. to prepare a substrate with an alignment film. SE7492 (manufactured by Nissan Chemical Industries, Ltd.) was used as the imide resin.
With respect 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 defoamed to be contained in the curable resin composition. After removing the foam, the resin was filled in a syringe for dispensing and defoamed 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 a dispenser, SHOTMASTER 300 (manufactured by Musashi Engineering Co., Ltd.) was used. Subsequently, fine droplets of TN liquid crystal were dropped and applied into the frame of the curable resin composition by a liquid crystal dropping device. Another substrate with an alignment film is laminated on a substrate with an alignment film to which TN liquid crystal is dropped and coated via a curable resin composition, and the two substrates are bonded together under a reduced pressure of 5 Pa with a vacuum bonding device. Got As the TN liquid crystal, JC-5001LA (manufactured by Chisso) was used. The obtained cell was irradiated with ultraviolet rays of 3000 mJ / cm ² with a metal halide lamp, and then heated at 120 ° C. for 60 minutes to cure the curable resin composition, thereby producing a liquid crystal display element. The obtained liquid crystal display element was stored in an environment of a temperature of 80 ° C. and a humidity of 90% RH for 144 hours, and then was driven by a voltage of AC3.5V, and the presence or absence of display unevenness (color unevenness) was visually observed. "◎" when there is no display unevenness around the liquid crystal display element, "○" when a slightly light display unevenness is seen, "△" when there is a clear dark display unevenness, clearly The display performance of the liquid crystal display element was evaluated as "x" when the dark display unevenness was spread not only to the peripheral portion but also to the central portion.
The liquid crystal display elements with evaluations of "◎" and "○" are at a level where there is no problem in practical use.

According to the present invention, it is possible to provide a curable resin composition having both excellent adhesiveness to an alignment film and moisture permeation prevention property. Further, according to the present invention, it is possible to provide a sealant for a liquid crystal display element, a vertical conductive material, and a liquid crystal display element using the curable resin composition.

Claims (6)

1. A curable resin composition containing a curable resin and a polymerization initiator and / or a thermosetting agent, wherein the curable resin contains a compound represented by the following formula (1).
   

   

   In formula (1), m is an integer of 2 or more and 4 or less, R ¹ represents a structure derived from an m-valent polyol, and R ² is derived from a optionally substituted dicarboxylic acid or an anhydride thereof. Represents the structure, R ³ represents the group represented by the following formula (2-1) or (2-2), X represents the ring-opening structure of the cyclic lactone, and n is 0 or more and 5 or less (mean). Value), and Ep represents a structure derived from a bifunctional or higher functional epoxy compound.
   

   

   In formulas (2-1) and (2-2), * represents a bond position, and in formula (2-2), R ⁴ represents a hydrogen atom or a methyl group.
2. The curable resin composition according to claim 1, wherein R ² in the formula (1) has a structure represented by the following formula (3).
   

   

   In the formula (3), * represents a bond position, and R ⁵ and R ⁶ each independently represent a hydrogen atom or an organic group having 1 or more and 60 or less carbon atoms, or R ⁵ and R. Represents a structure in which ⁶ is bonded.
3. The curable resin composition according to claim ² , wherein R ² in the formula (1) has a structure represented by the following formula (4-1) or (4-2).
   

   

   In formula (4-1), * represents a bond position, and in formula (4-1), R ⁷ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and formula (4-2). ), R ⁸ represents a hydrogen atom or an alkyl group having 1 or more and 10 or less carbon atoms.
4. A sealant for a liquid crystal display element using the curable resin composition according to claim 1, 2 or 3.
5. A vertically conductive material containing the sealant for a liquid crystal display element according to claim 4 and conductive fine particles.
6. A liquid crystal display element having a cured product of the sealant for a liquid crystal display element according to claim 4 or a cured product of a vertically conductive material according to claim 5.