TWI826652B - Curable resin compositions, sealants for liquid crystal display elements, vertical conductive materials, and liquid crystal display elements - Google Patents

Abstract

An object of the present invention is to provide a curable resin composition that is excellent in both adhesion and moisture permeability prevention properties to an alignment film. Furthermore, an object of the present invention is to provide a sealant for liquid crystal display elements, a vertical conductive material, and a liquid crystal display element using the curable resin composition. The curable resin composition of the present invention contains a curable resin, a polymerization initiator and/or a thermosetting agent, and the curable resin contains a compound represented by the following formula (1-1) and/or the following formula (1- 2) The compound represented. In formulas (1-1) and (1-2), R ¹ represents a hydrogen atom or a methyl group, and R ² represents a group represented by the following formula (2-1), (2-2) or (2-3). , R ³ represents a structure derived from an optionally substituted aliphatic dicarboxylic acid or anhydride thereof, structure. In formulas (2-1) to (2-3), ✽ represents the bonding position. In formula (2-2), a is an integer from 1 to 8. In formula (2-3), b is from 1 to 8. For the following integers, c is an integer from 1 to 3, and d is an integer from 1 to 8.

Description

Curable resin compositions, sealants for liquid crystal display elements, vertical conductive materials, and liquid crystal display elements

The present invention relates to a curable resin composition that is excellent in both adhesion and moisture permeability prevention properties to an alignment film. Furthermore, the present invention relates to a sealing compound for liquid crystal display elements, a vertical conductive material and a liquid crystal display element using the curable resin composition.

In recent years, as a manufacturing method of liquid crystal display elements such as liquid crystal display units, from the viewpoint of shortening the production lead time and optimizing the amount of liquid crystal used, a curable resin composition as disclosed in Patent Document 1 and Patent Document 2 has been used. The method of using materials as sealants is called the dripping method. In the dropping method, first, a sealant is applied to one of the two substrates with electrodes to form a frame-shaped sealing pattern. Secondly, while the sealant is not hardened, tiny drops of liquid crystal are dropped into the sealing frame of the substrate, another substrate is overlapped under vacuum, and the sealant is hardened by light irradiation or heating to produce a liquid crystal display element. . At present, the dropping method has become the mainstream method of manufacturing liquid crystal display elements.

In addition, in the modern era when various mobile devices with LCD panels such as mobile phones and portable game consoles have become popular, miniaturization of devices is an issue that is most demanded. As a method of miniaturization, there is a narrow bezel of the liquid crystal display part, for example, arranging the position of the sealing part under the black matrix (hereinafter also referred to as narrow bezel design). With such a narrow bezel design, the coating position of the sealant is increasingly located on the alignment film such as polyimide. Prior technical literature patent documents

Patent Document 1: Japanese Patent Application Publication No. 2001-133794 Patent Document 2: International Publication No. 02/092718

[Problem to be solved by the invention]

With the popularity of tablet terminals and mobile terminals, liquid crystal display elements are increasingly required to have moisture-resistant reliability when driven in high-temperature and high-humidity environments, and sealants are further required to prevent the penetration of water from the outside. In order to improve the moisture resistance reliability of liquid crystal display elements, it is necessary to improve the adhesion of the sealant to the substrate, etc. to prevent the penetration of water from the interface between the sealant and the substrate, etc., and to improve the moisture permeability prevention property of the sealant. As a method to improve the moisture permeability prevention of the sealant, it is considered to incorporate fillers such as talc. However, when strict moisture resistance reliability tests are carried out, the liquid crystal display element may display uneven display. Especially when the coating position of the sealant is located on an alignment film such as polyimide, it is difficult to achieve both adhesion to the alignment film and anti-moisture permeability.

An object of the present invention is to provide a curable resin composition that is excellent in both adhesion and moisture permeability prevention properties to an alignment film. Furthermore, an object of the present invention is to provide a sealant for liquid crystal display elements, a vertical conductive material, and a liquid crystal display element using the curable resin composition. [Technical means to solve the problem]

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

In formulas (1-1) and (1-2), R ¹ represents a hydrogen atom or a methyl group, and R ² represents a group represented by the following formula (2-1), (2-2) or (2-3). , R ³ represents a structure derived from an optionally substituted aliphatic dicarboxylic acid or anhydride thereof, structure.

In formulas (2-1) to (2-3), ✽ represents the bonding position. In formula (2-2), a is an integer from 1 to 8. In formula (2-3), b is from 1 to 8. For the following integers, c is an integer from 1 to 3, and d is an integer from 1 to 8. The present invention will be described in detail below.

The present inventors discovered that by using a compound with a specific structure as a curable resin, a curable resin composition excellent in both adhesion to the alignment film and moisture permeability prevention properties can be obtained, and completed the present invention.

The curable resin composition of the present invention contains curable resin. The said curable resin contains the compound represented by the said formula (1-1) and/or the compound represented by the said formula (1-2). The curable resin composition of the present invention contains the compound represented by the above formula (1-1) and/or the compound represented by the above formula (1-2), which improves both the adhesiveness and moisture permeability prevention of the alignment film. Excellent. In addition, from the viewpoint of low liquid crystal contamination when used as a sealant for liquid crystal display elements, the compound represented by the above formula (1-1) and the compound represented by the above formula (1-2) are both excellent. Low LCD contamination. The curable resin preferably contains the compound represented by the above formula (1-1).

In the above formulas (1-1) and (1-2), R ² represents the group represented by the above formula (2-1), (2-2) or (2-3). Among them, from the viewpoint of the adhesiveness of the curable resin composition obtained or the flexibility of the cured product, the above-mentioned R ² is preferably a group represented by the above-mentioned formula (2-2), and more preferably is a group represented by the above-mentioned formula (2- 2) a in 2 is the base of 2 (ethylidene). Furthermore, among the bonding positions shown by ✽ in the above formulas (2-1) and (2-3), the bonding position on the methylene side becomes the same as the above formulas (1-1) and (1 -2) The bonding position of the (meth)acryloxy group. In addition, in this specification, the above-mentioned "(meth)acrylyl group" means an acrylyl group or a methacrylyl group.

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

Examples of the substituent when the above-mentioned optionally substituted aliphatic dicarboxylic acid or its anhydride is substituted include a carbon chain having 1 to 60 carbon atoms which may have an unsaturated bond or a branched structure, and a hydrocarbon containing a cyclic structure. Skeleton etc. Among them, from the viewpoint of improving moisture permeability prevention, a hydrocarbon skeleton containing a cyclic structure is preferred.

Specific examples of the optionally substituted aliphatic dicarboxylic acid or anhydride thereof include: 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-tetrahydrophthalic anhydride, 4-methyl-4-cyclohexene-1,2-dicarboxylic anhydride, tetrapropenylsuccinic anhydride, decylsuccinic anhydride, tetradecylsuccinic anhydride Anhydride, tetradecyl succinic anhydride, hexadecyl succinic anhydride, isoctadecyl succinic anhydride, butyl succinic anhydride, allyl succinic anhydride, 4-hexene-1,2-dicarboxylic anhydride, 2- Dodecen-1-ylsuccinic anhydride, 2,2-dimethylsuccinic anhydride, 2-hexen-1-ylsuccinic anhydride, 4-methyl-4-pentene-1,2-dicarboxylic anhydride, 2 -Octenylsuccinic anhydride, 4,9-decadiene-1,2-dicarboxylic 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 the Dicarboxylic acid, etc.

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

In the formula (3-1) ~ (3-3), ✽ represents the bonding position. In the formula (3-1), R ⁴ represents a hydrogen atom or an alkyl group with a carbon number of 1 to 10, formula (3-2) in formula (3-3), ^{R 6 and} R ⁷ independently represent a hydrogen atom or an organic group with 1 to 60 carbon atoms, or R ^6. R ⁷ bonded structure.

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 those derived from 4-cyclohexene-1,2-dicarboxylic acid and 3-methyl-4-cyclohexene-1,2-dicarboxylic anhydride. , the structure of 3,4,5,6-tetrahydrophthalic anhydride, 4-methyl-4-cyclohexene-1,2-dicarboxylic anhydride, etc. 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. However, from the viewpoint of improving moisture permeability prevention, In other words, a structure in which R ⁶ and R ⁷ are bonded is preferred. Examples of structures in which R ⁶ and R ⁷ are not bonded include those derived from tetrapropenyl succinic anhydride, decyl succinic anhydride, tetradecyl succinic anhydride, tetradecyl succinic anhydride, and hexadecyl succinic anhydride. Isoctadecenyl succinic anhydride, butyl succinic anhydride, allyl succinic anhydride, 4-hexene-1,2-dicarboxylic anhydride, 2-dodecen-1-yl succinic anhydride, 2,2-dimethyl succinic anhydride, 2-hexen-1-yl succinic anhydride, 4-methyl-4-pentene-1,2-dicarboxylic anhydride, 2-octenyl succinic anhydride, 4,9-decadiene-1 , the structure of 2-dicarboxylic anhydride, etc. Examples of structures in which R ⁶ and R ⁷ are bonded include those derived from 5-norbornene-2,3-dicarboxylic anhydride and bicyclo[2.2.2]oct-5-ene-2,3-dicarboxylic acid. The structures of acid anhydride, 2-(2-carboxyethyl)-3-methylmaleic anhydride, 7-oxabicyclo[2.2.1]hept-5-en-2,3-dicarboxylic anhydride, etc.

In the above formulas (1-1) and (1-2), X represents the ring-opened structure of the cyclic lactone. Examples of the cyclic lactone include γ-undecanoic acid lactone, ε-caprolactone, γ-decanolactone, σ-laurolactone, γ-nonalactone, and γ-encaprolactone. , γ-valerolactone, σ-valerolactone, β-butyrolactone, γ-butyrolactone, β-propiolactone, σ-caprolactone, 7-butyl-2-oxepanone, etc. . Among them, those in which the number of carbon atoms in the linear portion of the main skeleton is 5 or more and 7 or less when the ring is opened is preferred. Furthermore, in the above formulas (1-1) and (1-2), even when n is 0, that is, when there is no ring-opened structure of the cyclic lactone represented by X, the curable resin obtained The composition also has excellent adhesion to the alignment film and anti-moisture permeability of the cured product. When n is 1 or more and 5 or less, the curable resin composition obtained has better adhesion to the alignment film. In addition, the compound represented by the above formula (1-1) and the compound represented by the above formula (1-2) may each be a mixture of compounds having different repeat numbers of X, and in this case, the above n is an average value.

In the above formulas (1-1) and (1-2), Ep represents a structure derived from a bifunctional or higher-functional epoxy compound. Examples of the epoxy compound that is a source of the above-mentioned Ep include bisphenol A-type epoxy compounds, bisphenol F-type epoxy compounds, bisphenol E-type epoxy compounds, bisphenol S-type epoxy compounds, and resorcinol. Phenolic epoxy compounds, dicyclopentadiene epoxy compounds, naphthalene epoxy compounds, rubber modified epoxy compounds, epoxy propyl ester compounds, etc. Among them, the above-mentioned Ep is preferably 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 methods for producing the compound represented by the above formula (1-1) include the following methods. That is, a method including the step of heating and stirring (meth)acrylic acid hydroxyalkyl ester and the above-mentioned optionally substituted aliphatic dicarboxylic acid or its anhydride in the presence of a polymerization inhibitor, etc. can be cited. and the step of reacting a part of the epoxy groups by adding the above-mentioned bifunctional or higher epoxy compound to the obtained reactant and heating and stirring. Moreover, as a method of producing the compound represented by the said formula (1-2), the following method etc. are mentioned, for example. That is, a method including the steps of heating and stirring (meth)acrylic acid hydroxyalkyl ester and the above-mentioned optionally substituted aliphatic dicarboxylic acid or its anhydride in the presence of a polymerization inhibitor, etc. can be cited. The steps of carrying out the reaction; and the step of reacting all the epoxy groups by adding the above-mentioned bifunctional or higher epoxy compound to the obtained reactant and heating and stirring. In addition, in this specification, the said "(meth)acrylate" means acrylate or methacrylate.

Examples of the hydroxyalkyl (meth)acrylate include: (2-hydroxyethylmeth)acrylate, 2-hydroxypropyl(meth)acrylate, 2-hydroxybutyl(meth)acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, etc. The above-mentioned hydroxyalkyl (meth)acrylate may be reacted with the above-mentioned cyclic lactone before reacting with the above-mentioned optionally substituted aliphatic dicarboxylic acid or anhydride thereof.

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

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 above-mentioned curable resin is 5 parts by weight, and the preferred upper limit is 90 parts by weight. . By having the content of the compound represented by the above formula (1-1) and/or the compound represented by the formula (1-2) within this range, the curable resin composition obtained has both adhesion to the alignment film and The moisture permeability prevention effect becomes even better. A more preferable lower limit of the content of the compound represented by the above formula (1-1) and/or the compound represented by the formula (1-2) is 10 parts by weight, and a more preferable upper limit is 80 parts by weight. Furthermore, regarding the above "content of the compound represented by formula (1-1) and/or the compound represented by formula (1-2)", when it contains only one of these compounds, it means that The content of one compound means the total content when it contains both.

The curable resin composition of the present invention may further contain other cured compounds other than the compound represented by the above formula (1-1) and the compound represented by the above formula (1-2) within the scope that does not hinder the object of the present invention. The curable resin is the above-mentioned curable resin. Examples of the other curable resin include epoxy compounds other than the compound represented by the above formula (1-1), and other (meth)acrylic compounds other than the compound represented by the above formula (1-2). Compounds etc. In addition, in this specification, the above-mentioned "(meth)acrylic acid" means acrylic acid or methacrylic acid, and the above-mentioned "(meth)acrylic acid compound" means a compound having a (meth)acrylyl group.

Examples of the other epoxy compounds include bisphenol A-type epoxy compounds, bisphenol F-type epoxy compounds, bisphenol S-type epoxy compounds, and 2,2'-diallylbisphenol A-type epoxy compounds. Compounds, hydrogenated bisphenol type epoxy compounds, propylene oxide addition bisphenol A type epoxy compounds, resorcinol type epoxy compounds, biphenyl type epoxy compounds, sulfide type epoxy compounds, di Phenyl ether type epoxy compound, dicyclopentadiene type epoxy compound, naphthalene type epoxy compound, phenol novolak type epoxy compound, o-cresol novolak type epoxy compound, dicyclopentadiene novolac type ring Oxygen compounds, biphenyl novolak type epoxy compounds, naphthol novolak type epoxy compounds, glycidylamine type epoxy compounds, alkyl polyol type epoxy compounds, rubber modified epoxy compounds, epoxy compounds Propyl ester compounds, etc.

Examples of commercially available bisphenol A-type epoxy compounds include jER828EL, jER1004 (both 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). Examples of commercially available resorcinol-type epoxy compounds include EX-201 (manufactured by Nagase Chemical Co., Ltd.). Examples of commercially available biphenyl epoxy compounds include jER YX-4000H (manufactured by Mitsubishi Chemical Corporation). Examples of commercially available sulfide-type epoxy compounds include YSLV-50TE (manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.). Examples of commercially available diphenyl ether type epoxy compounds include YSLV-80DE (manufactured by Nippon Steel & Sumitomo Metal 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, EPICLON EXA-4700 (both manufactured by DIC Corporation), and the like. Examples of commercially available phenol novolak type epoxy compounds include EPICLON N-770 (manufactured by DIC Corporation). Examples of commercially available o-cresol novolak type epoxy compounds include EPICLON N-670-EXP-S (manufactured by DIC Corporation). Examples of commercially available dicyclopentadiene novolak-type epoxy compounds include EPICLON HP7200 (manufactured by DIC Corporation). Examples of commercially available biphenyl novolak-type epoxy compounds include NC-3000P (manufactured by Nippon Kayaku Co., Ltd.). Examples of commercially available naphthol novolak-type epoxy compounds include ESN-165S (manufactured by Nippon Steel & Sumitomo Metal 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 Corporation), and the like. Examples of commercially available alkyl polyol type epoxy compounds include ZX-1542 (manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.), EPICLON 726 (manufactured by DIC Corporation), and Epolight 80MFA (manufactured by Kyoeisha Chemical Co., Ltd. ), DENACOL EX-611 (manufactured by Nagase Chemical Co., Ltd.), etc. Examples of commercially available rubber-modified epoxy compounds include YR-450, YR-207 (all manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.), Epolead PB (manufactured by Daicel), and the like. Examples of commercially available glycidyl ester compounds include DENACOL EX-147 (manufactured by Nagase Chemicals Co., Ltd.). Examples of other commercially available epoxy compounds mentioned above include: YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.), XAC4151 (manufactured by Asahi Kasei Co., Ltd.), jER1031, jER1032 ( All are manufactured by Mitsubishi Chemical Corporation), EXA-7120 (manufactured by DIC Corporation), TEPIC (manufactured by Nissan Chemical Corporation), etc.

In addition, the above-mentioned curable resin may contain a part of (meth)acrylic acid-modified epoxy resin as the above-mentioned other epoxy compound. Furthermore, in this specification, the above-mentioned partially (meth)acrylic modified epoxy resin means a compound which can be partially epoxylated by, for example, an epoxy compound having two or more epoxy groups in one molecule. It is obtained by reacting a group with (meth)acrylic acid, and has at least one epoxy group and one (meth)acrylyl group each in one molecule.

Examples of the other (meth)acrylic compounds include (meth)acrylic acid ester compounds, epoxy (meth)acrylic acid esters, (meth)acrylic acid amine esters, and the like. Among them, epoxy (meth)acrylate is preferred. Moreover, from the viewpoint of reactivity, the (meth)acrylic acid compound preferably has two or more (meth)acrylyl groups in one molecule. In addition, in this specification, the said "epoxy (meth)acrylate" means the compound obtained by reacting all the epoxy groups in an epoxy compound with (meth)acrylic acid.

Examples of the monofunctional ones among the above-mentioned (meth)acrylate compounds include: (meth)acrylic acid methyl ester, (meth)acrylic acid ethyl ester, (meth)acrylic acid propyl ester, (meth)acrylic acid n-butyl ester Ester, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate , isononyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, isomyristyl (meth)acrylate, stearyl (meth)acrylate, (meth) 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, cyclohexyl (meth)acrylate, ( Isocamphenyl methacrylate, dicyclopentenyl (meth)acrylate, benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate Ester, 2-butoxyethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, methoxyethylene glycol (meth)acrylate, methoxypolyethylene glycol (methoxyethylene glycol) acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxy polyethylene glycol (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, ethyl carbitol (meth)acrylate acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, 1H,1H,5H-(meth)acrylate Octafluoropentyl, imide (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, 2-(meth)acrylamide succinate Oxyethyl ester, 2-(meth)acryloxyethyl hexahydrophthalate, 2-(meth)acryloxyethyl 2-hydroxypropyl phthalate, 2-(methyl)phosphate Methacryloyloxyethyl ester, epoxypropyl (meth)acrylate, etc.

Moreover, examples of the bifunctional ones among the above-mentioned (meth)acrylate compounds include 1,3-butanediol di(meth)acrylate and 1,4-butanediol di(meth)acrylate. , 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, ethylene glycol diacrylate (Meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 2-n-butyl-2 -Ethyl-1,3-propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, neopentyl glycol Alcohol di(meth)acrylate, ethylene oxide added to bisphenol A di(meth)acrylate, propylene oxide added to bisphenol A di(meth)acrylate, ethylene oxide added to bisphenol F di(meth)acrylate, dihydroxymethyldicyclopentadienyl di(meth)acrylate, ethylene oxide modified isocyanurate di(meth)acrylate, (meth)acrylic acid 2-Hydroxy-3-(meth)acryloxypropyl ester, carbonate diol di(meth)acrylate, polyether diol di(meth)acrylate, polyester diol di(meth)acrylate Acrylate, polycaprolactone diol di(meth)acrylate, polybutadiene diol di(meth)acrylate, etc.

Furthermore, examples of the above-mentioned (meth)acrylate compounds having trifunctional or higher functions include: trimethylolpropane tri(meth)acrylate, ethylene oxide addition trimethylolpropane tri(meth)acrylate, ) Acrylate, propylene oxide added to trimethylolpropane tri(meth)acrylate, caprolactone modified trimethylolpropane tri(meth)acrylate, ethylene oxide added to isocyanuride Tri(meth)acrylate, glyceryl tri(meth)acrylate, propylene oxide plus tri(meth)acrylate, neopentylerythritol tri(meth)acrylate, tri(methyl)phosphate Acryloxyethyl ester, di-trimethylolpropane tetra(meth)acrylate, neopentylerythritol tetra(meth)acrylate, dineopenterythritol penta(meth)acrylate, dineopenterythritol Tetraol hexa(meth)acrylate, etc.

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

As the epoxy compound used as a raw material for synthesizing the above-mentioned epoxy (meth)acrylate, the same ones as the other above-mentioned epoxy compounds can be used.

Examples of commercially available epoxy (meth)acrylates include epoxy (meth)acrylate manufactured by Daicel Alchemy Co., Ltd. and epoxy (meth)acrylate manufactured by Shin-Nakamura Chemical Industry Co., Ltd. ester, epoxy (meth)acrylate manufactured by Kyeisha Chemical Co., Ltd., epoxy (meth)acrylate manufactured by Nagase Chemical Co., Ltd., etc. Examples of the above-mentioned epoxy (meth)acrylates manufactured by Daicel Allnex include: EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRYL3703, EBECRYL3708, EBECRYL3800, EB ECRYL6040, EBECRYL RDX63182, KRM8076 wait. 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, EMA-1020, and the like. Examples of the above-mentioned epoxy (meth)acrylates manufactured by Kyoeisha Chemical Co., Ltd. include: EPOXY ESTER M-600A, EPOXY ESTER 40EM, EPOXY ESTER 70PA, EPOXY ESTER 200PA, EPOXY ESTER 80MFA, EPOXY ESTER 3002M, EPOXY ESTER 3002A, EPOXY ESTER 1600A, EPOXY ESTER 3000M, EPOXY ESTER 3000A, EPOXY ESTER 200EA, EPOXY ESTER 400EA, etc. Examples of the epoxy (meth)acrylate manufactured by Nagase Chemicals Co., Ltd. include Denacol acrylate DA-141, Denacol acrylate DA-314, Denacol acrylate DA-911, and the like.

The above-mentioned (meth)acrylic amine ester can be obtained, for example, by reacting a (meth)acrylic acid derivative having a hydroxyl group and an isocyanate compound in the presence of a catalytic amount of a tin-based compound.

Examples of the isocyanate compound include isophorone diisocyanate, 2,4-methylphenylene diisocyanate, 2,6-methylphenylene diisocyanate, hexamethylene diisocyanate, and trimethylhexylene diisocyanate. Methyl diisocyanate, diphenylmethane-4,4'-diisocyanate (MDI), hydrogenated MDI, polymerized MDI, 1,5-naphthalene diisocyanate, reduced Alkane diisocyanate, toluidine diisocyanate, stubble diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris(isocyanatophenyl)thiophosphate, tetramethyl 1,6,11-Undecane triisocyanate, etc.

Furthermore, as the isocyanate compound, a chain-extended isocyanate compound obtained by reaction of a polyol and an excess isocyanate compound can also be used. Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, glycerol, sorbitol, trimethylolpropane, carbonate diol, polyether diol, polyester diol, polycaprolactone diol, and the like.

Examples of the (meth)acrylic acid derivatives having a hydroxyl group include: hydroxyalkyl mono(meth)acrylate, mono(meth)acrylate of dihydric alcohol, and mono(meth)acrylic acid of trihydric alcohol. Ester or di(meth)acrylate, epoxy (meth)acrylate, etc. Examples of the above-mentioned hydroxyalkyl mono(meth)acrylate include: (2-hydroxyethylmeth)acrylate, 2-hydroxypropyl(meth)acrylate, 2-hydroxybutyl(meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc. Examples of the glycol 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, glycerin, and the like. Examples of the epoxy (meth)acrylate include bisphenol A-type epoxy acrylate.

Examples of commercially available (meth)acrylic acid urethanes include: (meth)acrylic acid urethane manufactured by Toagosei Co., Ltd., (meth)acrylic acid urethane manufactured by Daicel Alchemy Co., Ltd., and Negami Industrial Co., Ltd. (Meth)acrylic acid urethane manufactured by Shin-Nakamura Chemical Industry Co., Ltd., (meth)acrylic acid urethane manufactured by Kyoeisha Chemical Co., Ltd., etc. Examples of the (meth)acrylic acid amine ester manufactured by Toagosei Co., Ltd. include M-1100, M-1200, M-1210, M-1600, and the like. Examples of the above-mentioned (meth)acrylic acid amide esters manufactured by Daicel Allnex include: EBECRYL210, EBECRYL220, EBECRYL230, EBECRYL270, EBECRYL1290, EBECRYL2220, EBECRYL4827, EBECRYL4842, EBECRYL4858, EBECRYL5129, EBECRYL6700, EBECRYL8 402、EBECRYL8803、EBECRYL8804、EBECRYL8807 , EBECRYL9260, etc. Examples of the above-mentioned (meth)acrylic acid urethane manufactured by Negami Kogyo Co., Ltd. include: Artresin UN-330, Artresin SH-500B, Artresin UN-1200TPK, Artresin UN-1255, Artresin UN-3320HB, Artresin UN-7100, Artresin UN-9000A, Artresin UN-9000H, etc. Examples of the above-mentioned (meth)acrylic acid amine ester 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, 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, etc. Examples of the above-mentioned (meth)acrylic amine esters manufactured by Kyoeisha Chemical Co., Ltd. include: AH-600, AI-600, AT-600, UA-101I, UA-101T, UA-306H, UA-306I, UA -306T etc.

From the viewpoint of suppressing liquid crystal contamination, the other (meth)acrylic compounds described above are preferably those having hydrogen-bonding units such as -OH groups, -NH- groups, and -NH ₂ groups.

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, cationic polymerization initiators, and the like.

Examples of the radical polymerization initiator include a photo radical 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, phosphine oxide compounds, titanocene compounds, oxime ester compounds, benzoin ether compounds, and 9-oxosulfide compounds. Compounds etc. Specific examples of the photoradical polymerization initiator include: 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1-(4-N- Phylinophenyl)butanone, 1,2-(dimethylamino)-2-((4-methylphenyl)methyl)-1-(4-(4- Phinyl)phenyl)-1-butanone, 2,2-dimethoxy-1,2-diphenylethan-1-one, bis(2,4,6-trimethylbenzyl) Phenylphosphine oxide, 2-methyl-1-(4-methylthienyl)-2-N- Phinylpropan-1-one, 1-(4-(2-hydroxyethoxy)-phenyl)-2-hydroxy-2-methyl-1-propan-1-one, 1-(4-(phenyl) Thio)phenyl)-1,2-octanedione 2-(O-benzoyl oxime), 2,4,6-trimethylbenzoyldiphenylphosphine oxide, benzoin methyl ether, benzoin Ether, benzoin isopropyl ether, etc.

Examples of the thermal radical polymerization initiator include azo compounds, organic peroxides, and the like. Among them, a initiator containing a polymer azo compound (hereinafter also referred to as a "polymer azo initiator") is preferred. Furthermore, in this specification, a polymeric azo compound means a compound having an azo group and having a number average molecular weight of 300 or more that generates free radicals capable of hardening (meth)acrylyl groups due to heat.

The preferred lower limit of the number average molecular weight of the above-mentioned polymeric azo compound is 1,000, and the preferred upper limit is 300,000. By setting the number average molecular weight of the polymeric azo compound within this range, liquid crystal contamination can be suppressed and it can be easily mixed with the curable resin. A more preferable lower limit of the number average molecular weight of the above-mentioned polymeric azo compound is 5,000, a more preferable upper limit is 100,000, a further preferable lower limit is 10,000, and a further preferable upper limit is 90,000. In addition, in this specification, the said number average molecular weight is the value calculated|required by measuring by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent, and converting it into polystyrene. Examples of a column for measuring the number average molecular weight in terms of polystyrene by GPC include Shodex LF-804 (manufactured by Showa Denko Co., Ltd.).

Examples of the polymeric azo compound include those having a structure in which a plurality of units such as polyalkylene oxide or polydimethylsiloxane are bonded via an azo group. As the above-mentioned polymeric azo compound having a structure in which a plurality of units such as polyalkylene oxide are bonded via an azo group, one having a polyethylene oxide structure is preferred. Specific examples of the polymeric azo compound include: a condensate of 4,4'-azobis(4-cyanovaleric acid) and polyalkylene glycol or 4,4'- Condensation polymers of azobis(4-cyanovaleric acid) and polydimethylsiloxane with terminal amine groups, etc. Examples of commercially available polymeric azo compounds include VPE-0201, VPE-0401, VPE-0601, VPS-0501, and VPS-1001 (all manufactured by Fuji Film Wako Pure Chemical Co., Ltd.). Examples of commercially available non-polymer azo compounds include V-65 and V-501 (both manufactured by Fuji Film Wako Pure Chemical Co., Ltd.).

Examples of the organic peroxide include ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, peroxyester, diyl peroxide, peroxydicarbonate, etc. .

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

Examples of the photocationic polymerization initiator include onium salts such as aromatic diazonium salts, aromatic halide salts, and aromatic sulfonium salts, iron-heavyene complexes, titanocene complexes, aromatic Organometallic complexes such as silanol-aluminum complexes, etc.

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

The preferable lower limit of the content of the above-mentioned polymerization initiator is 0.01 parts by weight, and the preferable upper limit is 10 parts by weight relative to 100 parts by weight of the above-mentioned curable resin. By setting the content of the polymerization initiator within this range, when the obtained curable resin composition is used as a sealant for liquid crystal display elements, liquid crystal contamination is suppressed and storage stability or curability is more excellent. A more preferable lower limit of the content of the above-mentioned 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, polyphenol compounds, acid anhydrides, and the like. Among them, solid organic acid hydrazine can be preferably used.

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

The preferable lower limit of the content of the thermal hardener is 1 part by weight, and the preferable upper limit is 50 parts by weight relative to 100 parts by weight of the entire curable resin. By setting the content of the thermosetting agent within this range, the curable resin composition obtained becomes more excellent in curing properties while maintaining excellent coating properties or storage stability. A better upper limit of the content of the above-mentioned thermal hardener is 30 parts by weight.

The curable resin composition of the present invention preferably contains a filler in order to increase the viscosity, further enhance the adhesion by utilizing the stress dispersion effect, improve the linear expansion rate, further enhance the moisture permeability prevention property of the cured product, etc.

As the above-mentioned 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, bentonite, bentonite, montmorillonite, sericite, activated clay, aluminum oxide, zinc oxide, oxide Iron, magnesium oxide, tin oxide, titanium oxide, calcium carbonate, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, aluminum nitride, silicon nitride, barium sulfate, calcium silicate, etc. Examples of the organic filler include polyester microparticles, polyurethane microparticles, vinyl polymer microparticles, and acrylic polymer microparticles.

The preferred lower limit of the content of the above-mentioned filler in 100 parts by weight of the curable resin composition of the present invention is 10 parts by weight, and the preferred upper limit is 70 parts by weight. By setting the content of the filler within this range, deterioration of coating properties and the like can be suppressed, and effects such as improvement of adhesiveness can be further exerted. A better lower limit of the content of the above-mentioned filler is 20 parts by weight, and a better upper limit is 60 parts by weight.

In order to further improve the adhesiveness, the curable resin composition of the present invention preferably contains a silane coupling agent. The above-mentioned silane coupling agent mainly functions as an adhesion aid 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, etc. can be preferably used.

The preferred lower limit of the content of the above-mentioned 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 preferred upper limit is 10 parts by weight. By setting the content of the silane coupling agent within this range, the occurrence of liquid crystal contamination when the obtained curable resin composition is used as a sealant for liquid crystal display elements can be suppressed, and the effect of improving adhesion can be further exerted. A more preferable lower limit of the content of the above-mentioned 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-blocking agent. By containing the above light-shielding agent, the curable resin composition of the present invention can be preferably 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. Among them, titanium black is preferred.

The above-mentioned titanium black is a substance that has a higher transmittance for light near the ultraviolet region, especially for light with a wavelength of 370 nm to 450 nm, compared to the average transmittance to light with a wavelength of 300 nm to 800 nm. That is, the above-mentioned titanium black is a light-shielding agent that imparts light-shielding properties to the curable resin composition of the present invention by fully blocking light of wavelengths in the visible light range, and on the other hand, transmits light of wavelengths near the ultraviolet range. . The light-shielding agent contained in the curable resin composition of the present invention is preferably a substance with high insulation properties, and the light-shielding agent with high insulation properties is also preferably titanium black.

The above-mentioned titanium black will exert sufficient effects even without surface treatment, but it can also be used with the surface treated with organic components such as coupling agents or inorganic materials such as silicon oxide, titanium oxide, germanium oxide, aluminum oxide, zirconium oxide, magnesium oxide, etc. Surface-treated titanium black with coating components. Among them, those treated with organic components are preferred in terms of further improving insulation properties. Furthermore, the liquid crystal display element manufactured by using the curable resin composition of the present invention containing the above-mentioned titanium black as a light-shielding agent as a sealing compound for a liquid crystal display element has sufficient light-shielding properties, and therefore has no light leakage and high contrast, and can realize Liquid crystal display element with excellent image display quality.

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

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

The preferred lower limit of the primary particle size of the above-mentioned sunscreen agent is 1 nm, and the preferred upper limit is 5 μm. By setting the primary particle diameter of the light-shielding agent within this range, the viscosity or thixotropy of the curable resin composition obtained can be improved without greatly increasing the coating properties. A more preferable lower limit of the primary particle size of the above-mentioned sunscreen agent is 5 nm, a more preferable upper limit is 200 nm, a further preferable lower limit is 10 nm, and a further preferable upper limit is 100 nm. Furthermore, the primary particle diameter of the above-mentioned sunscreen agent can be measured using a particle size distribution meter (for example, "NICOMP 380ZLS" manufactured by PARTICLE SIZING SYSTEMS).

The preferred lower limit of the content of the above-mentioned sunscreen agent in 100 parts by weight of the curable resin composition of the present invention is 5 parts by weight, and the preferred upper limit is 80 parts by weight. By setting the content of the light-shielding agent within this range, the adhesiveness, post-cured strength, and drawing properties of the cured resin composition can be maintained, and the effect of improving light-shielding properties can be further exerted. A more preferable lower limit of the content of the above-mentioned sunscreen agent is 10 parts by weight, a more preferable upper limit is 70 parts by weight, a further 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 relievers, reactive diluents, thixotropic agents, spacers, hardening accelerators, defoaming agents, leveling agents, and polymerization inhibitors as needed.

An example of a method for producing the curable resin composition of the present invention is a method of mixing a curable resin with a polymerization initiator and/or a thermosetting agent and optionally added additives such as a silane coupling agent using a mixer. Examples of the mixer include a homogeneous disperser, a homogeneous mixer, a universal mixer, a planetary mixer, a kneader, a three-roller kneader, and the like.

The curable resin composition of the present invention can be used as an adhesive, and is particularly preferably used as a sealant for liquid crystal display elements. Moreover, a sealing compound for a liquid crystal display element using the curable resin composition of the present invention is also one of the present invention. Furthermore, by blending conductive fine particles into the sealing compound for liquid crystal display elements of the present invention, a vertical conductive material can be produced. Furthermore, an upper and lower conductive material containing the sealant for liquid crystal display elements of the present invention and conductive fine particles is also one of the present invention.

As the conductive fine particles, metal balls, resin fine particles having a conductive metal layer formed on their surfaces, etc. can be used. Among them, those having a conductive metal layer formed on the surface of the resin particles are preferred because they can conduct conductive connection without damaging the transparent substrate etc. due to the excellent elasticity of the resin particles.

A liquid crystal display element having a cured product of the sealant for liquid crystal display elements of the present invention or a cured product of the upper and lower conductive material of the present invention is also one of the present invention.

The sealant for liquid crystal display elements of the present invention can be preferably used for manufacturing liquid crystal display elements using the liquid crystal dropping method. As a method for manufacturing the liquid crystal display element of the present invention using the sealing compound for liquid crystal display elements of the present invention, the liquid crystal dropping method can be preferably used. Specific examples include a method having the following steps. First, the step of applying the sealant for liquid crystal display elements of the present invention to one of two transparent substrates having electrodes such as an ITO film by screen printing, dispenser coating, etc. is performed to form a frame. Seal pattern. Next, the following steps are performed, that is, tiny drops of liquid crystal are applied to the entire surface of the frame of the sealing pattern, and another transparent substrate is overlapped under vacuum. Thereafter, a step of irradiating the sealing pattern portion with light such as ultraviolet light to temporarily harden the sealant, and a step of heating the temporarily hardened sealant to fully harden it are performed. By this method, a liquid crystal display element can be obtained. [Effects of the invention]

According to the present invention, it is possible to provide a curable resin composition that is excellent in both adhesion to an alignment film and moisture permeability prevention. Furthermore, according to the present invention, it is possible to provide a sealant for liquid crystal display elements, a vertical conductive material and a liquid crystal display element using the curable resin composition.

The following examples are given to illustrate the present invention in further detail, but the present invention is not limited only 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 parts by weight of polymerization inhibitor were added to the reaction flask. Add hydroquinone and stir using a heating pack at 90°C for 5 hours. Next, 340 parts by weight of bisphenol A diglycidyl ether and 0.5 parts by weight of triphenylphosphine were added to the obtained reactant, and the mixture was stirred at 110° C. for 5 hours, thereby obtaining curable resin A. It was confirmed by ¹ H-NMR and ¹³ C-NMR that the curable resin A is the following compound: in the above formula (1-2), R ¹ is a hydrogen atom, R ² is an ethylidene group, and R ³ is the above formula ( 3-1) The structure represented by (R ⁴ is methyl), n is 0, and Ep is a structure derived from bisphenol A diglycidyl ether.

(Preparation of Curable Resin B) The same procedure as the above "(Preparation of Curable Resin A)" was performed except that 232 parts by weight of 2-hydroxyethyl acrylate was changed to 256 parts by weight of 2-hydroxypropyl acrylate. In this way, hardening resin B is obtained. It was confirmed by ¹ H-NMR and ¹³ C-NMR that the curable resin B is the following compound: in the above formula (1-2), R ¹ is a hydrogen atom, R ² is a methylethylidene group, and R ³ is the above-mentioned In the structure represented by formula (3-1) (R ⁴ is methyl), n is 0, and Ep is a structure derived from bisphenol A diglycidyl ether.

(Preparation of Curable Resin C) Except for changing 232 parts by weight of 2-hydroxyethyl acrylate into 256 parts by weight of 2-hydroxyethyl methacrylate, the same procedure as above "(Preparation of Curable Resin A)" ” Obtain curable resin C in the same manner. It was confirmed by ¹ H-NMR and ¹³ C-NMR that the curable resin C is the following compound: in the above formula (1-2), R ¹ is a methyl group, R ² is an ethylene group, and R ³ is the above formula ( 3-1) The structure represented by (R ⁴ is methyl), n is 0, and Ep is a structure derived from bisphenol A diglycidyl ether.

(Preparation of Curable Resin D) Except for changing 340 parts by weight of bisphenol A diglycidyl ether into 268 parts by weight of dicyclopentadiene dialpoxypropyl ether, the same conditions as the above "(hardening (Preparation of Hardening Resin A)" Obtain hardening resin D in the same way. It was confirmed by ¹ H-NMR and ¹³ C-NMR that the curable resin D is the following compound: in the above formula (1-2), R ¹ is a hydrogen atom, R ² is an ethylidene group, and R ³ is the above formula ( 3-1) The structure represented by (R ⁴ is methyl), n is 0, and Ep is a structure derived from dicyclopentadiene dialpoxypropyl ether.

(Preparation of Hardening Resin E) Add 232 parts by weight of 2-hydroxyethyl acrylate, 228 parts by weight of ε-caprolactone, and 0.1 parts by weight of hydroquinone as a polymerization inhibitor to the reaction flask, and heat Stir at 90°C for 5 hours. Thereafter, 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 and 0.5 parts by weight of triphenylphosphine were added to the obtained reactant, and the mixture was stirred at 110° C. for 5 hours, thereby obtaining curable resin E. It was confirmed by ¹ H-NMR and ¹³ C-NMR that the curable resin E is the following compound: in the above formula (1-2), R ¹ is a hydrogen atom, R ² is an ethylene group, and R ³ is the above formula (3-1) The structure represented by (R ⁴ is methyl), X is the open ring structure of ε-caprolactone, n is 2.0 (average value), Ep is derived from bisphenol A diepoxypropyl ether structure.

(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. Except for this, the curable resin F is obtained in the same manner as the above "(Preparation of Curable Resin A)". It was confirmed by ¹ H-NMR and ¹³ C-NMR that the curable resin F is the following compound: in the above formula (1-2), R ¹ is a hydrogen atom, R ² is an ethylidene group, and R ³ is the above formula ( 3-2) The structure represented by (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) Except for changing 336 parts by weight of 4-methylcyclohexane-1,2-dicarboxylic anhydride into 536 parts by weight of tetrapropenylsuccinic anhydride, the same conditions as the above "(hardening (Preparation of Hardening Resin A)" Obtain hardening resin G in the same way. It was confirmed by ¹ H-NMR and ¹³ C-NMR that the curable resin G is the following compound: in the above formula (1-2), R ¹ is a hydrogen atom, R ² is an ethylidene group, and R ³ is the above formula ( 3-3) The structure represented by (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 polymerization inhibitor were added to the reaction flask. Add hydroquinone and stir using a heating pack at 90°C for 5 hours. Next, 340 parts by weight of bisphenol A diglycidyl ether and 0.5 parts by weight of triphenylphosphine were added to the obtained reactant, and the mixture was stirred at 110° C. for 5 hours, thereby obtaining curable resin H. It was confirmed by ¹ H-NMR and ¹³ C-NMR that the curable resin H contains the compound represented by the above formula (1-1), the compound represented by the above formula (1-2) and bisphenol A diepoxypropyl As for the ether, the content ratio of the compound represented by the above formula (1-1) is 57% by weight, and the content ratio of the compound represented by the above formula (1-2) is 23% by weight. Furthermore, it was confirmed that R ¹ of the compound represented by the above formula (1-1) contained in the curable resin H is a hydrogen atom, R ² is an ethylene group, and R ³ is a structure represented by the above formula (3-1) (R ⁴ is methyl), n is 0, and Ep is a structure derived from bisphenol A diglycidyl ether. Furthermore, it was confirmed that R ¹ of the compound represented by the above formula (1-2) contained in the curable resin H is a hydrogen atom, R ² is an ethylene group, and R ³ is a structure represented by the above formula (3-1) (R ⁴ is methyl), n is 0, and Ep is a structure derived from bisphenol A diglycidyl ether.

(Preparation of Curable Resin I) Except for changing 168 parts by weight of 4-methylcyclohexane-1,2-dicarboxylic anhydride into 268 parts by weight of tetrapropenylsuccinic anhydride, the same conditions as the above "(hardening Curable resin I was obtained in the same manner as "Preparation of curable resin H". It was confirmed by ¹ H-NMR and ¹³ C-NMR that the curable resin I contains the compound represented by the above formula (1-1), the compound represented by the above formula (1-2) and bisphenol A diglycidyl base ether, the content ratio of the compound represented by the above formula (1-1) is 60% by weight, and the content ratio of the compound represented by the above formula (1-2) is 22% by weight. Furthermore, it was confirmed that R ¹ of the compound represented by the above formula (1-1) contained in the curable resin I is a hydrogen atom, R ² is an ethylene group, and R ³ is a structure represented by the above formula (3-3) (R ⁶ is a hydrogen atom, R ⁷ is dodecyl group), n is 0, and Ep is a structure derived from bisphenol A diepoxypropyl ether. Furthermore, it was confirmed that R ¹ of the compound represented by the above formula (1-2) contained in the curable resin I is a hydrogen atom, R ² is an ethylene group, and R ³ is a structure represented by the above formula (3-3) (R ⁶ is a hydrogen atom, R ⁷ is dodecyl group), n is 0, and Ep is a structure derived from bisphenol A diepoxypropyl ether.

(Preparation of Hardening Resin J) Add 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 to the reaction flask, and heat Stir at 90°C for 5 hours. Thereafter, 168 parts by weight of 4-methylcyclohexane-1,2-dicarboxylic anhydride was added and further stirred for 5 hours. Next, 340 parts by weight of bisphenol A diglycidyl ether and 0.5 parts by weight of triphenylphosphine were added to the obtained reactant, and the mixture was stirred at 110° C. for 5 hours, thereby obtaining curable resin J. It was confirmed by ¹ H-NMR and ¹³ C-NMR that the curable resin J contains the compound represented by the above formula (1-1), the compound represented by the above formula (1-2), and bisphenol A diglycidyl base ether, the content ratio of the compound represented by the above formula (1-1) is 57% by weight, and the content ratio of the compound represented by the above formula (1-2) is 21% by weight. Furthermore, it was confirmed that R ¹ of the compound represented by the above formula (1-1) contained in the curable resin J is a hydrogen atom, R ² is an ethylene group, and R ³ is a structure represented by the above formula (3-1) (R ⁴ is methyl), X is the ring-opened structure of ε-caprolactone, n is 1.0 (average value), and Ep is the structure derived from bisphenol A diepoxypropyl ether. Furthermore, it was confirmed that R ¹ of the compound represented by the above formula (1-2) contained in the curable resin J is a hydrogen atom, R ² is an ethylene group, and R ³ is a structure represented by the above formula (3-1) (R ⁴ is methyl group),

(Preparation of Curable Resin K) Except for changing 168 parts by weight of 4-methylcyclohexane-1,2-dicarboxylic anhydride into 148 parts by weight of phthalic anhydride, the same conditions as the above "(hardening Hardening resin K is obtained in the same manner as "Preparation of Hardening Resin H". It was confirmed by ¹ H-NMR and ¹³ C-NMR that the curable resin K contains 55% by weight of the following compound: In the above formula (1-1), the part corresponding to R ¹ is a hydrogen atom, and the part corresponding to R ² The part corresponding to R 3 is ethylene group, the part corresponding to R ³ is 1,2-phenylene group, the value corresponding to n is 0, and the part corresponding to Ep is a structure derived from bisphenol A diepoxypropyl ether. Furthermore, it was confirmed that the curable resin K contains 24% by weight of the following compound: in the above formula (1-2), the part corresponding to R ¹ is a hydrogen atom, the part corresponding to R ² is an ethylene group, and the part corresponding to R ³ The part is 1,2-phenylene group, which corresponds to the value of n being 0, and the part corresponding to Ep is a structure derived from bisphenol A diglycidyl ether. Furthermore, it was confirmed that curable resin K contained 21% by weight of bisphenol A diglycidyl ether.

(Preparation of Curable Resin L) Except for changing 336 parts by weight of 4-methylcyclohexane-1,2-dicarboxylic anhydride into 296 parts by weight of phthalic anhydride, the same conditions as the above "(hardening Curable resin L is obtained in the same manner as "Preparation of curable resin A". It was confirmed by ¹ H-NMR and ¹³ C-NMR that the curable resin L is a compound in which the part corresponding to R ¹ in the above formula (1-2) is a hydrogen atom, and the part corresponding to R ² is an elastomer. Ethyl group, the part corresponding to R ³ is 1,2-phenylene group, the value corresponding to n is 0, and the part corresponding to Ep is a structure derived from bisphenol A diglycidyl ether.

(Preparation of hardening resin M) Add 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 the reaction flask. triphenylphosphine and stirred at 110° C. for 5 hours using a heating pack to obtain curable resin M. It was confirmed by ¹ H-NMR and ¹³ C-NMR that the content of the compound represented by the following formula (4-1) in the curable resin M was 53% by weight, and the content of the compound represented by the following formula (4-2) was 53% by weight. The content ratio of the compound was 22% by weight.

(Examples 1 to 12, Comparative Examples 1 to 4) According to the blending ratios described in Tables 1 and 2, each material was stirred using a planetary stirring device, and then uniformly mixed using a ceramic three-roller kneader to obtain the curable resin compositions of Examples 1 to 12 and Comparative Examples 1 to 4. things. As a planetary stirring device, a defoaming stirrer Taro (manufactured by Celgene Corporation) was used.

＜Evaluation＞ The following evaluation was performed on each curable resin composition obtained in the Examples and Comparative Examples. The results are shown in Tables 1 and 2.

(Adhesion to the alignment film) Coat the imine resin on the glass substrate with the ITO film by spin coating, pre-bake at 80°C, and then bake at 230°C to produce the alignment film. Membrane substrate. As the imine resin, SE7492 (manufactured by Nissan Chemical Co., Ltd.) was used. Using a planetary stirring device, 1 part by weight of the silica spacer was uniformly dispersed in 100 parts by weight of each of the curable resin compositions obtained in the examples and comparative examples. As the silica spacer, SI-H055 (manufactured by Sekisui Chemical Industry Co., Ltd.) was used. Secondly, tiny droplets of the curable resin composition dispersed with silicon dioxide spacers are dropped on the alignment film of the substrate with the alignment film. The other substrate with the alignment film is bonded to the substrate with the alignment film on which the curable resin composition is dropped in a cross shape through the curable resin composition, and then irradiated with ultraviolet light of 3000 mJ/cm ² using a metal halogen lamp. The adhesive test piece was obtained by heating at 120° C. for 60 minutes. Use a metal cylinder with a radius of 5 mm to press the end of the substrate in the prepared test piece at a speed of 5 mm/min, and measure the strength when the panel peels off at this time. When the value obtained by dividing the measured value (kgf) by the seal diameter (cm) is 3.0 kgf/cm or more, mark it as "◎". When it reaches 2.5 kgf/cm or more and less than 3.0 kgf/cm, mark it as "◎". "O", the case of 2.0 kgf/cm or more and less than 2.5 kgf/cm is recorded as "Δ", the case of less than 2.0 kgf/cm is recorded as "×", and the adhesion to the alignment film is evaluated.

(Anti-moisture permeability) Using a coater, apply each curable resin composition obtained in the Examples and Comparative Examples on a smooth release film to a thickness of 200 μm to 300 μm. Next, a metal halide lamp was used to irradiate ultraviolet light of 3000 mJ/cm ² and then heated at 120° C. for 60 minutes to obtain a film for moisture permeability measurement. Make a cup for the moisture permeability test using the moisture permeability test method for moisture-proof packaging materials (cup method) in accordance with JIS Z 0208, attach the obtained moisture permeability measurement film, and put it into a temperature of 80°C. A constant temperature and humidity oven with a humidity of 90%RH is used to measure the moisture permeability. When the obtained moisture permeability value is less than 50 g/m ² ·24hr, record it as "◎", and when it exceeds 50 g/m ² ·24hr and does not reach 60 g/m ² ·24hr, record it as "〇" , the case of 60 g/m ² ·24hr or more and less than 70 g/m ² ·24hr is recorded as "Δ", and the case of 70 g/m ² ·24hr or more is marked as "×" to evaluate the moisture permeability prevention sex.

(Display performance of liquid crystal display elements) Coating imine resin on a glass substrate with an ITO film by spin coating, pre-baking at 80°C, and then baking at 230°C to produce an oriented display. Membrane substrate. As the imine resin, SE7492 (manufactured by Nissan Chemical Co., Ltd.) was used. Using a planetary stirring device, 1 part by weight of the silica spacer was uniformly dispersed in 100 parts by weight of each of the curable resin compositions obtained in the examples and comparative examples, and degassing was performed to remove the curable resin composition. After soaking, fill the syringe for dispensing and perform defoaming again. As the silicon dioxide spacer, SI-H055 (manufactured by Sekisui Chemical Industry Co., Ltd.) was used, and as the dispensing syringe, PSY-10E (manufactured by Musashi Industrial Co., Ltd.) was used. Secondly, use a dispenser to apply the curable resin composition on the alignment film of the substrate with the alignment film in the form of a picture frame. As a distributor, SHOTMASTER300 (manufactured by Musashi Industrial Co., Ltd.) was used. Then, a liquid crystal dropping device is used to drop-coat tiny drops of TN liquid crystal into the frame of the curable resin composition. On the substrate with the alignment film coated with TN liquid crystal, another substrate with the alignment film was overlapped through the curable resin composition, and the two substrates were bonded together using a vacuum bonding device under a reduced pressure of 5 Pa. Get the unit. As the TN liquid crystal, JC-5001LA (manufactured by Chisso Corporation) was used. The obtained unit was irradiated with ultraviolet light of 3000 mJ/cm ² using a metal halide lamp, and then heated at 120° C. for 60 minutes to harden the curable resin composition, thereby producing a liquid crystal display element. After the obtained liquid crystal display element was stored for 144 hours in an environment with a temperature of 80°C and a humidity of 90% RH, it was driven with a voltage of AC3.5 V to visually observe whether there was any display unevenness (color unevenness). The case where no display unevenness is observed at all around the liquid crystal display element is marked as "◎", the case where slight and light display unevenness is found is marked as "O", the case where clear and deep display unevenness is present is marked as "◎" The display performance of the liquid crystal display element is evaluated as "Δ", and the situation where clear and deep display unevenness exists not only in the peripheral part but also extends to the central part is recorded as "×". Furthermore, liquid crystal display devices rated "◎" or "〇" are of a level that has no practical problems at all.

[Table 1] Example 1 2 3 4 5 6 7 8 9 10 11 12 Composition (parts by weight) hardening resin Hardening resin A 30 5 90 - - - - - - - - - Hardening resin B - - - 30 - - - - - - - - Hardening resin C - - - - 30 - - - - - - - Hardening resin D - - - - - 30 - - - - - - Hardening resin E - - - - - - 30 - - - - - Hardening resin F - - - - - - - 30 - - - - Hardening resin G - - - - - - - - 30 - - - Hardening resin H - - - - - - - - - 30 - - Hardening resin I - - - - - - - - - - 30 - Hardening resinJ - - - - - - - - - - - 30 Bisphenol A type epoxy acrylate (manufactured by Daicel Allnex, "EBECRYL 3700") 60 85 - 60 60 60 60 60 60 70 70 70 Bisphenol A type epoxy resin (manufactured by DIC Corporation, "EPICLON EXA-850CRP") 10 10 10 10 10 10 10 10 10 - - - Photoradical polymerization initiator 2,2-Dimethoxy-1,2-diphenylethane-1-one (manufactured by BASF, "IRGACURE 651")) 1 1 1 1 1 1 1 1 1 1 1 1 Thermal radical polymerization initiator Polymer azo compound (manufactured by Fuji Film Wako Pure Chemical Co., Ltd., "VPE-0201")) 2 2 2 2 2 2 2 2 2 2 2 2 heat hardener Malonic acid dihydrazine (manufactured by FineChem Japan, "MDH") 2 2 2 2 2 2 2 2 2 2 2 2 filler Silicon dioxide (manufactured by Admafine Technology Co., Ltd., "Admafine SO-C2") 20 20 20 20 20 20 20 20 20 20 20 20 Silane coupling agent 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Industry Co., Ltd., "KBM-403") 1 1 1 1 1 1 1 1 1 1 1 1 Evaluation Adhesion to alignment film ◎ 〇 ◎ 〇 〇 ◎ ◎ 〇 ◎ ◎ ◎ ◎ Anti moisture permeability ◎ 〇 ◎ ◎ ◎ 〇 〇 ◎ 〇 ◎ 〇 〇 Display performance of liquid crystal display elements ◎ 〇 ◎ ◎ ◎ ◎ 〇 ◎ ◎ ◎ 〇 〇

[Table 2] Comparative example 1 2 3 4 Composition (parts by weight) hardening resin Hardening resin K 30 - - - Hardening resin L - 30 - - Caprolactone modified bisphenol A type epoxy acrylate (manufactured by Daicel Allnex, "EBECRYL3708") - - 30 - Hardening resin M - - - 30 Bisphenol A type epoxy acrylate (manufactured by Daicel Allnex, "EBECRYL3700") 60 60 60 60 Bisphenol A type epoxy resin (manufactured by DIC Corporation, "EPICLON EXA-850CRP") 10 10 10 10 Photoradical polymerization initiator 2,2-Dimethoxy-1,2-diphenylethane-1-one (manufactured by BASF, "IRGACURE 651")) 1 1 1 1 Thermal radical polymerization initiator Polymer azo compound (manufactured by Fuji Film Wako Pure Chemical Co., Ltd., "VPE-0201")) 2 2 2 2 heat hardener Malonic acid dihydrazine (manufactured by FineChem Japan, "MDH") 2 2 2 2 filler Silicon dioxide (manufactured by Admafine Technology Co., Ltd., "Admafine SO-C2") 20 20 20 20 Silane coupling agent 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Industry Co., Ltd., "KBM-403") 1 1 1 1 Evaluation Adhesion to alignment film × × ◎ 〇 Anti moisture permeability ◎ ◎ × Δ Display performance of liquid crystal display elements 〇 〇 Δ × [Industrial availability]

According to the present invention, it is possible to provide a curable resin composition that is excellent in both adhesion to an alignment film and moisture permeability prevention. Furthermore, according to the present invention, it is possible to provide a sealant for liquid crystal display elements, a vertical conductive material and a liquid crystal display element using the curable resin composition.

without

without

Claims (6)

A curable resin composition containing a curable resin, a polymerization initiator and/or a thermosetting agent, the curable resin containing a compound represented by the following formula (1-1) and/or the following formula (1- 2) The compound represented; In formulas (1-1) and (1-2), R ¹ represents a hydrogen atom or a methyl group, and R ² represents a group represented by the following formula (2-1), (2-2) or (2-3). , R ³ represents a structure derived from an optionally substituted aliphatic dicarboxylic acid or anhydride thereof, the structure; In formulas (2-1) to (2-3), ✽ represents the bonding position. In formula (2-2), a is an integer from 1 to 8. In formula (2-3), b is from 1 to 8. For the following integers, c is an integer from 1 to 3, and d is an integer from 1 to 8. The curable resin composition of claim 1, wherein in the formulas (1-1) and (1-2), R ³ is the following formula (3-1), (3-2) or (3-3) ) the structure represented by; In the formula (3-1) ~ (3-3), ✽ represents the bonding position. In the formula (3-1), R ⁴ represents a hydrogen atom or an alkyl group with a carbon number of 1 to 10, formula (3-2) in formula ( ^3-3 ), R ⁶ and R ⁷ respectively independently represent a hydrogen atom or an organic group with a carbon number of 1 to 60, or R ⁶ , R ⁷ bonded structure. The curable resin composition of claim 1 or 2, wherein the curable resin contains the compound represented by the formula (1-1). A sealant for liquid crystal display elements using the curable resin composition of claim 1, 2 or 3. A vertical conductive material containing the sealant for liquid crystal display elements of claim 4 and conductive fine particles. A liquid crystal display element having a cured product of the sealant for liquid crystal display elements of claim 4 or a cured product of the upper and lower conductive material of claim 5.