JP7160907B2 - Sealant for liquid crystal display element for substrate with polyimide alignment film, vertical conduction material, and liquid crystal display element - Google Patents

Description

TECHNICAL FIELD The present invention relates to a curable resin composition that is excellent in both adhesion to alignment films and moisture permeation resistance. The present invention also relates to a sealant for liquid crystal display elements, a vertically conductive material, and a liquid crystal display element, each using the curable resin composition.

In recent years, as a method for manufacturing a liquid crystal display element such as a liquid crystal display cell, from the viewpoint of shortening the tact time and optimizing the amount of liquid crystal used, curable resin compositions such as those disclosed in Patent Documents 1 and 2 are used. is used as a sealant, which is called a dropping method.
In the dropping method, first, one of two substrates with electrodes is coated with a sealant to form a frame-shaped seal pattern. Next, liquid crystal microdroplets are dropped into the seal frame of the substrate while the sealant is not yet cured, and the other substrate is superimposed under vacuum, and the sealant is cured by light irradiation or heating to fabricate a liquid crystal display device. do. At present, this dripping method is the mainstream method for manufacturing liquid crystal display elements.

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

JP-A-2001-133794 WO 02/092718

With the spread of tablet devices and mobile devices, liquid crystal display elements are increasingly required to have moisture resistance reliability when driven in high-temperature and high-humidity environments. is more demanded. In order to improve the moisture resistance reliability of liquid crystal display elements, it is necessary to improve the adhesiveness of the sealant to the substrate, etc. in order to prevent water from entering from the interface between the sealant and the substrate, etc., and to prevent the sealant from permeating moisture. need to improve performance. As a method for improving the moisture permeation resistance of the sealant, it is conceivable to add a filler such as talc. there were. In particular, when the application position of the sealant is on an alignment film such as polyimide, it has been difficult to achieve both adhesion to the alignment film and moisture permeation resistance.

An object of the present invention is to provide a curable resin composition that is excellent in both adhesion to an alignment film and moisture permeation resistance. Another object of the present invention is to provide a sealant for liquid crystal display elements, a vertically conductive material, and a liquid crystal display element, each using the curable resin composition.

The present invention contains a curable resin and a polymerization initiator and / or a thermosetting agent, the curable resin is a compound represented by the following formula (1-1) and / or the following formula (1-2) It is a sealant for a liquid crystal display element for a substrate with a polyimide alignment film containing a compound represented by.

In 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 its anhydride, X represents a ring-opening structure of a cyclic lactone, n is 0 or more 5 or less, and Ep represents a structure derived from a bifunctional or higher epoxy compound.

In formulas (2-1) to (2-3), * represents a bonding position; in formula (2-2), a is an integer of 1 or more and 8 or less; 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 inventors of the present invention found that a curable resin composition having both excellent adhesion to an alignment film and excellent moisture permeability resistance can be obtained by using a compound having a specific structure as a curable resin. I came to complete it.

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 the alignment film. Excellent in both moisture resistance. In addition, from the viewpoint of low liquid crystal contamination when used as a sealant for liquid crystal display elements, both the compound represented by the above formula (1-1) and the compound represented by the above formula (1-2) are excellent. Shows low liquid crystal contamination. The curable resin preferably contains a compound represented by formula (1-1).

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

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

As the substituent when the optionally substituted aliphatic dicarboxylic acid or anhydride thereof is substituted, for example, a carbon chain having 1 to 60 carbon atoms which may have an unsaturated bond or a branched structure , a hydrocarbon skeleton containing a cyclic structure, and the like. Among them, a hydrocarbon skeleton containing a cyclic structure is preferable from the viewpoint of enhancing the moisture permeability prevention property.

Specific examples of the optionally substituted aliphatic dicarboxylic acid or anhydride thereof include, for example, 1,2-cyclohexanedicarboxylic anhydride, 3-methylcyclohexane-1,2-dicarboxylic anhydride, 4- Methylcyclohexane-1,2-dicarboxylic anhydride, 4-cyclohexene-1,2-dicarboxylic acid, 3-methyl-4-cyclohexene-1,2-dicarboxylic anhydride, 3,4,5,6-tetrahydrophthal acid anhydride, 4-methyl-4-cyclohexene-1,2-dicarboxylic anhydride, tetrapropenylsuccinic anhydride, decylsuccinic anhydride, tetradecylsuccinic anhydride, tetradecenylsuccinic anhydride, hexa decylsuccinic anhydride, isooctadecenylsuccinic anhydride, butylsuccinic anhydride, allylsuccinic anhydride, 4-hexene-1,2-dicarboxylic anhydride, 2-dodecen-1-ylsuccinic anhydride, 2,2-dimethylsuccinic anhydride, 2-hexene-1-ylsuccinic anhydride, 4-methyl-4-pentene-1,2-dicarboxylic anhydride, 2-octenylsuccinic anhydride, 4,9-decadiene -1,2-dicarboxylic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, bicyclo[2.2.2]oct-5-ene-2,3-dicarboxylic anhydride, 2-(2 -carboxyethyl)-3-methylmaleic anhydride, 7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride, and dicarboxylic acids thereof.

From the viewpoint of further improving the adhesiveness 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 formula (3-2), R ⁵ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and in formula (3-3), R ⁶ and R ⁷ 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 anhydride, 3-methylcyclohexane-1,2-dicarboxylic 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 anhydride, 3,4,5 ,6-tetrahydrophthalic anhydride, 4-methyl-4-cyclohexene-1,2-dicarboxylic 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. , a structure in which R ⁶ and R ⁷ are bonded is preferable from the viewpoint of enhancing moisture permeability prevention.
Examples of structures in which R ⁶ and R ⁷ are not bonded include tetrapropenylsuccinic anhydride, decylsuccinic anhydride, tetradecylsuccinic anhydride, tetradecenylsuccinic anhydride, and hexadecylsuccinic anhydride. , isooctadecenylsuccinic anhydride, butylsuccinic anhydride, allylsuccinic anhydride, 4-hexene-1,2-dicarboxylic anhydride, 2-dodecen-1-ylsuccinic anhydride, 2,2- dimethylsuccinic anhydride, 2-hexene-1-ylsuccinic anhydride, 4-methyl-4-pentene-1,2-dicarboxylic anhydride, 2-octenylsuccinic anhydride, 4,9-decadiene-1,2 - Structures derived from dicarboxylic anhydrides and the like.
Structures to which R ⁶ and R ⁷ are bonded include, for example, 5-norbornene-2,3-dicarboxylic 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 formulas (1-1) and (1-2) above, X represents an open ring 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 and β-butyrolactone. , γ-butyrolactone, β-propiolactone, σ-hexanolactone, 7-butyl-2-oxepanone and the like. Among them, those in which the straight-chain portion of the main skeleton has 5 or more and 7 or less carbon atoms when the ring is opened are preferable.
In the above formulas (1-1) and (1-2), when n is 0, that is, even when there is no ring-opened structure of the cyclic lactone represented by X, the resulting curable resin composition is It has excellent adhesion to the alignment film and moisture permeation resistance of the cured product. When the above n is 1 or more and 5 or less, the resulting curable resin composition is more excellent in adhesiveness to the alignment film. Further, the compound represented by the formula (1-1) and the compound represented by the formula (1-2) may be a mixture of compounds with different repeating numbers of X, in which case the above n 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.
Epoxy compounds from which Ep is derived include, for example, bisphenol A-type epoxy compounds, bisphenol F-type epoxy compounds, bisphenol E-type epoxy compounds, bisphenol S-type epoxy compounds, resorcinol-type epoxy compounds, dicyclopentadiene-type epoxy compounds, and naphthalene. epoxy compounds, rubber-modified epoxy compounds, glycidyl ester compounds, and the like.
Above all, 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 a hydroxyalkyl (meth)acrylate and 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 step of reacting a part of the epoxy groups by adding the above-mentioned difunctional or higher epoxy compound to the product and heating and stirring.
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 a hydroxyalkyl (meth)acrylate and 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 step of reacting all the epoxy groups by adding the above-mentioned difunctional or higher epoxy compound to the product and heating and stirring.
In addition, in this specification, the said "(meth)acrylate" means an acrylate or a methacrylate.

Examples of the hydroxyalkyl (meth)acrylates include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, acrylates and the like.
The hydroxyalkyl (meth)acrylate may be reacted with the cyclic lactone before reacting with the optionally substituted aliphatic dicarboxylic acid or anhydride thereof.

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

The preferred lower limit of the content of the compound represented by formula (1-1) and/or the compound represented by formula (1-2) in 100 parts by weight of the curable resin is 5 parts by weight, and the preferred upper limit is 90 parts by weight. Department. When the content of the compound represented by the formula (1-1) and/or the compound represented by the formula (1-2) is within this range, the resulting curable resin composition has adhesion to the alignment film. and moisture permeation prevention property. A more preferable lower limit to the content of the compound represented by formula (1-1) and/or the compound represented by formula (1-2) is 10 parts by weight, and a more preferable upper limit is 80 parts by weight.
Incidentally, the above "content of the compound represented by formula (1-1) and / or the compound represented by formula (1-2)", if only one of these compounds is contained, the content means the content of one of the compounds, and when it contains both, it means the total content.

The curable resin composition of the present invention further includes a compound represented by the above formula (1-1) and a compound represented by the above formula (1-2) as the curable resin, as long as the object of the present invention is not hindered. It may contain other curable resins other than the compound described above.
Examples of the other curable resins include, for example, epoxy compounds other than the compound represented by the above formula (1-1), and other (meth)acryl compounds other than the compound represented by the above formula (1-2). compounds and the like.
In addition, in this specification, the above-mentioned "(meth)acryl" means acryl or methacryl, and the above-mentioned "(meth)acrylic compound" means a compound having a (meth)acryloyl group.

Examples of the above other epoxy compounds include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol S type epoxy compounds, 2,2'-diallylbisphenol A type epoxy compounds, hydrogenated bisphenol type epoxy compounds, propylene oxide adducts. Bisphenol A type epoxy compounds, resorcinol type epoxy compounds, biphenyl type epoxy compounds, sulfide type epoxy compounds, diphenyl ether type epoxy compounds, dicyclopentadiene type epoxy compounds, naphthalene type epoxy compounds, phenol novolac type epoxy compounds, ortho-cresol novolac type epoxy compounds , dicyclopentadiene novolak-type epoxy compounds, biphenyl novolac-type epoxy compounds, naphthalenephenol novolak-type epoxy compounds, glycidylamine-type epoxy compounds, alkylpolyol-type epoxy compounds, rubber-modified epoxy compounds, glycidyl ester compounds, and the like.

Commercially available bisphenol A type epoxy compounds include, for example, 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).
Examples of commercially available 2,2'-diallylbisphenol A type epoxy compounds include RE-810NM (manufactured by Nippon Kayaku Co., Ltd.).
Examples of commercially available hydrogenated bisphenol type epoxy compounds include EPICLON EXA7015 (manufactured by DIC Corporation).
Examples of commercially available propylene oxide-added bisphenol A type epoxy compounds include EP-4000S (manufactured by ADEKA).
Commercially available resorcinol-type epoxy compounds include, for example, EX-201 (manufactured by Nagase ChemteX Corporation).
Commercially available biphenyl-type epoxy compounds include, for example, jER YX-4000H (manufactured by Mitsubishi Chemical Corporation).
Examples of commercially available sulfide-type epoxy compounds include YSLV-50TE (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.).
Examples of commercially available diphenyl ether type epoxy compounds include YSLV-80DE (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.).
Examples of commercially available dicyclopentadiene type epoxy compounds include EP-4088S (manufactured by ADEKA).
Examples of commercially available naphthalene-type epoxy compounds include EPICLON HP4032 and EPICLON EXA-4700 (both manufactured by DIC Corporation).
Examples of commercially available phenolic novolac type epoxy compounds include EPICLON N-770 (manufactured by DIC Corporation).
Examples of commercially available ortho-cresol novolac type epoxy compounds include EPICLON N-670-EXP-S (manufactured by DIC Corporation).
Examples of commercially available dicyclopentadiene novolac type epoxy compounds include EPICLON HP7200 (manufactured by DIC Corporation).
Commercially available biphenyl novolac type epoxy compounds include, for example, NC-3000P (manufactured by Nippon Kayaku Co., Ltd.).
Commercially available naphthalenephenol novolac type epoxy compounds include, for example, 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 Co., Ltd.), and the like.
Examples of commercially available alkyl polyol type epoxy compounds include ZX-1542 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), EPICLON 726 (manufactured by DIC), Epolite 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.), and Denacol EX-611. (manufactured by Nagase ChemteX Corporation) and the like.
Commercially available rubber-modified epoxy compounds include, for example, YR-450 and YR-207 (both manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) and Epolead PB (manufactured by Daicel Corporation).
Examples of commercially available glycidyl ester compounds include Denacol EX-147 (manufactured by Nagase ChemteX Corporation).
Other commercially available epoxy compounds include YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), XAC4151 (manufactured by Asahi Kasei Corporation), jER1031, jER1032 (any Mitsubishi Chemical Co., Ltd.), EXA-7120 (DIC Co., Ltd.), TEPIC (Nissan Chemical Co., Ltd.), and the like.

Further, the curable resin may contain a partially (meth)acrylic-modified epoxy resin as the other epoxy compound.
In this specification, the partially (meth)acrylic-modified epoxy resin refers to, for example, reacting some epoxy groups of an epoxy compound having two or more epoxy groups in one molecule with (meth)acrylic acid. means a compound having one or more epoxy groups and one or more (meth)acryloyl groups in one molecule, which can be obtained by

Examples of the other (meth)acrylic compounds include (meth)acrylic acid ester compounds, epoxy (meth)acrylates, urethane (meth)acrylates, and the like. Among them, epoxy (meth)acrylate is preferred. From the viewpoint of reactivity, the (meth)acrylic compound preferably has two or more (meth)acryloyl groups in one molecule.
In this specification, the term "epoxy (meth)acrylate" refers to a compound obtained by reacting all epoxy groups in an epoxy compound with (meth)acrylic acid.

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 ( 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, methoxypolyethyleneglycol (meth)acrylate, phenoxydiethyleneglycol (meth)acrylate, phenoxypolyethyleneglycol (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, ethyl carbi tall (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)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyethylhexahydrophthalate, 2-( meth)acryloyloxyethyl 2-hydroxypropyl phthalate, 2-(meth)acryloyloxyethyl phosphate, glycidyl (meth)acrylate and the like.

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, 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 (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, polyether diol di(meth)acrylate, polyester diol di(meth)acrylate, polycaprolactone diol di(meth)acrylate, polybutadiene diol di(meth)acrylate and the like.

Further, among the above (meth)acrylic acid ester compounds, trifunctional or higher ones include, for example, trimethylolpropane tri(meth)acrylate, ethylene oxide-added trimethylolpropane tri(meth)acrylate, 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, tris(meth)acryloyloxyethyl phosphate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate and the like.

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 that serves as 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 Allnex, epoxy (meth)acrylate manufactured by Shin-Nakamura Chemical Industry, epoxy (meth)acrylate manufactured by Kyoeisha Chemical Co., Ltd. ( meth) acrylate, epoxy (meth) acrylate manufactured by Nagase ChemteX Corporation, and the like.
上記ダイセル・オルネクス社製のエポキシ（メタ）アクリレートとしては、例えば、ＥＢＥＣＲＹＬ８６０、ＥＢＥＣＲＹＬ３２００、ＥＢＥＣＲＹＬ３２０１、ＥＢＥＣＲＹＬ３４１２、ＥＢＥＣＲＹＬ３６００、ＥＢＥＣＲＹＬ３７００、ＥＢＥＣＲＹＬ３７０１、ＥＢＥＣＲＹＬ３７０２、ＥＢＥＣＲＹＬ３７０３、ＥＢＥＣＲＹＬ３７０８、ＥＢＥＣＲＹＬ３８００、ＥＢＥＣＲＹＬ６０４０、ＥＢＥＣＲＹＬ ＲＤＸ６３１８２、ＫＲＭ８０７６等が挙げられる。
Examples of epoxy (meth)acrylates manufactured by Shin-Nakamura Chemical 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, for example, 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 and the like.
Examples of epoxy (meth)acrylates manufactured by Nagase ChemteX Co., Ltd. include Denacol acrylate DA-141, Denacol acrylate DA-314, Denacol acrylate DA-911, and the like.

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 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(isocyanatophenyl) thiophosphate, tetramethylxylylene isocyanate, 1,6,11-undecane triisocyanate, and the like.

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, polycaprolactone diol and the like.

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

Examples of commercially available urethane (meth) acrylates include urethane (meth) acrylate manufactured by Toagosei Co., Ltd., urethane (meth) acrylate manufactured by Daicel Allnex, and urethane (meth) acrylate manufactured by Negami Kogyo Co., Ltd. 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)acrylates manufactured by Toagosei Co., Ltd. include M-1100, M-1200, M-1210 and M-1600.
上記ダイセル・オルネクス社製のウレタン（メタ）アクリレートとしては、例えば、ＥＢＥＣＲＹＬ２１０、ＥＢＥＣＲＹＬ２２０、ＥＢＥＣＲＹＬ２３０、ＥＢＥＣＲＹＬ２７０、ＥＢＥＣＲＹＬ１２９０、ＥＢＥＣＲＹＬ２２２０、ＥＢＥＣＲＹＬ４８２７、ＥＢＥＣＲＹＬ４８４２、ＥＢＥＣＲＹＬ４８５８、ＥＢＥＣＲＹＬ５１２９、ＥＢＥＣＲＹＬ６７００、ＥＢＥＣＲＹＬ８４０２、ＥＢＥＣＲＹＬ８８０３、ＥＢＥＣＲＹＬ８８０４、ＥＢＥＣＲＹＬ８８０７、ＥＢＥＣＲＹＬ９２６０等がmentioned.
Examples of the urethane (meth)acrylate manufactured by Neagari Kogyo Co., Ltd. include, for example, Artresin UN-330, Artresin SH-500B, Artresin UN-1200TPK, Artresin UN-1255, Artresin UN-3320HB, Artresin UN- 7100, Artresin UN-9000A, Artresin UN-9000H and the like.
The urethane (meth)acrylates manufactured by Shin-Nakamura Chemical Co., Ltd. include, for example, 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, and UA-306T. be done.

From the viewpoint of suppressing liquid crystal contamination, the above other (meth)acrylic compounds preferably have a hydrogen-bonding unit such as an —OH group, —NH— group, or —NH ₂ group.

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

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

Examples of the radical photopolymerization initiator include benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, oxime ester compounds, benzoin ether compounds, and thioxanthone compounds.
Specific examples of the photoradical polymerization initiator include 1-hydroxycyclohexylphenyl 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 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 polymeric azo compound (hereinafter also referred to as "polymeric azo initiator") is preferable.
In the present specification, the polymeric azo compound means a compound having an azo group and a number average molecular weight of 300 or more, which generates a radical capable of curing a (meth)acryloyl group by heat.

A preferable lower limit of the number average molecular weight of the above high-molecular azo compound is 1,000, and a preferable upper limit thereof is 300,000. When the number average molecular weight of the high-molecular-weight azo compound is within this range, it can be easily mixed with the curable resin while suppressing liquid crystal contamination. The lower limit of the number average molecular weight of the high-molecular azo compound is more preferably 5,000, the upper limit is 100,000, the lower limit is still more preferably 10,000, and the upper limit is still more preferably 90,000.
In addition, in this specification, the said number average molecular weight is a value which measures by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent, and is calculated|required by polystyrene conversion. Examples of a column for measuring the number average molecular weight by GPC in terms of polystyrene include Shodex LF-804 (manufactured by 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, one having a polyethylene oxide structure is preferable.
Specific examples of the high-molecular azo compound include polycondensates 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.
Examples of commercially available polymeric 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.
Commercially available non-polymer azo compounds include, for example, V-65 and V-501 (both manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.).

Examples of the organic peroxides include ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, peroxyesters, diacyl peroxides and peroxydicarbonates.

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 a protonic acid or a Lewis acid by light irradiation, and may be of an ionic photoacid-generating type or a nonionic photoacid-generating type. may be

Examples of the photocationic polymerization initiator include aromatic diazonium salts, aromatic halonium salts, aromatic sulfonium salts and other onium salts, iron-allene complexes, titanocene complexes, arylsilanol-aluminum complexes and other organometallic complexes, and the like. is mentioned.

Commercially available photo cationic polymerization initiators include, for example, Adeka Optomer SP-150 and Adeka Optomer SP-170 (both manufactured by ADEKA).

The content of the polymerization initiator has a preferable lower limit of 0.01 parts by weight and a preferable upper limit of 10 parts by weight with respect to 100 parts by weight of the curable resin. When the content of the polymerization initiator is within this range, the resulting curable resin composition is excellent in storage stability and curability while suppressing liquid crystal contamination when used as a sealing agent for liquid crystal display elements. becomes. A more preferable lower limit to the content of the polymerization initiator is 0.1 parts by weight, and a more preferable upper limit 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 hydrazides are 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, and malonic acid dihydrazide.
Commercially available solid organic acid hydrazides include, for example, 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.
Examples of the organic acid hydrazides manufactured by Ajinomoto Fine-Techno Co., Inc. include Amicure VDH, Amicure VDH-J, and Amicure UDH.

A preferred lower limit to the content of the thermosetting agent is 1 part by weight, and a preferred upper limit is 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 resulting curable resin composition has excellent 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 viscosity, further improving adhesiveness due to the stress dispersion effect, improving the coefficient of linear expansion, further improving the moisture permeability of the cured product, etc. preferably.

An inorganic filler or an organic filler can be used as the filler.
Examples of inorganic fillers include silica, talc, glass beads, asbestos, gypsum, diatomaceous earth, smectite, bentonite, montmorillonite, sericite, activated 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.

A 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 a preferable upper limit thereof is 70 parts by weight. When the content of the filler is within this range, it is possible to further exhibit effects such as improvement of adhesiveness while suppressing deterioration of coating properties and the like. A more preferable lower limit of the filler content is 20 parts by weight, and a 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 adhesiveness. The silane coupling agent mainly serves as an adhesion aid for good adhesion between the curable resin composition and the substrate.
As the silane coupling agent, for example, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane and the like are preferably used.

A 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 a preferable upper limit thereof is 10 parts by weight. When the content of the silane coupling agent is within this range, the effect of improving adhesiveness while suppressing the occurrence of liquid crystal contamination when the resulting curable resin composition is used as a sealing agent for liquid crystal display elements. can be exhibited more. A more preferable lower limit to the content of the silane coupling agent is 0.3 parts by weight, and a 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 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, and resin-coated carbon black. Among them, titanium black is preferable.

Titanium black is a substance that exhibits a higher transmittance for light in the vicinity of the ultraviolet region, particularly light with a wavelength of 370 nm or more and 450 nm or less, than average transmittance for light with a wavelength of 300 nm or more and 800 nm or less. That is, the titanium black imparts a light-shielding property to the curable resin composition of the present invention by sufficiently shielding light with a wavelength in the visible light region, while transmitting light with a wavelength in the vicinity of 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 highly insulating substance is preferable, and titanium black is also suitable as the highly insulating light-shielding agent.

The above titanium black exerts a sufficient effect even if it is not surface-treated, but it can also be used when the surface is treated with an organic component such as a coupling agent, silicon oxide, titanium oxide, germanium oxide, aluminum oxide, oxide. Surface-treated titanium blacks, such as those coated with inorganic components such as zirconium and magnesium oxide, can also be used. Among them, those treated with an organic component are preferable because they can further improve the insulating properties.
Further, the liquid crystal display element produced by using the curable resin composition of the present invention containing the above titanium black as a light shielding agent as a sealing agent for a liquid crystal display element has sufficient light shielding properties, so that light does not leak out. A liquid crystal display device having high contrast and excellent image display quality can be realized.

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

The specific surface area of the titanium black has a preferred lower limit of 13 m ² /g, a preferred upper limit of 30 m ² /g, a more preferred lower limit of 15 m ² /g, and a more preferred upper limit of 25 m ² /g.
The preferred lower limit of the volume resistivity of 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.

A preferable lower limit of the primary particle size of the light shielding agent is 1 nm, and a preferable upper limit thereof is 5 μm. When the primary particle size of the light shielding agent is within this range, the viscosity and thixotropy of the resulting curable resin composition do not greatly increase, and the applicability is improved. The primary particle size of the light shielding agent has a more preferable lower limit of 5 nm, a more preferable upper limit of 200 nm, a still more preferable lower limit of 10 nm, and a still more preferable upper limit of 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).

A 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 a preferable upper limit thereof 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 exhibited while maintaining the adhesiveness, strength after curing, and drawability of the resulting curable resin composition. A more preferable lower limit of the content of the light shielding agent is 10 parts by weight, a more preferable upper limit is 70 parts by weight, a still more preferable lower limit is 30 parts by weight, and a further preferable upper limit is 60 parts by weight.

The curable resin composition of the present invention may further contain additives such as stress relaxation agents, reactive diluents, thixotropic agents, spacers, curing accelerators, antifoaming agents, leveling agents, polymerization inhibitors, etc. may contain.

As a method for producing the curable resin composition of the present invention, for example, using a mixer, a curable resin, a polymerization initiator and / or a thermosetting agent, a silane coupling agent to be added as necessary, etc. and a method of mixing the additive.
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 suitably used as a sealant for liquid crystal display elements. A sealant for liquid crystal display elements using the curable resin composition of the present invention is also one aspect of the present invention.
Further, by blending conductive fine particles into the liquid crystal display element sealant of the present invention, a vertically conducting material can be produced. A vertically conductive 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, a metal ball, a resin fine particle having a conductive metal layer formed on its surface, or the like can be used. Among them, the one in which a 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 liquid crystal display element having a cured product of the sealant for a liquid crystal display element of the present invention or a cured product of the vertically conducting material of the present invention is also one aspect of the present invention.

The sealing compound for liquid crystal display elements of the present invention can be suitably used for manufacturing liquid crystal display elements by the liquid crystal dropping method.
As a method for producing the liquid crystal display element of the present invention using the liquid crystal display element sealant of the present invention, a liquid crystal dripping method is preferably used, and specific examples thereof include a method including the following steps. be done.
First, one of two transparent substrates having electrodes such as ITO thin films is coated with the sealant for a liquid crystal display element of the present invention by screen printing, dispenser coating, or the like to form a frame-shaped seal pattern. Next, a step of applying liquid crystal microdroplets to the entire surface of the frame of the seal pattern and stacking the other transparent substrate under vacuum is performed. Thereafter, 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 sealant, and a step of heating the temporarily cured sealant to fully cure it. can.

ADVANTAGE OF THE INVENTION According to this invention, the curable resin composition which is excellent in both the adhesiveness with respect to an orientation film, and moisture permeation prevention property can be provided. Further, according to the present invention, it is possible to provide a sealant for a liquid crystal display element, a vertically conducting material, and a liquid crystal display element using the curable resin composition.

EXAMPLES The present invention will be described in more detail with reference to Examples below, 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 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. The mixture was stirred at 90° C. for 5 hours. Next, 340 parts by weight of bisphenol A diglycidyl ether was added to the obtained reaction product, and 0.5 part by weight of triphenylphosphine was added, and the mixture was stirred at 110° C. for 5 hours to obtain curable resin A.
By ¹ H-NMR and ¹³ C-NMR, the curable resin A is represented by the above formula (1-2), where R ¹ is a hydrogen atom, R ² is an ethylene group, and R ³ is the above formula (3-1). ( ^R4 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)” 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 is represented by the above formula (1-2), where R ¹ is a hydrogen atom, R ² is a methylethylene group, and R ³ is the above formula (3-1). It was confirmed to be a compound having the represented structure ( ^R4 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)” 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 is represented by the above formula (1-2), where R ¹ is a methyl group, R ² is an ethylene group, and R ³ is the above formula (3-1). ( ^R4 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)” except that 340 parts by weight of bisphenol A diglycidyl ether was changed to 268 parts by weight of dicyclopentadiene diglycidyl ether.
By ¹ H-NMR and ¹³ C-NMR, the curable resin D is represented by the above formula (1-2), where R ¹ is a hydrogen atom, R ² is an ethylene group, and R ³ is the above formula (3-1). ( ^R4 is a methyl group), n is 0, and Ep is 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 a reaction flask and stirred at 90° C. for 5 hours using a mantle heater. After that, 336 parts by weight of 4-methylcyclohexane-1,2-dicarboxylic 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, and 0.5 part by weight of triphenylphosphine was 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 is represented by the above formula (1-2), where 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 an open ring structure of ε-caprolactone, n is 2.0 (average value), and Ep is a structure derived from bisphenol A diglycidyl ether. .

(Preparation of curable resin F)
Except for changing 336 parts by weight of 4-methylcyclohexane-1,2-dicarboxylic anhydride to 332 parts by weight of 4-cyclohexene-1,2-dicarboxylic anhydride, the above "(Preparation of curable resin A)" A curable resin F was obtained in the same manner as above.
By ¹ H-NMR and ¹³ C-NMR, the curable resin F is represented by the above formula (1-2), where R ¹ is a hydrogen atom, R ² is an ethylene group, and R ³ is the above formula (3-2). (R ⁵ is a hydrogen atom), n is 0, and Ep is a structure derived from bisphenol A diglycidyl ether.

(Preparation of curable resin G)
A curable resin 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 anhydride was changed to 536 parts by weight of tetrapropenylsuccinic anhydride. got a G.
By ¹ H-NMR and ¹³ C-NMR, the curable resin G is represented by the above formula (1-2), where R ¹ is a hydrogen atom, R ² is an ethylene group, and R ³ is the above formula (3-3). (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)
116 parts by weight of 2-hydroxyethyl acrylate, 168 parts by weight of 4-methylcyclohexane-1,2-dicarboxylic anhydride, and 0.05 parts by weight of hydroquinone as a polymerization inhibitor were added to a reaction flask and heated using a mantle heater. The mixture was stirred at 90° C. for 5 hours. Next, 340 parts by weight of bisphenol A diglycidyl ether was added to the resulting reaction product, and 0.5 part by weight of triphenylphosphine was added, and the mixture was stirred at 110° C. for 5 hours to obtain curable resin H.
By ¹ H-NMR and ¹³ C-NMR, the curable resin H is 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 above formula (1-1) was 57% by weight and the content of the compound represented by the above formula (1-2) was 23% by weight. Further, the compound represented by the above formula (1-1) contained in the curable resin H has a structure in which R ¹ is a hydrogen atom, R ² is an ethylene group, and R ³ is represented by the above formula (3-1) ( ^R4 is a methyl group), n is 0, and Ep was confirmed to be a structure derived from bisphenol A diglycidyl ether. Furthermore, the compound represented by the above formula (1-2) contained in the curable resin H has a structure represented by the above formula (3-1) where R ¹ is a hydrogen atom, R ² is an ethylene group, and R ³ is the above formula (3-1). ( ^R4 is a methyl group), n is 0, and Ep was confirmed to be a structure derived from bisphenol A diglycidyl ether.

(Preparation of curable resin I)
A curable resin 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 anhydride was changed to 268 parts by weight of tetrapropenylsuccinic anhydride. obtained I.
By ¹ H-NMR and ¹³ C-NMR, the curable resin I is 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 above formula (1-1) was 60% by weight and the content of the compound represented by the above formula (1-2) was 22% by weight. Further, 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 represented by the above formula (3-3) It was confirmed that the structure ( ^R6 is a hydrogen atom, ^R7 is a dodecyl group), n is 0, and Ep is derived from bisphenol A diglycidyl ether. Furthermore, the compound represented by the above formula (1-2) contained in the curable resin I has a structure represented by the above formula (3-3) where R ¹ is a hydrogen atom, R ² is an ethylene group, and R ³ is the above formula (3-3). It was confirmed that the structure ( ^R6 is a hydrogen atom, ^R7 is a dodecyl group), n is 0, and Ep is derived from bisphenol A diglycidyl ether.

(Preparation of curable resin J)
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 were added to a reaction flask and stirred at 90° C. for 5 hours using a mantle heater. After that, 168 parts by weight of 4-methylcyclohexane-1,2-dicarboxylic 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, and 0.5 part by weight of triphenylphosphine was 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 is 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 above formula (1-1) was 57% by weight and the content of the compound represented by the above formula (1-2) was 21% by weight. Further, the compound represented by the above formula (1-1) contained in the curable resin J has a structure in which R ¹ is a hydrogen atom, R ² is an ethylene group, and R ³ is represented by the above formula (3-1) It was confirmed that (R ⁴ is a methyl group), X is the ring-opening structure of ε-caprolactone, n is 1.0 (average value), and Ep is a structure derived from bisphenol A diglycidyl ether. Furthermore, the compound represented by the above formula (1-2) contained in the curable resin J has a structure represented by the above formula (3-1) where 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 the 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 anhydride was changed to 148 parts by weight of phthalic anhydride. Obtained.
By ¹ H-NMR and ¹³ C-NMR, the curable resin K has a hydrogen atom in the portion corresponding to R ¹ in the above formula (1-1), an ethylene group in the portion corresponding to R ^{2 ,} and an ethylene group in the above formula (1-1). It was confirmed that 55% by weight of a compound containing a 1,2-phenylene group, a value corresponding to n being 0, and a structure derived from bisphenol A diglycidyl ether in a portion corresponding to Ep was contained. In the curable resin K, the portion corresponding to R ¹ in the above formula (1-2) is a hydrogen atom, the portion corresponding to R ² is an ethylene group, and the portion corresponding to R ³ is a 1,2-phenylene group. , the value corresponding to n is 0, and the portion corresponding to Ep contains 24% by weight of a compound having a structure derived from bisphenol A diglycidyl ether. Furthermore, it was confirmed that the curable resin K contained 21% by weight of bisphenol A diglycidyl ether.

(Preparation of curable resin L)
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 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 has a hydrogen atom in the portion corresponding to R ¹ in the above formula (1-2), an ethylene group in the portion corresponding to R ^{2 ,} and an ethylene group in the above formula (1-2). It was confirmed that the portion corresponding to 1,2-phenylene group, the value corresponding to n is 0, and the portion corresponding to Ep has a structure derived from bisphenol A diglycidyl ether.

(Preparation of curable resin M)
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 to a reaction flask, and heated using a mantle heater. A curable resin M was obtained by stirring at 110° C. for 5 hours.
According to 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 content of the compound represented by the following formula (4-2). It was confirmed that the content was 22% by weight.

(Examples 1-12, Comparative Examples 1-4)
According to the compounding ratios shown in Tables 1 and 2, each material was stirred with a planetary stirrer, and then uniformly mixed with three ceramic rolls to cure Examples 1 to 12 and Comparative Examples 1 to 4. A flexible resin composition was obtained. Awatori Mixer (manufactured by Thinky Corporation) was used as the planetary stirring device.

<Evaluation>
Each curable resin composition obtained in Examples and Comparative Examples was evaluated as follows. 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, pre-baked at 80°C, and then baked at 230°C to prepare a substrate with an alignment film. SE7492 (manufactured by Nissan Chemical Industries, Ltd.) was used as the imide resin.
1 part by weight of a silica spacer was uniformly dispersed in 100 parts by weight of each curable resin composition obtained in Examples and Comparative Examples using a planetary stirrer. SI-H055 (manufactured by Sekisui Chemical Co., Ltd.) was used as the silica spacer. Then, the curable resin composition in which the silica spacers were dispersed was minutely dropped onto the alignment film of the substrate with the alignment film. After the curable resin composition was dropped onto the alignment film-attached substrate, another alignment film-attached substrate was pasted in a cross shape via the curable resin composition, and irradiated with ultraviolet rays of 3000 mJ/cm ² using a metal halide lamp. An adhesive test piece was obtained by heating at 120° C. for 60 minutes. When the edge of the substrate in the prepared adhesion test piece was pushed using a metal cylinder with a radius of 5 mm at a rate of 5 mm/min, the strength at which panel peeling occurred was measured. When the value obtained by dividing the obtained measured value (kgf) by the seal diameter (cm) was 3.0 kgf/cm or more, "A" was given, and 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 as "Δ" and when it was less than 2.0 kgf/cm as "x". .

(moisture permeation prevention)
Each curable resin composition obtained in Examples and Comparative Examples was applied onto a smooth release film using a coater to a thickness of 200 μm or more and 300 μm or less. Next, after irradiating with ultraviolet rays of 3000 mJ/cm ² using a metal halide lamp, the film was heated at 120° C. for 60 minutes to obtain a film for moisture permeability measurement. 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, the obtained moisture permeability measurement film was attached, and the temperature was 80 ° C. and the humidity was 90% RH. It was placed in a constant temperature and humidity oven and the moisture permeability was measured. When the obtained moisture permeability value was less than 50 g/m ² · 24 hr, "⊚", when it was 50 g / m ² · 24 hr or more and less than 60 g / m ² · 24 hr, "○", 60 g / The moisture permeation resistance was evaluated as "Δ" when it was m ² ·24 hr or more and less than 70 g/m ² ·24 hr, and as "x" when it was 70 g/m ² ·24 hr 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, pre-baked at 80°C, and then baked 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 is uniformly dispersed by a planetary stirring device, and defoaming treatment is carried out in the curable resin composition. After removing the foam, it was filled into a syringe for dispensing and subjected to defoaming treatment 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 dispensing syringe. Next, 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, SHOTMASTER300 (manufactured by Musashi Engineering Co., Ltd.) was used. Subsequently, microdroplets of TN liquid crystal were applied dropwise to the frame of the curable resin composition using a liquid crystal dropping device. Another substrate with an alignment film was superimposed on the substrate with an alignment film onto which the TN liquid crystal was drip-coated via a curable resin composition. 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. After the obtained liquid crystal display element was stored for 144 hours under an environment of temperature of 80° C. and humidity of 90% RH, it was driven with a voltage of AC 3.5 V, and the presence or absence of display unevenness (color unevenness) was visually observed. "◎" indicates no display unevenness at all around the liquid crystal display element, "○" indicates slightly faint display unevenness, and "△" indicates clear dark display unevenness. The display performance of the liquid crystal display element was evaluated as "X" when the dark display unevenness spread not only to the peripheral portion but also to the central portion.
The liquid crystal display elements evaluated as "⊚" and "◯" are of a level that poses no problem for practical use.

ADVANTAGE OF THE INVENTION According to this invention, the curable resin composition which is excellent in both the adhesiveness with respect to an orientation film, and moisture permeation prevention property can be provided. Further, according to the present invention, it is possible to provide a sealant for a liquid crystal display element, a vertically conducting material, and a liquid crystal display element using the curable resin composition.

Claims (5)

It contains a curable resin and a polymerization initiator and / or a thermosetting agent, and the curable resin is a compound represented by the following formula (1-1) and / or represented by the following formula (1-2) A sealant for a liquid crystal display element for a substrate with a polyimide alignment film, characterized by containing a compound.

In 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 its anhydride, X represents a ring-opening structure of a cyclic lactone, n is 0 or more 5 or less, and Ep represents a structure derived from a bifunctional or higher epoxy compound.

In formulas (2-1) to (2-3), * represents a bonding position; in formula (2-2), a is an integer of 1 or more and 8 or less; 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. In the formulas (1-1) and (1-2), R ³ is a structure represented by the following formula (3-1), (3-2), or (3-3). A sealant for a liquid crystal display element for a substrate with a polyimide alignment film as described above.

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 formula (3-2), R ⁵ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and in formula (3-3), R ⁶ and R ⁷ 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. 3. The sealant for a liquid crystal display element for a substrate with a polyimide alignment film according to claim 1 or 2, wherein the curable resin contains a compound represented by the formula (1-1). 4. A vertically conducting material comprising the liquid crystal display device sealant for a substrate with a polyimide alignment film according to claim 1, 2 or 3, and conductive fine particles. A liquid crystal display device comprising a cured product of the liquid crystal display element sealant for a substrate with a polyimide alignment film according to claim 1, 2 or 3 or a cured product of the vertically conductive material according to claim 4.