TW201538461A - Polymerizable monomer, polymer compound, photocurable resin composition, sealing element for liquid crystal display element, vertical conduction material, and liquid crystal display element - Google Patents

Abstract

A purpose of the present invention is to provide a polymerizable monomer having low contamination with respect to liquid crystals, high sensitivity to light of long wavelengths, and an exceptional sensitizing effect, and a polymer compound obtained by polymerizing the polymerizable monomer. Another purpose of the present invention is to provide a photocurable resin composition containing the polymerizable monomer and/or the polymer compound; a sealing agent for liquid crystal display elements which uses the photocurable resin composition; and a vertical conduction material and liquid crystal display element which are manufactured using the sealing agent for liquid crystal display elements. The present invention is a polymerizable monomer obtained by causing a thioxanthone derivative that has a functional group capable of reacting with a dialkylaminobenzoic acid compound or epoxy group to react with an epoxy group having an unsaturated double bond or an epoxy group having an alkoxysilyl group.

Description

Polymerizable monomer, polymer compound, photocurable resin composition, sealing agent for liquid crystal display element, upper and lower conductive materials, and liquid crystal display element

The present invention relates to a polymerizable monomer which is low in contamination to liquid crystal, has high sensitivity to long-wavelength light, and is excellent in sensitizing effect, and a polymer compound obtained by polymerizing the polymerizable monomer. Furthermore, the present invention relates to a photocurable resin composition containing the polymerizable monomer and/or the polymer compound, a sealing agent for a liquid crystal display element using the photocurable resin composition, and a liquid crystal display device using the liquid crystal display device. The upper and lower conductive materials and the liquid crystal display element are used for the display element sealing agent.

In recent years, as a method of manufacturing a liquid crystal display element such as a liquid crystal display unit, as disclosed in Patent Document 1 and Patent Document 2, from the viewpoints of shortening the tact time and optimizing the amount of liquid crystal. A liquid crystal dropping method called a dropping method, which is a photocuring and curing agent containing a curable resin, a photopolymerization initiator, and a thermosetting agent, is used.

In the dropping method, first, a rectangular sealing pattern is formed by dispensing on one of the two sheets of the electrode-attached transparent substrate. Then, the liquid crystal droplets are dropped onto the entire surface of the transparent substrate in a state where the sealant is not cured, and the other transparent substrate is immediately superposed, and the sealing portion is temporarily hardened by irradiating light such as ultraviolet rays. Thereafter, heating is performed during liquid crystal annealing to perform formal hardening. Production of liquid crystal display elements. If the substrate is to be bonded under reduced pressure, the liquid crystal display element can be manufactured with extremely high efficiency. Now, the dropping method is the mainstream of the manufacturing method of the liquid crystal display element.

In addition, in the modernization of various mobile devices including liquid crystal panels such as mobile phones and portable game machines, the miniaturization of devices is the most sought-after issue. As a method of downsizing the device, a narrow edge of the liquid crystal display portion can be cited. For example, the position of the sealing portion is placed under a black matrix (hereinafter also referred to as a narrow edge design).

However, in the narrow edge design, since the sealant is disposed directly under the black matrix, if the dropping method is performed, the light irradiated when the sealant is photocured is blocked, and the light cannot reach the inside of the sealant. And the problem of hardening becomes insufficient. If the curing of the sealant is insufficient, the uncured sealant component is eluted into the liquid crystal to cause liquid crystal contamination.

Patent Document 3 discloses a photopolymerization initiator which is formulated with a high sensitivity in a sealant. However, when only a high-sensitivity photopolymerization initiator is blended, the sealant cannot be sufficiently photocured. Further, Patent Document 4 discloses that a high-sensitivity photopolymerization initiator and a sensitizer are combined and formulated in a sealant. However, there is a problem that liquid crystal contamination is liable to occur due to the use of a sensitizer.

Patent Document 1: Japanese Laid-Open Patent Publication No. 2001-133794

Patent Document 2: International Publication No. 02/092718

Patent Document 3: International Publication No. 2011/002028

Patent Document 4: Japanese Laid-Open Patent Publication No. 2010-286640

An object of the present invention is to provide a polymerizable monomer which is low in pollution to liquid crystal, has high sensitivity to long-wavelength light, and is excellent in sensitizing effect, and a polymer compound obtained by polymerizing the polymerizable monomer. Moreover, an object of the present invention is to provide a photocurable resin composition containing the polymerizable monomer and/or the polymer compound, a sealing agent for a liquid crystal display element using the photocurable resin composition, and the like. The upper and lower conductive materials and the liquid crystal display element are used for the liquid crystal display element sealing agent.

The present invention is a 2-alkylaminobenzoic acid-based compound or a 9-oxosulfuric acid having a functional group reactive with an epoxy group. A polymerizable monomer obtained by reacting a derivative with an epoxy compound having an unsaturated double bond or an epoxy compound having an alkoxysilyl group.

Hereinafter, the present invention will be described in detail.

The present inventors have surprisingly found that a polymerizable monomer having a specific structure or a polymer compound obtained by polymerizing the polymerizable monomer has low contamination to liquid crystal, high sensitivity to long-wavelength light, and excellent sensitization effect. . Therefore, the present inventors have found that a photocurable resin composition obtained by blending the polymerizable monomer or the polymer compound as a photopolymerization initiator or a sensitizer is excellent in photocurability. The present invention can be completed by a sealing agent for a liquid crystal display element which can suppress liquid crystal contamination.

The polymerizable single system of the present invention is a dialkylaminobenzoic acid compound or a 9-oxosulfuric acid having a functional group reactive with an epoxy group. Derivative (hereinafter, referred to as "9-oxygen sulfide" The derivative ") is obtained by a reaction with an epoxy compound having an unsaturated double bond or an epoxy compound having an alkoxyfluorenyl group (hereinafter referred to as "the epoxy compound of the present invention").

Examples of the dialkylaminobenzoic acid-based compound include a compound represented by the following formula (1-1), a compound represented by the following formula (1-2), and the following formula (1-3). The compound represented, 7-(dimethylamino)coumarin-3-carboxylic acid, and the like. In particular, the compound represented by the following formula (1-1), the compound represented by the following formula (1-2), or the compound represented by the following formula (1-3) is more preferably the following. A compound represented by the formula (2-1), a compound represented by the following formula (2-2), or a compound represented by the following formula (2-3).

The above 9-oxygen sulfur The derivative has a functional group reactive with an epoxy group. Examples of the functional group reactive with the epoxy group include a hydroxyl group, a carboxyl group, and an amine group. Among them, a hydroxyl group or a carboxyl group is preferred.

As the above 9-oxygen sulfur The derivative may, for example, be a compound represented by the following formula (3), 2-amino-9H-sulfur -9 ketone and the like. Among them, a compound represented by the following formula (3) is preferred, and a compound represented by the following formula (5-1) or a compound represented by the formula (5-2) is more preferred.

In the formula (3), X is hydrogen, a hydroxyl group, or a group represented by the following formula (4). Each X may be the same or different, but at least one X is a hydroxyl group or a group represented by the following formula (4).

And the above dialkylaminobenzoic acid compound or the above 9-oxygen sulfur The epoxy compound of the present invention in which the derivative is reacted is an epoxy compound having an unsaturated double bond or an epoxy compound having an alkoxyfluorenyl group.

The above unsaturated double bond or alkoxyfluorenyl group has a polycondensation as a polymerizable monomer of the present invention The role of the associated polymeric reactive group.

Examples of the functional group having an unsaturated double bond include (meth)acryloxy group, vinyl group, allyl group and the like. Among them, a (meth)acryloxy group is preferred.

In the present specification, the above-mentioned "(meth)acryloxyloxy group" means an acryloxy group or a methacryloxy group.

Examples of the alkoxyfluorenyl group include a trimethoxysilyl group, a triethoxysulfonyl group, a methyldimethoxyfluorenyl group, and a methyldiethoxyfluorenyl group. Among them, a trimethoxyindenyl group is preferred.

As the epoxy compound of the present invention, a compound represented by the following formula (6-1) or (6-2) can be preferably used.

In the formula (6-1), R ¹ represents hydrogen or a methyl group. In the formula (6-2), R ² represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. Each R ² may be the same or different, but at least one R ² is an alkoxy group having a carbon number of 1 to 10.

As the above dialkylaminobenzoic acid compound or the above 9-oxosulfur The method for obtaining a polymerizable monomer of the present invention by reacting a derivative with the epoxy compound of the present invention includes the above-mentioned dialkylaminobenzoic acid compound or the above 9-side in the presence of a basic catalyst. Oxygen and sulfur A method in which the derivative and the epoxy compound of the present invention are stirred at 80 to 130 ° C for 6 to 72 hours to carry out a reaction. The above dialkylaminobenzoic acid compound or the above 9-oxygen sulfur The reaction of the derivative with the epoxy compound of the present invention is preferably carried out in the presence of a trivalent organic phosphoric acid compound and/or an amine compound from the viewpoint of reactivity.

Making the above dialkylaminobenzoic acid compound or the above 9-oxygen sulfur When the derivative is reacted with the epoxy compound of the present invention, the above dialkylaminobenzoic acid compound or the above 9-oxygen sulfur The ratio of use of the derivative to the epoxy compound of the present invention is preferably a molar ratio of the above-mentioned dialkylaminobenzoic acid compound or the above 9-oxygen sulfur. Derivative: The epoxy compound of the present invention = 1:1 to 10:1. By using the above dialkylaminobenzoic acid compound or the above 9-oxygen sulfur The ratio of use of the derivative to the epoxy compound of the present invention is in this range, and the polymerizable monomer of the present invention having a photoreactive group can be produced in a high yield.

As the above dialkylaminobenzoic acid compound or the above 9-oxosulfur The basic catalyst used in the reaction of the derivative with the epoxy compound of the present invention may, for example, be triphenylphosphine, triethylamine, tripropylamine, tetramethylethylenediamine or dimethyllaurylamine. And triethylbenzylammonium chloride, trimethyl cetyl ammonium bromide, tetrabutylammonium bromide, trimethylbutylphosphonium bromide, tetrabutylphosphonium bromide, and the like. Among them, triphenylphosphine is preferred.

Further, the basic catalyst may be carried on a polymer and used as a polymer-supporting alkaline catalyst.

The polymerizable monomer of the present invention obtained by reacting the above-mentioned dialkylaminobenzoic acid-based compound with the epoxy compound of the present invention (hereinafter, also referred to as "polymerization obtained from a dialkylaminobenzoic acid-based compound" The specific monomer "), specifically, for example, the following formula (7) a compound represented by -1) to (7-6).

In the formulae (7-1) to (7-3), R ¹ represents hydrogen or a methyl group. In the formulae (7-4) to (7-6), R ² represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. Each R ² may be the same or different, but at least one R ² is an alkoxy group having a carbon number of 1 to 10.

As the above 9-oxygen sulfur The polymerizable monomer of the present invention obtained by reacting a derivative with the epoxy compound of the present invention (hereinafter, also referred to as "from 9-oxosulfuric acid Specific examples of the polymerizable monomer obtained by the derivative are, for example, compounds represented by the following formulas (8-1) to (8-4).

In the formulae (8-1) and (8-2), R ¹ represents hydrogen or a methyl group. In the formulae (8-3) and (8-4), R ² represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. Each R ² may be the same or different, but at least one R ² is an alkoxy group having a carbon number of 1 to 10.

The polymer compound obtained by polymerizing the polymerizable monomer of the present invention (hereinafter also referred to as "the polymer compound of the present invention") is also one of the present inventions.

The method of polymerizing the polymerizable monomer obtained from the above-described dialkylaminobenzoic acid-based compound in the polymerizable monomer of the present invention includes, for example, cationic polymerization, anionic polymerization, and radical polymerization. Among them, a method in which a compound dissolved in a toluene solvent is stirred at 60 to 100 ° C for 4 to 12 hours in the presence of a radical polymerization initiator such as azobisisobutyronitrile is preferably carried out.

The cationic polymerization catalyst used for cationic polymerization of the polymerizable monomer obtained from the above-mentioned dialkylaminobenzoic acid-based compound may, for example, be a mineral acid such as hydrochloric acid, nitric acid, sulfuric acid or phosphoric acid, or formic acid or acetic acid. A carboxylic acid such as propionic acid or a sulfonic acid such as methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid or p-toluenesulfonic acid. Among them, hydrochloric acid is preferred.

The anionic polymerization catalyst used for anionic polymerization of the polymerizable monomer obtained from the above dialkylaminobenzoic acid-based compound may, for example, be n-butyllithium, second butyllithium or t-butyllithium. Alkali lithium, 1,4-dilithium butane, etc. alkyl dilithium, phenyl lithium, ruthenium lithium, lithium naphthalene, sodium naphthalene, potassium naphthalate, n-butyl magnesium, n-hexyl magnesium, calcium ethoxylate Ethoxy calcium), calcium stearate, barium butoxide, barium ethoxylate, cesium isopropoxide, hydrazinium ethoxide, cesium oxyhydroxide, phenoxy hydrazine, diethylamino hydrazine, Barium stearate and the like. Among them, n-butyllithium is preferred.

The radical polymerization initiator used for radical polymerization of the polymerizable monomer obtained from the above dialkylaminobenzoic acid-based compound may, for example, be azobisiso An azo compound such as nitrile, azobiscyclohexanenitrite or azobis(2,4-dimethylvaleronitrile), or benzamidine peroxide, lauric acid peroxide, ortho-benzyl peroxybenzoate, ortho Organic peroxidation of benzamidine methoxybenzoate, 3,5,5-trimethylhexyl peroxide, tert-butyl peroxy-2-ethylhexanoate, di-tert-butyl peroxide Things and so on. Among them, azobisisobutyronitrile is preferred.

As the polymerizable monomer of the present invention, the above-mentioned 9-oxosulfur The method of polymerizing the polymerizable monomer obtained by the derivative is, for example, polymerization by a sol-gel method in the presence of an acidic catalyst or a basic catalyst, and preferably dissolved in an ethanol solvent. The method wherein the polymerizable monomer of the invention is mixed with water and stirred under an acidic catalyst at 60 to 120 ° C for 2 to 24 hours.

As a result of the above 9-oxosulfur Examples of the acidic catalyst used for the polymerization of the polymerizable monomer obtained by the derivative include inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid, or carboxylic acids such as formic acid, acetic acid, and propionic acid, or methanesulfonic acid or ethyl sulfonate. A sulfonic acid such as acid, benzenesulfonic acid or p-toluenesulfonic acid. Among them, hydrochloric acid is preferred.

As a result of the above 9-oxosulfur The basic catalyst used for the polymerization of the polymerizable monomer obtained by the derivative may, for example, be an inorganic compound such as sodium hydroxide, potassium hydroxide or ammonia, or an organic compound such as an amine compound. Among them, sodium hydroxide is preferred.

A preferred lower limit of the degree of polymerization of the polymer compound of the present invention is 3. When the degree of polymerization of the polymer compound of the present invention is 2, that is, a dimer, when it is used as a photopolymerization initiator or a sensitizer for a sealing agent for a liquid crystal display element, liquid crystal contamination cannot be sufficiently suppressed. . A more preferred lower limit of the degree of polymerization of the polymer compound of the present invention is 10.

Further, a preferred upper limit of the degree of polymerization of the polymer compound of the present invention is 1,000. When the polymerization degree of the polymer compound of the present invention exceeds 1,000, it is used as a photopolymerization initiator or sensitizer In the case of a sealant for a liquid crystal display element, the coatability may be deteriorated. A more preferable upper limit of the degree of polymerization of the polymer compound of the present invention is 100.

A preferred lower limit of the number average molecular weight of the polymer compound of the present invention is 2,000, and a preferred upper limit is 30,000. When the number average molecular weight of the polymer compound of the present invention is less than 2,000, the liquid crystal contamination may not be sufficiently suppressed when it is used as a photopolymerization initiator or a sensitizer for a sealing agent for a liquid crystal display device. When the number average molecular weight of the polymer compound of the present invention is more than 30,000, the coating property may be deteriorated when it is used as a photopolymerization initiator or a sensitizer for a sealing agent for a liquid crystal display device. The lower limit of the number average molecular weight of the polymer compound of the present invention is 5,000, and the upper limit is more preferably 10,000.

In the present specification, the above-mentioned number average molecular weight is a value measured by gel permeation chromatography (GPC) and determined by polystyrene conversion. For example, Shodex LF-804 (manufactured by Showa Denko KK) can be used as the column for measuring the number average molecular weight in terms of polystyrene by GPC.

The polymer compound of the present invention is highly sensitive to long-wavelength light and excellent in sensitizing effect, and thus can be preferably used as a photopolymerization initiator or a sensitizer.

A photocurable resin composition containing a curable resin, a polymerizable monomer of the present invention, and/or a polymer compound of the present invention is also one of the present inventions.

The photocurable resin composition of the present invention preferably contains the polymer compound of the present invention from the viewpoint of not reacting with a curable resin immediately after application to a substrate or the like and preventing liquid crystal contamination. The polymer compound of the present invention has a function as a photopolymerization initiator or a sensitizer.

In the photocurable resin composition of the present invention, the polymer compound of the present invention The content is preferably 0.5 parts by weight, and preferably 20 parts by weight, based on 100 parts by weight of the curable resin. When the content of the polymer compound of the present invention is less than 0.5 part by weight, the photocurable resin composition obtained may be inferior in photocurability. When the content of the polymer compound of the present invention exceeds 20 parts by weight, the photocurable resin composition obtained may have poor weather resistance or storage stability, or may be used in the case of a sealant for a liquid crystal display element. The situation of pollution. A more preferred lower limit of the content of the polymer compound of the present invention is 2 parts by weight, and a more preferred upper limit is 10 parts by weight.

The photocurable resin composition of the present invention is preferably a polymer compound of the present invention obtained by polymerizing a polymerizable monomer obtained from the above dialkylaminobenzoic acid-based compound (hereinafter also referred to as "two a polymer compound obtained by an alkylaminobenzoic acid compound"), and a 9-oxosulfuric acid obtained by the above The polymer compound of the present invention obtained by polymerizing a polymerizable monomer obtained by a derivative (hereinafter, also referred to as "from 9-oxosulfuric acid The polymer compound obtained by the derivative") is contained in combination, and it is more preferable to use the polymer compound obtained from the above dialkylaminobenzoic acid compound as a photopolymerization initiator, and the above 9-oxygen sulfur The polymer compound obtained by the derivative is used as a sensitizer.

In the photocurable resin composition of the present invention, the polymer compound obtained from the above dialkylaminobenzoic acid compound and the above 9-oxosulfuric acid When the polymer compound obtained by the derivative is contained in combination, the polymer compound obtained from the above dialkylaminobenzoic acid compound and the above-mentioned 9-oxosulfuric acid The content ratio of the polymer compound obtained by the derivative is preferably a polymer compound obtained from a dialkylaminobenzoic acid compound by weight ratio: 9-oxosulfur The polymer compound obtained by the derivative = 1:1~5:1. By polymerizing a polymer compound obtained from a dialkylaminobenzoic acid compound with 9-oxosulfur The content ratio of the polymer compound obtained by the derivative is in this range, and the photocurable resin composition obtained is particularly excellent in photocurability using light of a long wavelength.

When the photocurable resin composition of the present invention is used as a sealing agent for a liquid crystal display device, in addition to the polymer compound of the present invention, other photopolymerization initiators may be contained in a range that does not cause adverse effects such as liquid crystal contamination. Or other sensitizers.

Examples of the other photopolymerization initiator include a benzophenone compound, an acetophenone compound, a mercaptophosphine oxide compound, a titanocene compound, an oxime ester compound, and a benzoin ether compound. Benzene oxime, 9-oxo sulphur A compound represented by the following formula (9-1), a compound represented by the following formula (9-2), and the like.

As a commercially available one of the other photopolymerization initiators, for example, IRGACURE 184, IRGACURE 369, IRGACURE 379, IRGACURE 651, IRGACURE 819, IRGACURE 907, IRGACURE 2959, IRGACURE OXE01, LUCIRIN TPO (all manufactured by BASF Corporation), benzoin methyl ether, benzoin Ether, benzoin isopropyl ether (all manufactured by Tokyo Chemical Industry Co., Ltd.), Adeka Optomer-N-1414, Adeka Optomer-N-1717, Adeka Optomer-N-1919, Adeka Optomer-NCI-839, Adeka Optomer-NCI-930, etc. (all manufactured by ADEKA).

Examples of the other sensitizer include an anthracene derivative, an anthracene derivative, a coumarin derivative, and 9-oxosulfuric acid. A derivative, a phthalocyanine derivative, a compound represented by the following formula (10-1), a compound represented by the following formula (10-2), and the like.

Examples of the above anthracene derivative include 9,10-dibutoxyanthracene, 9,10-dipropoxyanthracene, and 9,10-ethoxyanthracene.

Examples of the anthracene derivative include 2-ethylhydrazine, 1-methylhydrazine, 1,4-dihydroxyindole, and 2-(2-hydroxyethoxy)-hydrazine.

Examples of the coumarin derivative include 7-diethylamino-4-methylcoumarin and the like.

As the above 9-oxygen sulfur Derivatives, for example, 2,4-diethyl 9-oxosulfur 2-chloro 9-oxosulfur 4-isopropyl 9-oxosulfur 1-chloro-4-propyl 9-oxosulfur Wait.

Examples of the phthalocyanine derivative include phthalocyanine and the like.

Further, the benzophenone-based compound exemplified above as another photopolymerization initiator may be used as the other sensitizer.

The photocurable resin composition of the present invention contains a curable resin.

The curable resin preferably contains a (meth)acrylic resin.

The (meth)acrylic resin preferably has 2 to 3 (meth)acryloxy groups in the molecule in terms of reactivity.

Examples of the (meth)acrylic resin include an ester compound obtained by reacting a compound having a hydroxyl group with (meth)acrylic acid, and a ring obtained by reacting (meth)acrylic acid with an epoxy compound. Oxy (meth) acrylate, urethane (meth) acrylate obtained by reacting a (meth)acrylic acid derivative having a hydroxyl group with an isocyanate compound. Among them, epoxy (meth) acrylate is preferred. In the present specification, the above-mentioned "(meth)acryl oxime" means propylene oxime or methacryl oxime, and the above-mentioned "(meth)acrylic resin" means having (meth) propylene oxime Base resin. Moreover, the above-mentioned "(meth) acrylate" means acrylate or methacrylate. Further, the above-mentioned "epoxy (meth) acrylate" means a compound obtained by reacting all of the epoxy groups in the epoxy resin with (meth)acrylic acid.

Examples of the monofunctional ones of the above ester compounds include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and (methyl). ) 2-hydroxybutyl acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, isooctyl (meth)acrylate, lauryl (meth)acrylate, (meth)acrylic acid Fatty ester, isodecyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, methoxyethylene glycol (meth) acrylate, (methyl) ) 2-ethoxyethyl acrylate, tetrahydrofuran methyl (meth) acrylate, benzyl (meth) acrylate, ethyl carbitol (meth) acrylate, phenoxyethyl (meth) acrylate, Phenoxydiethylene glycol (meth) acrylate, phenoxy polyethylene glycol (A Acrylate, methoxypolyethylene glycol (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoro (meth) acrylate Propyl ester, (meth)acrylic acid 1H, 1H, 5H-octafluoropentyl ester, quinone imine (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylate N-butyl acrylate, propyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isodecyl (meth) acrylate, isomyristate (meth) acrylate Ester, 2-butoxyethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, isodecyl (meth)acrylate, (methyl) ) diethylaminoethyl acrylate, dimethylaminoethyl (meth) acrylate, 2-(methyl) propylene methoxyethyl succinate, 2-(methyl hexahydrophthalate) ) propylene methoxyethyl ester, 2-(methyl) propylene oxiranyl 2-hydroxypropyl phthalate, glycidyl (meth) acrylate, 2-(methyl) propylene decyl phosphate Ethyl ester and the like.

Further, examples of the difunctional one of the above ester compounds include 1,4-butanediol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, and 1,6- Hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-nonanediol 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 (meth)acrylate, ethylene glycol di(a) Acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene oxide addition bisphenol A (Meth) acrylate, ethylene oxide addition bisphenol A di(meth) acrylate, ethylene oxide addition bisphenol F di(meth) acrylate, dimethylol dicyclopentadiene Di-(meth) acrylate, neopentyl glycol di(meth) acrylate, ethylene oxide modified di(meth) acrylate, 2-hydroxy-3 (meth) acrylate -(Meth)propylene methoxypropyl ester, carbonate diol di(meth) acrylate, polyether Glycol di (meth) acrylate, polyester diol di (meth) acrylate, polycaprolactone Diol (meth) acrylate, polybutadiene diol di (meth) acrylate, and the like.

Further, examples of the trifunctional or higher of the above ester compounds include pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, and propylene oxide addition tris. Propane tri(meth)acrylate, ethylene oxide addition trimethylolpropane tri(meth)acrylate, caprolactone modified trimethylolpropane tri(meth)acrylate, epoxy B Alkane addition of tris(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, di-trimethylolpropane IV (Meth) acrylate, pentaerythritol tetra(meth) acrylate, glycerol tri(meth) acrylate, propylene oxide addition glycerol tri(meth) acrylate, tris(meth) propylene oxime Ethyl ethyl phosphate and the like.

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

Examples of the epoxy resin which is a raw material for synthesizing the above epoxy (meth) acrylate include bisphenol A epoxy resin, bisphenol F epoxy resin, and bisphenol S epoxy resin. 2'-Diallyl bisphenol A type epoxy resin, hydrogenated bisphenol type epoxy resin, propylene oxide addition bisphenol A type epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy Resin, thioether epoxy resin, diphenyl ether epoxy resin, dicyclopentadiene epoxy resin, naphthalene epoxy resin, phenol novolak epoxy resin, o-cresol novolac epoxy resin , dicyclopentadiene novolac type epoxy resin, biphenyl novolac type epoxy resin, naphthol novolac type epoxy resin, glycidylamine type epoxy resin, alkyl polyol type epoxy resin, rubber modification A quality epoxy resin, a glycidyl ester compound, or the like.

As a commercial item of the said bisphenol A type epoxy resin, the jER828EL and jER1004 (The manufacture of the Mitsubishi Chemical company), EPICLON 850 (DIC Manufacturing) and so on.

The commercially available one of the bisphenol F-type epoxy resins may, for example, be jER806 or jER4004 (all manufactured by Mitsubishi Chemical Corporation).

The commercially available one of the bisphenol S-type epoxy resins is, for example, EPICLON EXA1514 (manufactured by DIC Corporation).

The commercially available one of the 2,2'-diallyl bisphenol A type epoxy resins is, for example, RE-810NM (manufactured by Nippon Kayaku Co., Ltd.).

The commercially available one of the hydrogenated bisphenol type epoxy resins is, for example, EPICLON EXA7015 (manufactured by DIC Corporation).

The commercially available one of the above-mentioned propylene oxide-added bisphenol A-type epoxy resins is, for example, EP-4000S (manufactured by Adeka Co., Ltd.).

The commercially available one of the resorcinol-type epoxy resins is, for example, EX-201 (manufactured by Nagase ChemteX Co., Ltd.).

As a commercial item of the above-mentioned biphenyl type epoxy resin, jER YX-4000H (made by Mitsubishi Chemical Corporation), etc. are mentioned, for example.

For example, YSLV-50TE (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.) and the like are mentioned as a commercial product of the above-mentioned thioether type epoxy resin.

As a commercial item of the above-mentioned diphenyl ether type epoxy resin, YSLV-80DE (made by Nippon Steel & Sumitomo Chemical Co., Ltd.), etc. are mentioned, for example.

The commercially available one of the above-mentioned dicyclopentadiene type epoxy resins is, for example, EP-4088S (manufactured by Adeka Co., Ltd.).

As a commercially available one of the above-mentioned naphthalene type epoxy resins, for example, EPICLON HP4032 can be cited. EPICLON EXA-4700 (all manufactured by DIC Corporation).

As a commercial item of the above-mentioned phenol novolak type epoxy resin, EPICLON N-770 (made by DIC Corporation) etc. are mentioned, for example.

As a commercial item of the said o-cresol novolak-type epoxy resin, EPICLON N-670-EXP-S (made by the DIC company) etc. are mentioned, for example.

The commercially available one of the above-mentioned dicyclopentadiene novolac type epoxy resins is, for example, EPICLON HP7200 (manufactured by DIC Corporation).

The commercially available one of the above-mentioned biphenol novolak type epoxy resins is, for example, NC-3000P (manufactured by Nippon Kayaku Co., Ltd.).

As a commercial item of the above-mentioned naphthol novolac type epoxy resin, ESN-165S (made by Nippon Steel & Sumitomo Chemical Co., Ltd.), etc. are mentioned, for example.

For example, jER630 (manufactured by Mitsubishi Chemical Corporation), EPICLON 430 (manufactured by DIC Corporation), TETRAD-X (manufactured by Mitsubishi Gas Chemical Co., Ltd.), and the like are exemplified as the commercially available ones of the glycidylamine-type epoxy resins.

For example, ZX-1542 (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), EPICLON 726 (manufactured by DIC Corporation), and Epolight 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.) are listed as a commercial product of the above-mentioned alkyl polyol type epoxy resin. ), DENACOL EX-611 (manufactured by Nagase ChemteX), and the like.

For example, YR-450, YR-207 (all manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), Epolead PB (manufactured by Daicel Co., Ltd.), and the like are mentioned as a commercially available one of the rubber-modified epoxy resins.

As a commercial one of the above glycidyl ester compounds, for example, DENACOL EX can be cited. -147 (manufactured by Nagase ChemteX Co., Ltd.) and the like.

Other commercially available ones of the above-mentioned epoxy resins include YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), XAC4151 (made by Asahi Kasei Corporation), and jER7031 and jER1032 ( All are manufactured by Mitsubishi Chemical Corporation, EXA-7120 (manufactured by DIC Corporation), TEPIC (manufactured by Nissan Chemical Co., Ltd.), and the like.

As a method of producing the above-mentioned epoxy (meth) acrylate, specifically, for example, 360 parts by weight of a resorcinol type epoxy resin ("EX-201" manufactured by Nagase ChemteX Co., Ltd.) is used as a polymerization inhibitor. 2 parts by weight of p-methoxyphenol, 2 parts by weight of triethylamine as a reaction catalyst, and 210 parts by weight of acrylic acid were sent to air, and refluxed while stirring, and reacted at 90 ° C for 5 hours, thereby obtaining an interval. Hydroquinone type epoxy acrylate.

As a commercially available one of the above-mentioned epoxy (meth)acrylates, EBECRYL 860, EBECRYL 3200, EBECRYL 3201, EBECRYL 3412, EBECRYL 3600, EBECRYL 3700, EBECRYL 3701, EBECRYL 3702, EBECRYL 3703, EBECRYL 3800, EBECRYL 6040, EBECRRYLRDX 63182 (both are Daicel-Allnex) Manufactured), EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, EMA-1020 (all manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), epoxy ester M-600A, epoxy ester 40EM, ring Oxygen 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 (both It is manufactured by Kyoeisha Chemical Co., Ltd.), Denacol Acrylate DA-141, Denacol Acrylate DA-314, Denacol Acrylate DA-911 (all manufactured by Nagase ChemteX Co., Ltd.) and the like.

As a (meth)acrylic acid derivative having a hydroxyl group and isocyanate The (meth)acrylic acid amine ester obtained by the reaction of the compound can be obtained, for example, by making 2 equivalents of the (meth)acrylic acid derivative having a hydroxyl group with respect to 1 equivalent of the isocyanate compound having two isocyanate groups. The reaction is carried out in the presence of a catalytic amount of a tin-based compound.

Examples of the isocyanate compound which is a raw material of the above (meth)acrylic acid amide ester include isophorone diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, hexamethylene diisocyanate, and trimethyl ketone. Hexamethylene diisocyanate, diphenylmethane-4,4'-diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, Benzyl diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris(isocyanate phenyl) phosphorothioate, tetramethyl xylene diisocyanate, 1,6,11-undecane triisocyanate or the like.

Further, as the isocyanate compound which is a raw material of the above (meth)acrylic acid amide, for example, ethylene glycol, glycerin, sorbitol, trimethylolpropane, (poly)propylene glycol, carbonate diol, or polyglycol can also be used. A chain extended isocyanate compound obtained by reacting a polyol such as an ether diol, a polyester diol or a polycaprolactone diol with an excess of an isocyanate compound.

Examples of the (meth)acrylic acid derivative having a hydroxyl group as a raw material of the above (meth)acrylic acid amide include 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate. Hydroxyalkyl (meth) acrylate such as 4-hydroxybutyl methacrylate or 2-hydroxybutyl (meth) acrylate, or ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butane a mono (meth) acrylate of a glycol such as an alcohol, 1,4-butanediol or polyethylene glycol, or a monohydric alcohol such as trimethylolethane, trimethylolpropane or glycerin. Epoxy (meth) acrylate such as acrylate or di(meth) acrylate or bisphenol A epoxy acrylate.

The above-mentioned (meth)acrylic acid amine ester can be obtained, for example, by adding 134 parts by weight of trimethylolpropane, 0.2 parts by weight of BHT as a polymerization inhibitor, and dibutyltin dilaurate as a reaction catalyst. 0.01 parts by weight and 666 parts by weight of isophorone diisocyanate were reacted under reflux at 60 ° C for 2 hours, and then 51 parts by weight of 2-hydroxyethyl acrylate was added thereto, and air was blown while stirring at 90 °. The reaction was carried out at ° C for 2 hours.

For example, M-1100, M-1200, M-1210, M-1600 (all manufactured by Toagosei Co., Ltd.), EBECRYL230, EBECRYL270, EBECRYL4858, EBECRYL8402 are exemplified as the commercially available (meth) acrylate. ,EBECRYL8804,EBECRYL8803,EBECRYL8807,EBECRYL9260,EBECRYL1290,EBECRYL5129,EBECRYL4842,EBECRYL210,EBECRYL4827,EBECRYL6700,EBECRYL220,EBECRYL2220 (all manufactured by Daicel-Allnex), Artresin UN-9000H, Artresin UN-9000A, Artresin UN-7100, Artresin UN-1255, Artresin UN-330, Artresin UN-3320HB, Artresin UN-1200TPK, Artresin SH-500B (all manufactured by Gensei Industrial Co., Ltd.), U-122P, U-108A, U-340P, U-4HA, U- 6HA, U-324A, U-15HA, UA-5201P, UA-W2A, U-1084A, U-6LPA, U-2HA, U-2PHA, UA-4100, UA-7100, UA-4200, UA-4400, UA-340P, U-3HA, UA-7200, U-2061BA, U-10H, U-122A, U-340A, U-108, U-6H, UA-4000 (all manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), AH-600, AT-600, UA-306H, AI-600, UA-101T, UA-101I, UA-306T, UA-306I (all manufactured by Kyoeisha Chemical Co., Ltd.).

In order to improve the adhesion of the obtained photocurable resin composition, the curable resin preferably further contains an epoxy resin. Examples of the epoxy resin include an epoxy resin which is a raw material for synthesizing the above epoxy (meth)acrylate, or a partially modified (meth)acrylic epoxy resin.

In the present specification, the above-mentioned partial (meth)acrylic acid-modified epoxy resin means a resin having one or more epoxy groups and (meth)acrylonitrile groups in one molecule, for example, by It is obtained by reacting a partial epoxy group of one of epoxy resins having two or more epoxy groups with (meth)acrylic acid.

In the case where the photocurable resin composition of the present invention contains the above (meth)acrylic resin and the above epoxy resin, the ratio of (meth)acryloxy group to epoxy group is preferably 50:50. The above (meth)acrylic resin and the above epoxy resin are blended in a manner of ~95:5. When the ratio of the (meth) propylene methoxy group is less than 50%, a large amount of uncured epoxy resin component is present even after the polymerization is completed, so that liquid crystal contamination occurs in the case of use as a sealing agent for a liquid crystal display device. . When the ratio of the (meth)acryloxy group is more than 95%, the obtained photocurable resin composition may be inferior in adhesion.

In the case of suppressing liquid crystal contamination in the case of using a sealing agent for a liquid crystal display element, the curable resin preferably has a hydrogen bonding unit such as an -OH group, a -NH- group or a -NH ₂ group.

The photocurable resin composition of the present invention may further contain a thermal radical polymerization initiator. Examples of the thermal radical polymerization initiator include those composed of an azo compound, an organic peroxide, and the like. Among them, a starter composed of a polymer azo compound (hereinafter also referred to as "polymer azo starter") is preferred.

In the present specification, the term "polymer azo initiator" means a radical having an azo group to form a (meth) propylene oxime group which is hardened by heat, and has a number average molecular weight of 300. The above compounds.

A preferred lower limit of the number average molecular weight of the above polymer azo initiator is 1000, and a preferred upper limit is 300,000. When the number average molecular weight of the above polymer azo initiator is less than 1,000, the polymer azo initiator may adversely affect the liquid crystal when used in a sealing agent for a liquid crystal display device. When the number average molecular weight of the above polymer azo initiator is more than 300,000, it may be difficult to mix it in the curable resin. A lower limit of the number average molecular weight of the above polymer azo initiator is 5,000, a higher limit is 100,000, and a preferred lower limit is 10,000, and a preferred upper limit is 90,000.

Examples of the polymer azo initiator include those having a structure in which a plurality of units such as polyalkylene oxide or polydimethyl siloxane are bonded via an azo group.

The polymer azo initiator having a structure in which a plurality of units such as polyalkylene oxide are bonded via an azo group is preferably a polyethylene oxide structure. Examples of such a polymer azo initiator include a condensed polymer of 4,4'-azobis(4-cyanovaleric acid) and a polyalkylene glycol, or a 4,4'-couple. A condensed polymer of nitrogen bis(4-cyanovaleric acid) and polydimethyl methoxy oxane having an amine group at the terminal, and specific examples thereof include VPE-0201, VPE-4401, VPE-0601, and VPS. -0501, VPS-1001 (all manufactured by Wako Pure Chemical Industries, Ltd.) and the like.

In addition, examples of the azo compound which is not a polymer include V-65 and V-501 (all manufactured by Wako Pure Chemical Industries, Ltd.).

Examples of the organic peroxide include ketone peroxide and peroxy condensate. Ketone, hydrogen peroxide, dialkyl peroxide, peroxyester, dinonyl peroxide, peroxydicarbonate, and the like.

The content of the above-mentioned thermal radical polymerization initiator is preferably 0.1 part by weight, and preferably 30 parts by weight, based on 100 parts by weight of the curable resin. When the content of the above-mentioned thermal radical polymerization initiator is less than 0.1 part by weight, the thermal polymerization of the obtained photocurable resin composition may not sufficiently proceed. When the content of the thermal radical polymerization initiator is more than 30 parts by weight, liquid crystal contamination may occur due to an unreacted thermal radical polymerization initiator in the case of a sealant for a liquid crystal display device. A more preferred lower limit of the content of the above thermal radical polymerization initiator is 0.5 part by weight, and a still more preferred upper limit is 10 parts by weight.

The photocurable resin composition of the present invention may further contain a thermosetting agent.

Examples of the above-mentioned thermosetting agent include organic acid hydrazide, an imidazole derivative, an amine compound, a polyhydric phenol compound, and an acid anhydride. Among them, organic acid hydrazine can be preferably used.

Examples of the organic acid cerium include cerium azelate, bismuth isophthalate, bismuth adipate, and strontium malonate.

For example, SDH, ADH (all manufactured by Otsuka Chemical Co., Ltd.), Amicure VDH, Amicure VDH-J, and Amicure UDH (all manufactured by Ajinomoto Fine-Techno Co., Ltd.) may be mentioned.

The content of the above-mentioned thermosetting agent is preferably 1 part by weight, and preferably 50 parts by weight, based on 100 parts by weight of the curable resin. When the content of the above-mentioned thermosetting agent is less than 1 part by weight, the obtained photocurable resin composition may not be sufficiently thermally cured. If the content of the above thermal hardener exceeds 50 parts by weight, the obtained photohardenability tree The viscosity of the fat composition becomes too high and the coatability deteriorates. A more preferable upper limit of the content of the above thermal curing agent is 30 parts by weight.

The photocurable resin composition of the present invention preferably contains a filler in order to improve the viscosity, improve the adhesion by the stress dispersion effect, improve the linear expansion ratio, and improve the moisture resistance of the cured product.

Examples of the filler include talc, asbestos, alumina, diatomaceous earth, bentonite, bentonite, calcium carbonate, magnesium carbonate, alumina, montmorillonite, zinc oxide, iron oxide, magnesium oxide, and tin oxide. Inorganic fillers such as titanium oxide, magnesium hydroxide, aluminum hydroxide, glass beads, tantalum nitride, barium sulfate, gypsum, calcium silicate, sericite, activated clay, aluminum nitride, or polyester microparticles, polyurethane microparticles, ethylene An organic filler such as a base polymer fine particle or an acrylic polymer fine particle. These fillers may be used singly or in combination of two or more.

A preferred lower limit of the content of the above filler in 100 parts by weight of the photocurable resin composition of the present invention is 10 parts by weight, and a preferred upper limit is 70 parts by weight. When the content of the filler is less than 10 parts by weight, the effect of improving the adhesion or the like may not be sufficiently exhibited. When the content of the filler exceeds 70 parts by weight, the viscosity of the obtained photocurable resin composition is excessively increased and the coatability is deteriorated. A more preferred lower limit of the content of the above filler is 20 parts by weight, and a still more preferred upper limit is 60 parts by weight.

The photocurable resin composition of the present invention preferably contains a decane coupling agent. The decane coupling agent mainly functions as a secondary auxiliary agent for allowing the photocurable resin composition of the present invention to adhere well to a substrate or the like.

The decane coupling agent is excellent in the effect of improving the adhesion to a substrate or the like, and the curable resin is discharged into the liquid crystal when it is used as a sealing agent for a liquid crystal display element. From the viewpoint, for example, 3-aminopropyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-isocyanatepropylpropane can be preferably used. Trimethoxy decane and the like. These decane coupling agents may be used singly or in combination of two or more.

A preferred lower limit of the content of the above decane coupling agent in 100 parts by weight of the photocurable resin composition of the present invention is 0.1 part by weight, and a preferred upper limit is 20 parts by weight. When the content of the above decane coupling agent is less than 0.1 part by weight, the effect obtained by blending a decane coupling agent may not be sufficiently exhibited. When the content of the above-mentioned decane coupling agent exceeds 20 parts by weight, liquid crystal contamination may occur when the obtained photocurable resin composition is used for a sealing agent for a liquid crystal display element. A more preferred lower limit of the content of the above decane coupling agent is 0.5 part by weight, and a more preferred upper limit is 10 parts by weight.

The photocurable resin composition of the present invention may further contain an opacifier. The photocurable resin composition of the present invention can be preferably used as a light-shielding sealant by containing the above-mentioned opacifier.

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 preferred.

The titanium black is a substance which has a higher transmittance to light in the vicinity of the ultraviolet region, particularly at a wavelength of 370 to 450 nm, as compared with the average transmittance of light having a wavelength of 300 to 800 nm. In other words, the titanium black is provided with a light-shielding property of the photocurable resin composition of the present invention by sufficiently shielding light of a wavelength in the visible light region, and has a property of transmitting light of a wavelength near the ultraviolet region. The light-shielding agent contained in the photocurable resin composition of the present invention is preferably a material having high insulating properties, and is preferably a titanium black as a light-shielding agent having high insulating properties.

The optical density (OD value) per 1 μm of the titanium black system is preferably 3 or more, more preferably 4 the above. The higher the light blocking property of the titanium black, the better, and the OD value of the titanium black is not particularly preferably an upper limit, and is usually 5 or less.

The above-mentioned titanium black exhibits sufficient effects even if it is not surface-treated, but the following surface-treated titanium black may be used: the surface is treated with an organic component such as a coupling agent, or is oxidized by cerium oxide, titanium oxide, or oxidized. A coating of inorganic components such as cerium, alumina, zirconia or magnesia. Among them, it is preferable that the organic component treatment can further improve the insulation property.

In addition, the liquid crystal display element produced by using the photocurable resin composition of the present invention containing the titanium black as a light-shielding agent as a sealing agent for a liquid crystal display element has sufficient light-shielding property, so that it can be realized without leakage of light. A liquid crystal display element with high contrast and excellent image display quality.

The commercially available ones of the titanium blacks include, for example, 12S, 13M, 13M-C, 13R-N, and 14M-C (all manufactured by Mitsubishi Materials Co., Ltd.) and Tilack D (manufactured by Ako-Kasei Co., Ltd.).

A preferred lower limit of the specific surface area of the above titanium black is 13 m ² /g, a preferred upper limit is 30 m ² /g, a more preferred lower limit is 15 m ² /g, and a more preferred upper limit is 25 m ² /g.

Further, the preferred lower limit of the volume resistance of the titanium black is 0.5 Ω ‧ cm, the upper limit is preferably 3 Ω ‧ cm, the lower limit is preferably 1 Ω ‧ cm, and the upper limit is more preferably 2.5 Ω ‧ cm

The primary particle diameter of the light-shielding agent is not particularly limited as long as it is equal to or less than the distance between the substrates of the liquid crystal display element or the like, and a preferred lower limit is 1 nm, and a preferred upper limit is 5 μm. When the primary particle diameter of the light-shielding agent is less than 1 nm, the viscosity or the shakeability of the obtained photocurable resin composition is greatly increased, and the workability is deteriorated. When the primary particle diameter of the light-shielding agent exceeds 5 μm, the coatability of the obtained photocurable resin composition may be deteriorated. Above A lower limit of the primary particle diameter of the opacifier is 5 nm, a more preferred upper limit is 200 nm, and a further preferred lower limit is 10 nm, and further preferably, the upper limit is 100 nm.

A preferred lower limit of the content of the above-mentioned sunscreen agent in 100 parts by weight of the photocurable resin composition of the present invention is 5 parts by weight, and a preferred upper limit is 80 parts by weight. If the content of the above-mentioned sunscreen agent is less than 5 parts by weight, sufficient light-shielding properties may not be obtained. When the content of the light-shielding agent is more than 80 parts by weight, the adhesion of the obtained photocurable resin composition to the substrate or the strength after curing may be lowered or the drawability may be lowered. A more preferred lower limit of the content of the above-mentioned opacifier is 10 parts by weight, more preferably 70 parts by weight, still more preferably 30 parts by weight, and still more preferably 60 parts by weight.

The method for producing the photocurable resin composition of the present invention includes, for example, a homogenizer, a homomixer, a universal mixer, a planetary mixer, a kneader, a three-roll mill, and the like, and a curable resin. A method of mixing a polymerizable monomer of the present invention and/or a polymer compound of the present invention, and optionally a photopolymerization initiator or other sensitizer or a decane coupling agent.

The photocurable resin composition of the present invention can be preferably used as a sealant for liquid crystal display elements.

The sealing agent for liquid crystal display elements which used the photocurable resin composition of this invention is also one of this invention.

By disposing the conductive fine particles in the sealing agent for liquid crystal display elements of the present invention, the upper and lower conductive materials can be produced. Such a sealing agent for a liquid crystal display element of the present invention and a conductive fine particle upper and lower conductive material are also one of the present inventions.

The conductive fine particles can be used for metal balls or resin fine particles. A surface having a conductive metal layer formed thereon. Among them, a conductive metal layer formed on the surface of the resin fine particles can be electrically connected by the excellent elasticity of the resin fine particles without damaging the transparent substrate or the like, which is preferable.

The liquid crystal display element produced by using the sealing agent for liquid crystal display elements of the present invention or the underlying conductive material of the present invention is also one of the present inventions.

As a method of producing the liquid crystal display element of the present invention, for example, a method in which one of two transparent substrates such as a glass substrate or a polyethylene terephthalate substrate having an electrode such as an ITO film is used is used. a step of forming a rectangular seal pattern by a sealant or the like for a liquid crystal display element of the present invention by screen printing, dispenser application, or the like; and a liquid crystal display in a state in which an encapsulant for a liquid crystal display element of the present invention is uncured. The step of applying the entire surface of the transparent substrate to the surface of the transparent substrate and immediately superposing the other substrate; and irradiating the portion of the sealing pattern of the sealing agent for a liquid crystal display element of the present invention with ultraviolet light or the like to temporarily harden the sealing agent. And a step of heating the temporarily hardened sealant to form a hardening process.

According to the present invention, it is possible to provide a polymerizable monomer which is low in contamination to liquid crystal, has high sensitivity to long-wavelength light, and is excellent in sensitizing effect, and a polymer compound obtained by polymerizing the polymerizable monomer. Moreover, according to the present invention, a photocurable resin composition containing the polymerizable monomer and/or the polymer compound, a sealing agent for a liquid crystal display element using the photocurable resin composition, and the like can be provided. The upper and lower conductive materials and the liquid crystal display element are used for the liquid crystal display element sealing agent.

1‧‧‧Sealant

2‧‧‧Black matrix

3‧‧‧LCD

1 is a cross-sectional view schematically showing a liquid crystal display element produced by using each of the sealing agents for liquid crystal display elements obtained in the examples and the comparative examples in a state in which no light shielding portion is provided.

2 is a cross-sectional view schematically showing a liquid crystal display element produced by using a sealing agent for liquid crystal display elements obtained in the examples and the comparative examples in a state in which a light shielding portion is provided.

Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited to the examples.

(Production of Polymerizable Monomer A)

16.5 parts by weight of the compound represented by the formula (2-1) and 6.4 parts by weight of the compound represented by the formula (6-1) wherein R ¹ is hydrogen, in the PS-PPH3 (Biotage Japan Co., Ltd.) as an alkaline catalyst The reaction was carried out while stirring at 110 ° C for 48 hours in the presence of 0.7 part by weight of a basic catalyst containing triphenylphosphine supported on polystyrene (PS), thereby obtaining a formula (7-1). A compound (polymerizable monomer A) in which R ¹ is hydrogen.

Further, the compounding ratio of the compound represented by the formula (2-1) and the compound represented by the formula (6-1) wherein R ¹ is hydrogen is a compound represented by the formula (2-1) in terms of a molar ratio: The compound represented by the formula (6-1) wherein R ¹ is hydrogen = 2:1.

(Production of Polymer Compound A)

In the presence of 10 parts by weight of the obtained polymerizable monomer A in an amount of 0.5 part by weight of azobisisobutyronitrile as a polymerization initiator, the mixture was stirred at 70 ° C for 7 hours while reacting with nitrogen to cause a reaction. This gave the polymer compound A. The obtained polymer compound A had a number average molecular weight of 14,200 (degree of polymerization 50).

(Production of Polymerizable Monomer B)

16.5 parts by weight of the compound represented by the formula (2-2) and 5.5 parts by weight of the compound represented by the formula (6-1) wherein R ¹ is hydrogen, in the PS-PPH3 (Biotage Japan Co., Ltd.) as an alkaline catalyst The reaction was carried out while stirring at 110 ° C for 48 hours in the presence of 0.7 part by weight of a basic catalyst containing triphenylphosphine supported on polystyrene (PS), thereby obtaining the formula (7-2). A compound (polymerizable monomer B) in which R ¹ is hydrogen.

Further, the compounding ratio of the compound represented by the formula (2-2) and the compound represented by the formula (6-1) wherein R ¹ is hydrogen is a compound represented by the formula (2-2) in terms of a molar ratio: The compound represented by the formula (6-1) wherein R ¹ is hydrogen = 85.3: 42.9.

(Production of Polymer Compound B)

In the presence of 0.5 part by weight of the azobisisobutyronitrile as a polymerization initiator, the obtained polymerizable monomer B was stirred at 70 ° C for 7 hours in the presence of 0.5 part by weight of azobisisobutyronitrile. The polymer compound B was obtained. The obtained polymer compound B had a number average molecular weight of 12,900 (degree of polymerization 40).

(Production of Polymerizable Monomer C)

16.5 parts by weight of the compound represented by the formula (2-3) and 4.1 parts by weight of the compound represented by the formula (6-1) wherein R ¹ is hydrogen, PS-PPH3 (Biotage Japan Co., Ltd.) as an alkaline catalyst. The reaction was carried out while stirring at 110 ° C for 48 hours in the presence of 0.7 part by weight of a polystyrene (PS)-supported basic catalyst of triphenylphosphine, thereby obtaining the formula (7-3). R ¹ is a compound of hydrogen (polymerizable monomer C).

Further, the compounding ratio of the compound represented by the formula (2-3) and the compound represented by the formula (6-1) wherein R ¹ is hydrogen is a compound represented by the formula (2-3) in terms of a molar ratio: The compound represented by the formula (6-1) wherein R ¹ is hydrogen = 63.2: 32.0.

(Production of Polymer Compound C)

In the presence of 10 parts by weight of the obtained polymerizable monomer C in an amount of 0.5 part by weight of azobisisobutyronitrile as a polymerization initiator, the mixture was stirred at 70 ° C for 7 hours while reacting with nitrogen to cause a reaction. This gave the polymer compound C. The obtained polymer compound C had a number average molecular weight of 10,200 (degree of polymerization 26).

(Production of polymerizable monomer D)

16.5 parts by weight of the compound represented by the formula (2-1) and 11.8 parts by weight of the compound represented by the formula (6-2) in which all of R ² is a methoxy group, and PS-PPH3 (Biotage) as a basic catalyst The reaction was carried out by stirring at a temperature of 110 ° C for 48 hours in the presence of 0.7 parts by weight of a basic catalyst containing triphenylphosphine supported on polystyrene (PS), to obtain a formula (7- 4) A compound (polymerizable monomer D) represented.

Further, the compounding ratio of the compound represented by the formula (2-1) and the compound in which all R ² represented by the formula (6-2) is a methoxy group is expressed by the formula (2-1) in terms of a molar ratio. The compound represented by the formula (6-2) wherein all R ² is a methoxy group = 2:1.

(Production of Polymer Compound D)

In the presence of 10 parts by weight of the obtained polymerizable monomer D in an amount of 0.5 part by weight of azobisisobutyronitrile as a polymerization initiator, the mixture was stirred at 70 ° C for 7 hours while reacting with nitrogen to cause a reaction. This gave the polymer compound D. The number average molecular weight of the obtained polymer compound D was 8,900 (degree of polymerization 22).

(Production of polymerizable monomer E)

16.5 parts by weight of the compound represented by the formula (5-1) and 3.7 parts by weight of the compound represented by the formula (6-1), wherein R ¹ is hydrogen, in the PS-PPH3 (Biotage Japan Co., Ltd.) as an alkaline catalyst The reaction was carried out while stirring at 110 ° C for 48 hours in the presence of 0.7 part by weight of a basic catalyst containing triphenylphosphine supported on polystyrene (PS), thereby obtaining the formula (8-1). A compound (polymerizable monomer E) in which R ¹ is hydrogen.

Further, the compounding ratio of the compound represented by the formula (5-1) and the compound represented by the formula (6-1) wherein R ¹ is hydrogen is a compound represented by the formula (5-1) in terms of a molar ratio: The compound represented by the formula (6-1) wherein R ¹ is hydrogen = 57.63: 28.9.

(Production of Polymer Compound E)

10 parts by weight of the polymerizable monomer E obtained was stirred at 70 ° C for 4 hours while flowing nitrogen gas in the presence of 20.0 g of ethanol, 0.5 g of water, and 0.6 parts by weight of 6N-hydrochloric acid as an acid catalyst. This was allowed to react, whereby a polymer compound E was obtained. The number average molecular weight of the obtained polymer compound E was 15,200 (degree of polymerization 37).

(Production of polymerizable monomer F)

16.5 parts by weight of the compound represented by the formula (5-2) and 4.7 parts by weight of the compound represented by the formula (6-1) wherein R ¹ is hydrogen, in the PS-PPH3 (Biotage Japan Co., Ltd.) as an alkaline catalyst The reaction was carried out while stirring at 110 ° C for 48 hours in the presence of 0.7 part by weight of a basic catalyst containing triphenylphosphine supported on polystyrene (PS), thereby obtaining the formula (8-2). A compound (polymerizable monomer F) in which R ¹ is hydrogen.

Further, the compounding ratio of the compound represented by the formula (5-2) and the compound represented by the formula (6-1) wherein R ¹ is hydrogen is a compound represented by the formula (5-2) in terms of a molar ratio: The compound represented by the formula (6-1) wherein R ¹ is hydrogen = 72.3: 36.7.

(Production of Polymer Compound F)

10 parts by weight of the polymerizable monomer F obtained was stirred at 70 ° C for 4 hours while flowing nitrogen gas in the presence of 20.0 g of ethanol, 0.5 g of water, and 0.6 parts by weight of 6N-hydrochloric acid as an acid catalyst. This is allowed to react, whereby the polymer compound F is obtained. The number average molecular weight of the obtained polymer compound F was 16,500 (degree of polymerization 46).

(Production of polymerizable monomer G)

16.5 parts by weight of the compound represented by the formula (5-1) and 6.8 parts by weight of the compound represented by the formula (6-2) in which all of R ² is a methoxy group, and PS-PPH3 (Biotage) as a basic catalyst Manufactured by Japan Corporation, the reaction was carried out by stirring at 110 ° C for 48 hours under 0.7 parts by weight of a basic catalyst containing triphenylphosphine supported on polystyrene (PS), thereby obtaining the formula (8-3). The compound represented (polymerizable monomer G).

Further, the compounding ratio of the compound represented by the formula (5-1) and the compound in which all R ² represented by the formula (6-2) is a methoxy group is expressed by the formula (5-1) in terms of a molar ratio. The compound: the compound represented by the formula (6-2) wherein all R ² is a methoxy group = 57.6: 28.8.

(Production of Polymer Compound G)

10 parts by weight of the polymerizable monomer G obtained was stirred at 70 ° C for 4 hours while flowing nitrogen gas in the presence of 20.0 g of ethanol, 0.5 g of water, and 0.6 parts by weight of 6N-hydrochloric acid as an acid catalyst. This was allowed to react, whereby a polymer compound G was obtained. The number average molecular weight of the obtained polymer compound G was 7,600 (degree of polymerization 15).

(Examples 1 to 17 and Comparative Example 1)

According to the blending ratios described in Tables 1 and 2, each material was mixed using a planetary mixer ("Drying Stirred Taro" manufactured by Thinky Co., Ltd.), and then mixed using a three-roll mill to prepare Example 1 ~17. Each of the sealing agents for liquid crystal display elements of Comparative Example 1.

<evaluation>

Each of the sealants for liquid crystal display elements obtained in the examples and the comparative examples was subjected to the following evaluation. The results are shown in Tables 1 and 2.

(photohardenability)

Applying the sealing agent for liquid crystal display elements obtained in the examples and the comparative examples to the glass substrate so that the gap after bonding the glass substrate is about 5 μm, and superimposing the glass substrate of the same size on the substrate, and then Ultraviolet light (wavelength 365 nm) of 100 mW/cm ^{2 was} irradiated for 10 seconds using a metal halide lamp. The amount of change in the peak derived from the (meth) acrylonitrile group before and after the light irradiation was measured using an infrared spectroscopic device ("FTS3000" manufactured by BIORAD Co., Ltd.), whereby the photocurability was evaluated. The case where the peak derived from the (meth) acrylonitrile group is reduced by 93% or more after the light irradiation is referred to as "◎", and the peak derived from the (meth) acrylonitrile group after light irradiation is reduced by 85% or more. The case of 93% is recorded as "○", and the case where the peak derived from the (meth) acrylonitrile group is reduced by 75% or more and less than 85% after the light irradiation is recorded as "Δ", which will be after the light irradiation. The case where the decrease in the peak derived from the (meth) acrylonitrile group was less than 75% was referred to as "x" to evaluate the photocurability.

(liquid crystal contamination)

1 part by weight of the spacer fine particles ("Micropearl SI-H050", manufactured by Sekisui Chemical Co., Ltd.) was dispersed in 100 parts by weight of each of the sealing agents for liquid crystal display elements obtained in the examples and the comparative examples to prepare a liquid crystal display device. The sealant was applied to one of the two rubbed alignment films and the substrate with the transparent electrode by means of a dispenser in such a manner that the line width of the sealant was 1 mm.

Then, a droplet of liquid crystal (manufactured by Chisso Co., Ltd., "JC-5004LA") was applied dropwise to the entire surface of the sealing agent of the substrate with the transparent electrode, and another color filter substrate with a transparent electrode was immediately applied. The bonding was carried out, and the sealing agent was irradiated with ultraviolet rays (wavelength: 365 nm) of 100 mW/cm ^{2 for} 30 seconds using a metal halide lamp, and further heated at 120 ° C for 1 hour to obtain a liquid crystal display element.

The liquid crystal display element uses a dispenser to control the application position of the sealant, and the liquid crystal display element (without the light-shielding portion) in which the sealant is completely irradiated to the light, and the color filter substrate is covered with the sealant at 50% of the line width. There are two kinds of liquid crystal display elements (with light-shielding portions) coated by a black matrix. 1 is a cross-sectional view showing a liquid crystal display element produced by using a sealing agent for liquid crystal display elements obtained in Examples and Comparative Examples in a state where no light-shielding portion is formed, and FIG. 2 is a view schematically showing an example of use. And a cross-sectional view of the liquid crystal display element produced by the sealing agent for liquid crystal display elements obtained in the comparative example in the state which has a light-shielding part. As shown in Fig. 1, the sealant 1 has no light-shielding portion, and the sealant 1 is completely irradiated with light. On the other hand, as shown in Fig. 2, the sealant 1 has a light-shielding portion of the liquid crystal display element and liquid crystal. The sealant 1 of the portion 3 in contact is shielded by the black matrix 2 and completely illuminates the light.

The liquid crystal display element obtained was subjected to a 100-hour operation test, and after applying a voltage of 1000 hours at 80 ° C, it was confirmed by visual observation that the liquid crystal alignment in the vicinity of the sealant was disordered.

The alignment disorder is judged based on the unevenness of the color of the display portion, and the case where there is no color unevenness is described as "◎" according to the degree of color unevenness, and the case of slight color unevenness is referred to as "○". The case where there is less color unevenness is referred to as "Δ", and the case where there is a considerable amount of color unevenness is referred to as "X", and liquid crystal contamination is evaluated.

In addition, the liquid crystal display elements evaluated as "◎" and "○" are grades which are completely problem-free in practical use.

[Industrial availability]

According to the present invention, it is possible to provide a polymerizable monomer which is low in contamination to liquid crystal, has high sensitivity to long-wavelength light, and is excellent in sensitizing effect, and a polymer compound obtained by polymerizing the polymerizable monomer. Moreover, according to the present invention, a photocurable resin composition containing the polymerizable monomer and/or the polymer compound, a sealing agent for a liquid crystal display element using the photocurable resin composition, and the like can be provided. The upper and lower conductive materials and the liquid crystal display element are used for the liquid crystal display element sealing agent.

Claims (11)

A polymerizable monomer which is a dialkylaminobenzoic acid compound or a 9-oxosulfuric acid having a functional group reactive with an epoxy group. A derivative obtained by reacting with an epoxy compound having an unsaturated double bond or an epoxy compound having an alkoxysilyl group. The polymerizable monomer according to the first aspect of the invention, wherein the dialkylaminobenzoic acid-based compound is a compound represented by the following formula (2-1), a compound represented by (2-2), or ( 2-3) the compound represented For example, the polymerizable monomer of claim 1 of the patent scope, wherein 9-oxygen sulfur The derivative is a compound represented by the following formula (5-1) or (5-2) The polymerizable monomer according to claim 1, 2 or 3, wherein the epoxy compound is a compound represented by the following formula (6-1) or (6-2) In the formula (6-1), R ¹ represents hydrogen or a methyl group; in the formula (6-2), R ² represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms; ² may be the same or different, but at least one R ² is an alkoxy group having a carbon number of 1 to 10. A polymer compound which is a polymerizable single article of claim 1, 2, 3 or 4 The body is obtained by polymerization. The polymer compound of the fifth aspect of the patent application has a degree of polymerization of 3 or more. A photocurable resin composition comprising a curable resin, and a polymerizable monomer of claim 1, 2, 3 or 4 and/or a polymer compound of claim 5 or 6. The photocurable resin composition of claim 7, which contains an opacifier. A sealant for a liquid crystal display element which is obtained by using the photocurable resin composition of claim 7 or 8. A vertical conduction material comprising the sealing agent for a liquid crystal display element of claim 9 and the conductive fine particles. A liquid crystal display element produced by using the sealing agent for liquid crystal display elements of claim 9 or the upper conductive material of claim 10 of the patent application.