CN105683225B - Sealant for liquid crystal display element, upper and lower conduction material, and liquid crystal display element - Google Patents

Abstract

The high sensitivity of the purpose of the present invention is to provide the pollutions to liquid crystal light low, to long wavelength, sensitization effect also excellent polymerizable monomer and by high-molecular compound obtained from polymerizable monomer polymerization.In addition, the purpose of the present invention is to provide the Photocurable resin composition containing the polymerizable monomer and/or the high-molecular compound, using the Photocurable resin composition manufactured sealing material for liquid crystal display device and the conductive material up and down and liquid crystal display element that are manufactured using the sealing material for liquid crystal display device.The present invention relates to make dialkyl amino yl benzoic acid based compound or with can with the thioxanthone derivates of the functional group of epoxy reaction, with epoxide with unsaturated double-bond or the epoxide with alkoxysilyl react obtained from polymerizable monomer.

Description

Sealant for liquid crystal display element, upper and lower conduction material, and liquid crystal display element

technical field

The present invention relates to a polymerizable monomer that has low contamination of liquid crystals, high sensitivity to long-wavelength light, and excellent sensitization effect, and a polymer compound obtained by polymerizing the polymerizable monomer. Also, the present invention relates to a photocurable resin composition containing the polymerizable monomer and/or the polymer compound, a sealant for a liquid crystal display element produced using the photocurable resin composition, and a liquid crystal display device using the photocurable resin composition. The upper and lower conduction materials and liquid crystal display elements manufactured by the element sealant.

Background technique

In recent years, as a method of manufacturing liquid crystal display elements such as liquid crystal display units, from the viewpoints of shortening takt time and optimizing the amount of liquid crystals used, the method disclosed in Patent Document 1 and Patent Document 2 using a curable resin containing A liquid crystal dropping method called a dropping method, which uses a photothermal combination of a photopolymerization initiator and a thermal curing agent to cure a sealant.

In the dropping process, first, a rectangular seal pattern is formed on one of two transparent substrates with electrodes by a dispenser. Next, in an uncured state of the sealant, liquid crystal droplets are dropped onto the entire surface of the frame of the transparent substrate, and then another transparent substrate is superimposed, and the sealed portion is irradiated with light such as ultraviolet rays to be temporarily cured. Then, heating is performed at the time of liquid crystal annealing to perform main curing, and a liquid crystal display element is produced. If the bonding of the substrates is performed under reduced pressure, a liquid crystal display element can be manufactured extremely efficiently, and this dropping process has become the mainstream of a method for manufacturing a liquid crystal display element at present.

In addition, at present when various mobile devices equipped with liquid crystal panels, such as mobile phones and portable game machines, are widely used, miniaturization of devices is the most desired issue. As a method of reducing the size of the device, narrowing the frame of the liquid crystal display part, for example, disposing the position of the sealing part under the black matrix (hereinafter also referred to as narrow frame design) is mentioned.

However, in the narrow bezel design, the sealant is placed directly under the black matrix. Therefore, if the dripping process is performed, the light irradiated when the sealant is photocured is blocked, and the light does not reach the inside of the sealant. A problem that curing becomes insufficient. If the curing of the sealant becomes insufficient in this way, there is a problem that uncured sealant components are eluted into liquid crystals, and liquid crystal contamination is likely to occur.

Patent Document 3 discloses blending a highly sensitive photopolymerization initiator into a sealing compound. However, if only a highly sensitive photopolymerization initiator is mixed, it will not be possible to sufficiently photocure the sealant. In addition, Patent Document 4 discloses that a highly sensitive photopolymerization initiator and a sensitizer are combined and blended into a sealing compound. However, since a sensitizer is used, there is a problem that liquid crystal contamination is easily generated.

prior art literature

patent documents

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

Patent Document 2: International Publication No. 02/092718

Patent Document 3: International Publication No. 2011/002028

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

Contents of the invention

The problem to be solved by the invention

An object of the present invention is to provide a polymerizable monomer that has low contamination to liquid crystals, high sensitivity to long-wavelength light, and excellent sensitization effect, and a polymer compound obtained by polymerizing the polymerizable monomer. In addition, the object of the present invention is to provide a photocurable resin composition containing the polymerizable monomer and/or the polymer compound, a sealant for a liquid crystal display element produced using the photocurable resin composition, and A vertical conduction material and a liquid crystal display element manufactured using this sealing compound for liquid crystal display elements.

means to solve the problem

The present invention is to make a dialkyl aminobenzoic acid compound or a thioxanthone derivative with a functional group capable of reacting with an epoxy group, and an epoxy compound with an unsaturated double bond or an epoxy compound with an alkoxysilyl group A polymerizable monomer obtained by reacting compounds.

The present invention is described in detail below.

The present inventors have surprisingly found that a polymerizable monomer having a specific structure and a polymer compound obtained by polymerizing the polymerizable monomer have low contamination of liquid crystals, high sensitivity to long-wavelength light, and low sensitization effect. excellent. Therefore, the present inventors have found that by using a photocurable resin composition containing the polymerizable monomer and the polymer compound as a photopolymerization initiator or a sensitizer, it is possible to obtain a resin that is excellent in photocurability and can suppress liquid crystal contamination. sealant for liquid crystal display elements, thus completing the present invention.

The polymerizable monomer of the present invention is a dialkylaminobenzoic acid compound or a thioxanthone derivative having a functional group capable of reacting with an epoxy group (hereinafter simply referred to as "thioxanthone derivative"), and a compound having It is obtained by reacting an epoxy compound having an unsaturated double bond or an epoxy compound having an alkoxysilyl group (hereinafter collectively referred to as "the epoxy compound of the present invention").

Examples of the dialkylaminobenzoic acid-based compounds include: compounds represented by the following formula (1-1), compounds represented by the following formula (1-2), compounds represented by the following formula (1-3), The compound shown, 7-(dimethylamino)coumarin-3-carboxylic acid, etc. Among them, the compound shown in the following formula (1-1), the compound shown in the following formula (1-2) or the compound shown in the following formula (1-3) are preferred, and the following formula (2- A compound represented by 1), a compound represented by the following formula (2-2), or a compound represented by the following formula (2-3).

The aforementioned thioxanthone derivatives have functional groups capable of reacting with epoxy groups.

As a functional group which can react with the said epoxy group, a hydroxyl group, a carboxyl group, an amino group etc. are mentioned, for example. Among them, a hydroxyl group or a carboxyl group is preferable.

As said thioxanthone derivative, the compound represented by following formula (3), 2-amino-9H-thioxanth-9-one, etc. are mentioned, for example. Among them, the compound represented by the following formula (3) is preferable, and the compound represented by the following formula (5-1) or (5-2) is more preferable.

In 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).

The epoxy compound of the present invention to be reacted with the above-mentioned dialkylaminobenzoic acid-based compound or the above-mentioned thioxanthone derivative is an epoxy compound having an unsaturated double bond or an epoxy compound having an alkoxysilyl group.

The unsaturated double bond or alkoxysilyl group functions as a polymerizable reactive group involved in the polymerization of the polymerizable monomer of the present invention.

As a functional group which has the said unsaturated double bond, a (meth)acryloyloxy group, a vinyl group, an allyl group etc. are mentioned, for example. Among them, a (meth)acryloyloxy group is preferable.

In addition, in this specification, the said "(meth)acryloyloxy group" means an acryloyloxy group or a methacryloyloxy group.

As said alkoxysilyl group, a trimethoxysilyl group, a triethoxysilyl group, a methyldimethoxysilyl group, a methyldiethoxysilyl group etc. are mentioned, for example. Among them, a trimethoxysilyl group is preferable.

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

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

As a method for obtaining the polymerizable monomer of the present invention by reacting the above-mentioned dialkylaminobenzoic acid-based compound or the above-mentioned thioxanthone derivative with the epoxy compound of the present invention, in the presence of a basic catalyst, using A method in which the above-mentioned dialkylaminobenzoic acid-based compound or the above-mentioned thioxanthone derivative and the epoxy compound of the present invention are reacted while stirring at 80 to 130° C. for 6 to 72 hours, and the like.

From the viewpoint of reactivity, the reaction of the above-mentioned dialkylaminobenzoic acid-based compound or the above-mentioned thioxanthone derivative with the epoxy compound of the present invention is preferably performed in the presence of a trivalent organic phosphoric acid compound and/or an amine compound.

As the above-mentioned dialkylaminobenzoic acid-based compound or the above-mentioned thioxanthone derivative and the epoxy compound of the present invention when the above-mentioned dialkylaminobenzoic acid-based compound or the above-mentioned thioxanthone derivative is reacted The use ratio of the compound is preferably the above-mentioned dialkylaminobenzoic acid-based compound or the above-mentioned thioxanthone derivative: epoxy compound of the present invention = 1:1 to 10:1 in terms of molar ratio. By making the use ratio of the above-mentioned dialkylaminobenzoic acid-based compound or the above-mentioned thioxanthone derivative and the epoxy compound of the present invention within this range, the polymeric compound of the present invention having a photoreactive group can be produced with a high yield. sexual monomer.

As the basic catalyst used when the above-mentioned dialkylaminobenzoic acid-based compound or the above-mentioned thioxanthone derivative is reacted with the epoxy compound of the present invention, for example, triphenylphosphine, triethylamine, tripropylamine, Tetramethylethylenediamine, dimethyllaurylamine, triethylbenzylammonium chloride, trimethylhexadecylammonium bromide, tetrabutylammonium bromide, trimethylbutylphosphonium bromide, Butylphosphonium bromide, etc. Among them, triphenylphosphine is preferable.

In addition, the above-mentioned basic catalyst may be supported on a polymer to be used as a polymer-supported basic catalyst.

As 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 "polymerizable monomer derived from a dialkylaminobenzoic acid-based compound), "), specific examples include compounds represented by the following formulas (7-1) to (7-6).

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

As the polymerizable monomer of the present invention obtained by reacting the above-mentioned thioxanthone derivative with the epoxy compound of the present invention (hereinafter also referred to as "polymerizable monomer derived from thioxanthone derivative"), for example, Compounds etc. represented by the following formulas (8-1) to (8-4) are listed.

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

A 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 invention.

Among the polymerizable monomers of the present invention, examples of a method for polymerizing the polymerizable monomer derived from the dialkylaminobenzoic acid-based compound include cationic polymerization, anionic polymerization, and radical polymerization. Among them, a method of reacting a compound dissolved in a toluene solvent in the presence of a radical polymerization initiator such as azobisisobutyronitrile under stirring at 60 to 100°C for 4 to 12 hours is preferred.

Examples of cationic polymerization catalysts used for cationic polymerization of the above-mentioned polymerizable monomers derived from dialkylaminobenzoic acid-based compounds include inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid, formic acid, acetic acid, and propionic acid. Sulfonic acids such as carboxylic acid, methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, etc. Among them, hydrochloric acid is preferred.

Examples of the anionic polymerization catalyst used for anionic polymerization of the polymerizable monomer derived from the dialkylaminobenzoic acid-based compound include: n-butyllithium, sec-butyllithium, tert-butyllithium, and other alkyl lithiums , 1,4-dilithium butane (1,4-dilithium butane) and other alkylene dilithiums (alkylenjirichus), phenyllithium, lithium stilbene, lithium naphthalene, sodium naphthalene, potassium naphthalene, n-butylmagnesium, n-hexyl magnesium, calcium ethoxide, calcium stearate, strontium tert-butoxide, barium ethoxide, barium isopropoxide, barium ethanethiolate, barium tert-butoxide, barium phenate, barium diethylamide, barium stearate, etc. Among them, n-butyllithium is preferable.

As a radical polymerization initiator used when radically polymerizing the above-mentioned polymerizable monomer derived from a dialkylaminobenzoic acid-based compound, for example, azobisisobutyronitrile, azobicyclohexylnitrile, azobiscyclohexanenitrile, Azo compounds such as nitrogen bis(2,4-dimethylvaleronitrile), benzoyl peroxide, lauroyl peroxide, o-chlorobenzoyl peroxide, o-methoxybenzoyl peroxide, peroxide Organic peroxides such as 3,5,5-trimethylhexanoyl, tert-butyl peroxy 2-ethylhexanoate, di-tert-butyl peroxide, etc. Among them, azobisisobutyronitrile is preferable.

Among the polymerizable monomers of the present invention, the method of polymerizing the above-mentioned polymerizable monomer derived from a thioxanthone derivative includes, for example, polymerization using a sol-gel method in the presence of an acidic catalyst or a basic catalyst. etc., but it is preferably a method of mixing the polymerizable monomer of the present invention dissolved in an ethanol solvent and water, and reacting under an acidic catalyst at 60 to 120° C. for 2 to 24 hours while stirring.

Examples of the acidic catalyst used for polymerizing the polymerizable monomer derived from thioxanthone derivatives include inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid, carboxylic acids such as formic acid, acetic acid, and propionic acid, and methanesulfonic acid. , ethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid and other sulfonic acids. Among them, hydrochloric acid is preferred.

Examples of the basic catalyst used for polymerizing the polymerizable monomer derived from the thioxanthone derivative include inorganic compounds such as sodium hydroxide, potassium hydroxide and ammonia, organic compounds such as amine compounds, and the like. Among them, sodium hydroxide is preferable.

The preferable lower limit of the polymerization degree of the polymer compound of this invention is 3. When the degree of polymerization of the polymer compound of the present invention is 2, that is, a dimer, liquid crystal contamination may not be sufficiently suppressed when used as a photopolymerization initiator or a sensitizer for a sealing agent for liquid crystal display elements. A more preferable lower limit of the degree of polymerization of the polymer compound of the present invention is 10.

In addition, the preferable upper limit of the polymerization degree of the polymer compound of this invention is 1000. When the degree of polymerization of the high molecular compound of this invention exceeds 1000, when it is used for the sealing compound for liquid crystal display elements as a photoinitiator or a sensitizer, applicability may worsen. A more preferable upper limit of the degree of polymerization of the polymer compound of the present invention is 100.

The preferable lower limit of the number average molecular weight of the polymer compound of this invention is 2000, and a preferable upper limit is 30,000. When the number average molecular weight of the polymer compound of this invention is less than 2000, when using it as a photoinitiator or a sensitizer for liquid crystal display element sealing agents, liquid crystal contamination may not be fully suppressed. When the number average molecular weight of the polymer compound of this invention is more than 30,000, when it is used for the sealing compound for liquid crystal display elements as a photoinitiator or a sensitizer, applicability may worsen. A more preferable lower limit of the number average molecular weight of the polymer compound of the present invention is 5,000, and a more preferable upper limit is 10,000.

In addition, in this specification, the said number average molecular weight is the value calculated|required by polystyrene conversion measured by gel permeation chromatography (GPC). As a column at the time of measuring the number average molecular weight by polystyrene conversion by GPC, ShodexLF-804 (made by Showa Denko Co., Ltd.) etc. are mentioned, for example.

Since the polymer compound of the present invention has high sensitivity to long-wavelength light and is excellent in a sensitization effect, it is preferably used as a photopolymerization initiator or a sensitizer.

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

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

The content of the polymer compound of the present invention in the photocurable resin composition of the present invention has a preferable lower limit of 0.5 parts by weight and a preferable upper limit of 20 parts by weight with respect to 100 parts by weight of curable resin. When content of the polymer compound of this invention is less than 0.5 weight part, the photocurability of the photocurable resin composition obtained may worsen. When the content of the polymer compound of the present invention exceeds 20 parts by weight, weather resistance and storage stability of the obtained photocurable resin composition may deteriorate, or liquid crystal contamination may occur when used for a sealant for liquid crystal display elements. A more preferable lower limit of the content of the polymer compound of the present invention is 2 parts by weight, and a more preferable upper limit is 10 parts by weight.

The photocurable resin composition of the present invention preferably contains in combination the polymer compound of the present invention (hereinafter also referred to as "dialkyl-derived Polymer compound of aminobenzoic acid-based compound"), and the polymer compound of the present invention obtained by polymerizing the polymerizable monomer derived from thioxanthone derivatives (hereinafter also referred to as "derived from thioxanthone derivatives") polymer compound"), it is more preferable to use the polymer compound derived from the dialkylaminobenzoic acid-based compound as the photopolymerization initiator, and to use the polymer compound derived from the thioxanthone derivative as the sensitive agent.

When the photocurable resin composition of the present invention contains both the above-mentioned high molecular compound derived from a dialkylaminobenzoic acid-based compound and the above-mentioned high molecular compound derived from a thioxanthone derivative, the above-mentioned high molecular compound derived from The content ratio of the polymer compound derived from a dialkylaminobenzoic acid-based compound to the polymer compound derived from a thioxanthone derivative is preferably a polymer compound derived from a dialkylaminobenzoic acid-based compound in terms of weight ratio. : polymer compound derived from thioxanthone derivatives = 1:1 to 5:1. By making the content ratio of the high molecular compound derived from the dialkylaminobenzoic acid-based compound and the high molecular compound derived from the thioxanthone derivative within this range, the photocurable resin composition obtained can be made to use a long wavelength. The photocurability of the light becomes particularly excellent.

In addition to the polymer compound of the present invention, the photocurable resin composition of the present invention may contain other photopolymerization initiators, other sensitive compounds, and other photopolymerization initiators within the range that does not cause adverse effects such as liquid crystal contamination when used as a sealant for liquid crystal display elements. agent.

Examples of the above-mentioned other photopolymerization initiators include: benzophenone-based compounds, acetophenone-based compounds, acylphosphine oxide-based compounds, titanocene-based compounds, oxime ester-based compounds, benzoin ether-based compounds, benzene Diacyl, thioxanthone, a compound represented by the following formula (9-1), a compound represented by the following formula (9-2), and the like.

Examples of commercially available products among the above-mentioned other photopolymerization initiators include: IRGACURE 184, IRGACURE 369, IRGACURE 379, IRGACURE 651, IRGACURE 819, IRGACURE 907, IRGACURE 2959, IRGACURE OXE01, and Lucirin TPO (all manufactured by BASF Corporation) , benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether (all manufactured by Tokyo Chemical Industry Co., Ltd.), ADEKA OPTMERN-1414, ADEKA OPTMER N-1717, ADEKA OPTMER N-1919, ADEKA OPTMER NCI-839, ADEKA OPTMER NCI-930 and the like (both are manufactured by ADEKA).

Examples of other sensitizers include: anthracene derivatives, anthraquinone derivatives, coumarin derivatives, thioxanthone derivatives, phthalocyanine derivatives, compounds represented by the following formula (10-1), A compound represented by the following formula (10-2), etc.

Examples of the above-mentioned anthracene derivatives include 9,10-dibutoxyanthracene, 9,10-dipropoxyanthraquinone, 9,10-ethoxyanthraquinone, and the like.

Examples of the above-mentioned anthraquinone derivatives include 2-ethylanthraquinone, 1-methylanthraquinone, 1,4-dihydroxyanthraquinone, 2-(2-hydroxyethoxy)-anthraquinone, and the like.

As said coumarin derivative, 7-diethylamino-4-methylcoumarin etc. are mentioned, for example.

Examples of the thioxanthone derivatives include 2,4-diethylthioxanthone, 2-chlorothioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propylthioxanthone, etc. .

As said phthalocyanine derivative, a phthalocyanine etc. are mentioned, for example.

Moreover, the benzophenone type compound mentioned as said other photoinitiator can be used as said other sensitizer.

The photocurable resin composition of this invention contains curable resin.

The above-mentioned curable resin preferably contains a (meth)acrylic resin.

It is preferable that the said (meth)acryl-type resin has 2-3 (meth)acryloyloxy groups in a molecule|numerator from a high reactive point.

Examples of the (meth)acrylic resins include: ester compounds obtained by reacting a compound having a hydroxyl group with (meth)acrylic acid; epoxy (meth)acrylic acid obtained by reacting (meth)acrylic acid with an epoxy compound; base) acrylate, urethane (meth)acrylate obtained by reacting a (meth)acrylic acid derivative having a hydroxyl group with an isocyanate compound, and the like. Among them, epoxy (meth)acrylate is preferable.

In addition, in this specification, the said "(meth)acrylic acid" means acrylic acid or methacrylic acid, and the said "(meth)acrylic resin" means resin which has a (meth)acryloyloxy group. In addition, the said "(meth)acrylate" means acrylate or methacrylate. In addition, the said "epoxy (meth)acrylate" shows the compound which made all the epoxy groups in an epoxy resin react with (meth)acrylic acid.

As the monofunctional ester compound among the above-mentioned ester compounds, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, ( 2-Hydroxybutyl methacrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, isooctyl (meth)acrylate, lauryl (meth)acrylate, (meth)acrylic acid Stearyl ester, isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, methoxyethylene glycol (meth)acrylate, (meth) base) 2-ethoxyethyl acrylate, tetrahydrofurfuryl (meth)acrylate, benzyl (meth)acrylate, ethyl carbitol (meth)acrylate, phenoxyethyl (meth)acrylate ester, phenoxydiethylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, (meth)acrylic acid- 2,2,2-trifluoroethyl ester, 2,2,3,3-tetrafluoropropyl (meth)acrylate, 1H,1H,5H-octafluoropentyl (meth)acrylate, imide (form base) acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, propyl (meth)acrylate, 2-ethylhexyl (meth)acrylate , n-octyl (meth)acrylate, isononyl (meth)acrylate, isomyristyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, 2-benzene (meth)acrylate Oxyethyl ester, dicyclopentenyl (meth)acrylate, isodecyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, 2-(methyl)acrylate base) acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyethyl hexahydrophthalic acid, 2-(meth)acryloyloxyethyl 2-hydroxypropyl phthalic acid Formate, glycidyl (meth)acrylate, 2-(meth)acryloyloxyethyl phosphate, etc.

In addition, examples of the difunctional ester compound among the above ester compounds include 1,4-butanediol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1, 6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol 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(meth)acrylate (Meth)acrylate, Diethylene glycol di(meth)acrylate, Tetraethylene glycol di(meth)acrylate, Polyethylene glycol di(meth)acrylate, Propylene oxide added bisphenol A di(meth)acrylate, ethylene oxide added bisphenol A di(meth)acrylate, ethylene oxide added bisphenol F di(meth)acrylate, dimethylol dicyclopenta Dienyl di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene oxide modified isocyanurate di(meth)acrylate, (meth)acrylate 2-hydroxy- 3-(meth)acryloyloxypropyl ester, carbonate diol di(meth)acrylate, polyether diol di(meth)acrylate, polyester diol di(meth)acrylate, poly Caprolactone diol di(meth)acrylate, polybutadiene diol di(meth)acrylate, and the like.

In addition, examples of ester compounds having more than trifunctionality among the above-mentioned ester compounds include pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, propylene oxide-added trimethylol Trimethylolpropane tri(meth)acrylate, ethylene oxide addition trimethylolpropane tri(meth)acrylate, caprolactone modified trimethylolpropane tri(meth)acrylate, ethylene oxide Alkane addition isocyanurate tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol Tetra(meth)acrylate, glycerol tri(meth)acrylate, propylene oxide added glycerol tri(meth)acrylate, tri(meth)acryloyloxyethyl phosphate, etc.

As said epoxy (meth)acrylate, the epoxy (meth)acrylate obtained by reacting an epoxy resin and (meth)acrylic acid in presence of a basic catalyst according to the usual method, etc. are mentioned, for example.

As an epoxy resin used as a raw material for synthesizing the above-mentioned epoxy (meth)acrylate, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin , 2,2'-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 type epoxy resin, diphenyl ether type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, phenol novolak type epoxy resin, o-cresol novolak type Epoxy resin, dicyclopentadiene novolak type epoxy resin, biphenyl novolak type epoxy resin, naphthol novolac type epoxy resin, glycidylamine type epoxy resin, alkyl polyol type epoxy resin, Rubber-modified epoxy resins, glycidyl ester compounds, etc.

As what is marketed among the said bisphenol A type epoxy resin, jER828EL, jER1004 (all are the Mitsubishi Chemical Corporation make), Epiclon850 (the DIC Corporation make), etc. are mentioned, for example.

As what is marketed among the said bisphenol F type epoxy resins, jER806, jER4004 (all are the Mitsubishi Chemical Corporation make), etc. are mentioned, for example.

As what is marketed among the said bisphenol S type epoxy resins, Epiclon EXA1514 (made by DIC Corporation) etc. are mentioned, for example.

Among the above-mentioned 2,2'-diallyl bisphenol A epoxy resins, commercially available ones include, for example, RE-810NM (manufactured by Nippon Kayaku Co., Ltd.).

As what is marketed among the said hydrogenated bisphenol type epoxy resins, Epiclon EXA7015 (made by DIC Corporation) etc. are mentioned, for example.

As what is marketed among the said propylene oxide addition bisphenol A type epoxy resins, EP-4000S (made by ADEKA company) etc. are mentioned, for example.

As what is marketed among the said resorcinol type epoxy resins, EX-201 (made by a Nagase Chemtex company) etc. are mentioned, for example.

As what is marketed among the said biphenyl type epoxy resins, jERYX-4000H (made by Mitsubishi Chemical Corporation) etc. are mentioned, for example.

As what is marketed among the said sulfide type epoxy resins, YSLV-50TE (made by Nippon Steel Sumikin Chemicals Co., Ltd.), etc. are mentioned, for example.

As what is marketed among the said diphenyl ether type epoxy resins, YSLV-80DE (made by Nippon Steel Sumikin Chemicals Co., Ltd.) etc. are mentioned, for example.

As what is marketed among the said dicyclopentadiene type epoxy resins, EP-4088S (made by ADEKA company) etc. are mentioned, for example.

As what is marketed among the said naphthalene type epoxy resins, Epiclon HP4032, Epiclon EXA-4700 (all are the DIC company make), etc. are mentioned, for example.

As what is marketed among the said phenol novolak type epoxy resins, Epiclon N-770 (made by DIC Corporation) etc. are mentioned, for example.

As what is marketed among the said ortho-cresol novolak type epoxy resins, Epiclon N-670-EXP-S (made by DIC Corporation) etc. are mentioned, for example.

As what is marketed among the said dicyclopentadiene novolac type epoxy resins, Epiclon HP7200 (made by DIC Corporation) etc. are mentioned, for example.

As what is marketed among the said biphenyl novolak type epoxy resins, NC-3000P (made by Nippon Kayaku Co., Ltd.) etc. are mentioned, for example.

As what is marketed among the said naphthol novolac type epoxy resins, ESN-165S (made by Nippon Steel Sumikin Chemicals Co., Ltd.) etc. are mentioned, for example.

As what is marketed among the said glycidylamine type epoxy resins, jER630 (made by Mitsubishi Chemical Corporation), Epiclon 430 (made by DIC Corporation), TETRAD-X (made by Mitsubishi Gas Chemical Corporation), etc. are mentioned, for example.

As what is marketed among the said alkyl polyol type epoxy resins, ZX-1542 (made by Nippon Steel Sumikin Chemical Co., Ltd.), Epiclon726 (made by DIC Corporation), EPOLIGHT80MFA (made by Kyoeisha Chemical Co., Ltd.) are mentioned, for example , Denacol EX-611 (manufactured by Nagase Chemtex), etc.

As what is marketed among the said rubber-modified epoxy resins, YR-450, YR-207 (all are Nippon Steel Sumikin Chemical Co., Ltd. make), EPOLEAD PB (Daicel Corporation make), etc. are mentioned, for example.

As what is marketed among the said glycidyl ester compounds, Denacol EX-147 (made by a Nagase Chemtex company) etc. are mentioned, for example.

As other commercial products among the above-mentioned epoxy resins, for example, YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.), XAC4151 (manufactured by Asahi Kasei Corporation), jER1031, jER1032 are mentioned, for example. (all are manufactured by Mitsubishi Chemical Corporation), EXA-7120 (manufactured by DIC Corporation), TEPIC (manufactured by Nissan Chemical Corporation), and the like.

As a method for producing the above-mentioned epoxy (meth)acrylate, specifically, for example, 360 parts by weight of a resorcinol-type epoxy resin (manufactured by Nagase Chemtex, "EX-201"), p-formaldehyde as a polymerization inhibitor, 2 parts by weight of oxyphenol, 2 parts by weight of triethylamine as a reaction catalyst, and 210 parts by weight of acrylic acid are reacted at 90°C for 5 hours while feeding air and stirring under reflux, thereby obtaining resorcinol-type epoxy Acrylate.

Examples of commercially available epoxy (meth)acrylates include: EBEC RYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRYL3703, EBECRYL3800, EBECRYL6040 Allnex Inc.), 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 、EPOXY ESTER 70PA、EPOXYESTER 200PA、EPOXY ESTER 80MFA、EPOXY ESTER 3002M、E POXY ESTER3002A、EPOXYESTER1600A、EPOXY ESTER3000M、EPOXY ESTER3000A、EPOXY ESTER 200EA、EPOXY ESTER400EA(均为共荣社化学公司制造)、Denacol Acrylate DA-141 , Denacol Acrylate DA-314, Denacol Acrylate DA-911 (all manufactured by Nagase Chemt ex Co., Ltd.) and the like.

As the urethane (meth)acrylate obtained by reacting the above-mentioned (meth)acrylic acid derivative having a hydroxyl group with an isocyanate compound, it can be obtained, for example, as follows: It is obtained by reacting 2 equivalents of a (meth)acrylic acid derivative having a hydroxyl group in the presence of a catalyst amount of a tin-based compound.

As the isocyanate compound as a raw material of the above-mentioned urethane (meth)acrylate, for example, isophorone diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, hexaethylene diisocyanate, Methyl diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4,4'-diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate , xylylene diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris(isocyanate phenyl) phosphorothioate, tetramethylxylene diisocyanate , 1,6,11-undecane triisocyanate, etc.

In addition, as the isocyanate compound used as the raw material of the above-mentioned urethane (meth)acrylate, for example, ethylene glycol, glycerol, sorbitol, trimethylolpropane, (poly)propylene glycol can also be used. , Carbonate diol, polyether diol, polyester diol, polycaprolactone diol and other polyols react with excess isocyanate compounds to obtain chain-extended isocyanate compounds.

As a raw material of the above-mentioned urethane (meth)acrylate, (meth)acrylic acid derivatives having a hydroxyl group include, for example, 2-hydroxyethyl (meth)acrylate, (meth)acrylic acid 2 - Hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate and other hydroxyalkyl (meth)acrylates; ethylene glycol, propylene glycol, 1,3-propanediol, 1 , Mono(meth)acrylates of glycols such as 3-butanediol, 1,4-butanediol, and polyethylene glycol; trimethylolethane, trimethylolpropane, glycerin, etc. Mono(meth)acrylate or di(meth)acrylate of alcohol; epoxy (meth)acrylate such as bisphenol A type epoxy acrylate, etc.

The above-mentioned urethane (meth)acrylate can be specifically obtained as follows: add 134 parts by weight of trimethylolpropane, 0.2 parts by weight of BHT as a polymerization inhibitor, and 0.01 parts by weight of dibutyltin dilaurate as a reaction catalyst Parts, 666 parts by weight of isophorone diisocyanate, reacted at 60°C for 2 hours while stirring under reflux, then added 51 parts by weight of 2-hydroxyethyl acrylate, and reacted at 90°C while feeding air and stirring under reflux 2 hours, thus obtained.

As what is marketed among the said urethane (meth)acrylates, M-1100, M-1200, M-1210, M-1600 (all are manufactured by Toagosei Co., Ltd.), EBECRYL230, EBECRYL270 are mentioned, for example 、EBECRYL4858、EBECRYL8402、EBECRYL8804、EBECRYL8803、EBECRYL8807、EBECRYL9260、EBECRYL1290、EBECRYL5129、EBECRYL4842、EBECRYL210、EBECRYL4827、EBECRYL6700、EBECRYL220、EBECRYL2220(均为Daicel-Allnex公司制造)、Artresin UN-9000H、Artresin UN-9000A、Artresin UN -7100, Artresin UN-1255, Artresin UN-330, Artresin UN-3320HB, ArtresinUN-1200TPK, Artresin SH-500B (all manufactured by Negami Industry 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 Shin Nakamura Chemical Industry Company Manufacturing), AH-600, AT-600, UA-306H, AI-600, UA-101T, UA-101I, UA-306T, UA-306I (all manufactured by Kyoeisha Chemical Co., Ltd.), etc.

It is preferable that the said curable resin further contains an epoxy resin for the purpose of improving the adhesiveness of the photocurable resin composition obtained. As said epoxy resin, the epoxy resin which is a raw material for synthesizing the said epoxy (meth)acrylate, a partial (meth)acryl-modified epoxy resin, etc. are mentioned, for example.

It should be noted that, in this specification, the above-mentioned partially (meth)acrylic modified epoxy resin refers to a resin having one or more epoxy groups and (meth)acryloyl groups in one molecule. For example, it can be obtained by using It is obtained by reacting some epoxy groups of two or more epoxy resins with (meth)acrylic acid.

When the photocurable resin composition of the present invention contains the above-mentioned (meth)acrylic resin and the above-mentioned epoxy resin, it is preferable that the ratio of (meth)acryloyloxy group to epoxy group is 50:50-95 : Embodiment 5 The above-mentioned (meth)acrylic resin and the above-mentioned epoxy resin were blended. If the ratio of the (meth)acryloxy group is less than 50%, since a large amount of uncured epoxy resin components will still exist even if polymerization is complete|finished, liquid crystal contamination may generate|occur|produce when it uses for the sealing compound for liquid crystal display elements. When the ratio of a (meth)acryloyloxy group exceeds 95 %, the adhesiveness of the photocurable resin composition obtained may worsen.

From the viewpoint of suppressing liquid crystal contamination when used in a sealing compound for liquid crystal display elements, it is preferable that the curable resin has hydrogen-bonding units such as —OH group, —NH— group, and —NH ₂ group.

The photocurable resin composition of this invention may contain a thermal radical polymerization initiator further.

As said thermal radical polymerization initiator, the thermal radical polymerization initiator which consists of an azo compound, an organic peroxide, etc. is mentioned, for example. Among them, an initiator composed of a polymeric azo compound (hereinafter also referred to as a "polymeric azo initiator") is preferable.

In this specification, a polymeric azo initiator refers to a polymer having an azo group and generating radicals capable of curing (meth)acryloyloxy groups by heat, and having a number average molecular weight of 300 or more. compound of.

The preferable lower limit of the number average molecular weight of the said high molecular weight azo initiator is 1000, and a preferable upper limit is 300,000. When the number average molecular weight of the said polymeric azo initiator is less than 1000, a polymeric azo initiator may exert a bad influence on a liquid crystal when it is used for the sealing compound for liquid crystal display elements. When the number average molecular weight of the said polymeric azo initiator exceeds 300,000, it may become difficult to mix with curable resin. The more preferable lower limit of the number average molecular weight of the said polymeric azo initiator is 5000, the more preferable upper limit is 100,000, the more preferable lower limit is 10,000, and the more preferable upper limit is 90,000.

As said polymeric azo initiator, the polymeric azo initiator which has the structure which unites, such as a polyalkylene oxide and a polydimethylsiloxane, couple|bonded via an azo group, is mentioned, for example.

As the polymeric azo initiator having a structure in which units such as polyalkylene oxide are bonded via an azo group, a polymeric azo initiator having a polyethylene oxide structure is preferable. As such a polymeric azo initiator, for example, a polycondensate of 4,4'-azobis(4-cyanovaleric acid) and polyalkylene glycol, 4,4'-azobis(4 - cyanovaleric acid) and polydimethylsiloxane polycondensate having terminal amino groups, etc., specifically, VPE-0201, VPE-0401, VPE-0601, VPS-0501, VPS-1001 (both are manufactured by Wako Pure Chemical Industries, Ltd.), etc.

Moreover, as a non-polymeric azo compound, V-65, V-501 (both are Wako Pure Chemical Industries, Ltd. make), etc. are mentioned, for example.

As said organic peroxide, a ketone peroxide, a peroxyketal, a hydrogen peroxide, a dialkyl peroxide, a peroxyester, a diacyl peroxide, a peroxydicarbonate etc. are mentioned, for example.

With respect to 100 weight part of curable resins, the preferable minimum is 0.1 weight part about content of the said thermal radical polymerization initiator, and a preferable upper limit is 30 weight part. When content of the said thermal radical polymerization initiator is less than 0.1 weight part, thermal polymerization of the photocurable resin composition obtained may not fully advance. When content of the said thermal radical polymerization initiator exceeds 30 weight part, when using for the sealing compound for liquid crystal display elements, liquid-crystal contamination may generate|occur|produce by the unreacted thermal radical polymerization initiator. The more preferable minimum of content of the said thermal radical polymerization initiator is 0.5 weight part, and a more preferable upper limit is 10 weight part.

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

As said thermosetting agent, organic acid hydrazide, an imidazole derivative, an amine compound, a polyhydric phenol type compound, an acid anhydride, etc. are mentioned, for example. Among them, organic acid hydrazides are preferably used.

As said organic acid hydrazide, sebacic hydrazide, isophthalic hydrazide, adipic hydrazide, malonyl hydrazide etc. are mentioned, for example.

As a commercial item among the said organic acid hydrazides, SDH, ADH (both are manufactured by Otsuka Chemical Co., Ltd.), AMICURE VDH, AMICURE VDH-J, AMICURE UDH (both are manufactured by Ajinomoto Fine-Techno Co., Ltd.) etc. are mentioned, for example. .

With respect to 100 parts by weight of the curable resin, the lower limit of the content of the thermosetting agent is preferably 1 part by weight, and the upper limit is preferably 50 parts by weight. When content of the said thermosetting agent is less than 1 weight part, the photocurable resin composition obtained may not fully be thermally hardened. When content of the said thermosetting agent exceeds 50 weight part, the viscosity of the photocurable resin composition obtained may become high too much, and applicability may worsen. The more preferable upper limit of content of the said thermosetting agent is 30 weight part.

The photocurable resin composition of the present invention preferably contains a filler for purposes such as improvement of viscosity, improvement of adhesiveness due to stress dispersion effect, improvement of linear expansion coefficient, and improvement of moisture resistance of cured product.

Examples of the filler include talc, asbestos, silica, diatomaceous earth, smectite, bentonite, calcium carbonate, magnesium carbonate, alumina, montmorillonite, zinc oxide, iron oxide, magnesium oxide, and tin oxide. , titanium dioxide, magnesium hydroxide, aluminum hydroxide, glass beads, silicon nitride, barium sulfate, gypsum, calcium silicate, sericite, activated clay, aluminum nitride and other inorganic fillers, polyester particles, polyurethane particles, vinyl Organic fillers such as base polymer particles and acrylic polymer particles. These fillers may be used alone or in combination of two or more.

The preferable minimum of content of the said filler in 100 weight part of photocurable resin compositions of this invention is 10 weight part, and a preferable upper limit is 70 weight part. When content of the said filler is less than 10 weight part, effects, such as improvement of adhesiveness, may not fully be exhibited. When content of the said filler exceeds 70 weight part, the viscosity of the photocurable resin composition obtained may become high too much, and applicability may worsen. The more preferable lower limit of content of the said filler is 20 weight part, and a more preferable upper limit is 60 weight part.

The photocurable resin composition of the present invention preferably contains a silane coupling agent. The above-mentioned silane coupling agent mainly functions as an adhesion auxiliary agent for bonding the photocurable resin composition of the present invention to a substrate or the like favorably.

As the above-mentioned silane coupling agent, it is preferable to use, for example, 3-aminopropane, which is excellent in the effect of improving the adhesiveness with the substrate, and suppresses the outflow of the curable resin into the liquid crystal when used as a sealant for liquid crystal display elements. Trimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanatepropyltrimethoxysilane, etc. These silane coupling agents may be used alone or in combination of two or more.

The preferable minimum of content of the said silane coupling agent in 100 weight part of photocurable resin compositions of this invention is 0.1 weight part, and a preferable upper limit is 20 weight part. When content of the said silane coupling agent is less than 0.1 weight part, the effect by mix|blending a silane coupling agent may not fully be exhibited. When content of the said silane coupling agent exceeds 20 weight part, when using the obtained photocurable resin composition for the sealing compound for liquid crystal display elements, liquid-crystal contamination may arise. The more preferable minimum of content of the said silane coupling agent is 0.5 weight part, and a more preferable upper limit is 10 weight part.

The photocurable resin composition of this invention may contain a light-shielding agent further. By containing the said light-shielding agent, the photocurable resin composition of this invention can be used suitably as a light-shielding sealing agent.

As said light-shielding agent, iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, resin-coated carbon black etc. are mentioned, for example. Among them, titanium black is preferable.

The above-mentioned titanium black is a substance that has a higher transmittance to light in the vicinity of the ultraviolet region, particularly a wavelength of 370 to 450 nm, than the average transmittance to light of a wavelength of 300 to 800 nm. That is, the above-mentioned titanium black is a light-shielding agent having the property of imparting light-shielding properties to the photocurable resin composition of the present invention by sufficiently shielding light of wavelengths in the visible light region, and on the other hand, allowing light of wavelengths near the ultraviolet region transmission. The light-shielding agent contained in the photocurable resin composition of the present invention is preferably a substance with high insulating properties, and titanium black is also preferable as the light-shielding agent with high insulating properties.

The optical density (OD value) per 1 μm of the titanium black is preferably 3 or more, more preferably 4 or more. The higher the light-shielding property of the titanium black, the better. There is no upper limit to the OD value of the titanium black, but it is usually 5 or less.

For the above-mentioned titanium black, even titanium black without surface treatment can exert a sufficient effect, but it is also possible to use titanium black whose surface has been treated with organic components such as coupling agents, or titanium black that has been treated with silicon oxide, titanium dioxide, acidified, etc. Surface-treated titanium black such as titanium black covered with inorganic components such as germanium, alumina, zirconia, and magnesia. Among these, titanium black treated with an organic component is preferable from the viewpoint of further improving insulation.

In addition, a liquid crystal display element produced by using the photocurable resin composition of the present invention containing the above-mentioned titanium black as a light-shielding agent as a sealant for a liquid crystal display element has sufficient light-shielding properties, and therefore has high contrast without light leakage, A liquid crystal display element having excellent image display quality can be realized.

As a commercial item among the said titanium blacks, 12S, 13M, 13M-C, 13R-N, 14M-C (all are manufactured by Mitsubishi Materials Co., Ltd.), Tilack D (made by Ako Kasei Co., Ltd.) etc. are mentioned, for example.

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

In addition, the volume resistance of the titanium black has a preferable lower limit of 0.5Ω·cm, a preferable upper limit of 3Ω·cm, a more preferable lower limit of 1Ω·cm, and a more preferable upper limit of 2.5Ω·cm.

The primary particle size of the light-shielding agent is not particularly limited as long as it is equal to or less than the distance between substrates such as a liquid crystal display element, but the lower limit is preferably 1 nm, and the upper limit is preferably 5 μm. When the primary particle diameter of the said light-shielding agent is less than 1 nm, the viscosity and thixotropy of the photocurable resin composition obtained may increase significantly, and handleability may worsen. When the primary particle diameter of the said light-shielding agent exceeds 5 micrometers, the coating property of the photocurable resin composition obtained may worsen. The more preferable lower limit of the primary particle diameter of the said light-shielding agent is 5 nm, the more preferable upper limit is 200 nm, the more preferable lower limit is 10 nm, and the more preferable upper limit is 100 nm.

The preferable minimum of content of the said light-shielding agent in 100 weight part of photocurable resin compositions of this invention is 5 weight part, and a preferable upper limit is 80 weight part. When content of the said light-shielding agent is less than 5 weight part, sufficient light-shielding property may not be acquired. When content of the said light-shielding agent exceeds 80 weight part, the adhesiveness to the board|substrate of the photocurable resin composition obtained, and the intensity|strength after hardening may fall, or drawing property may fall. A more preferable lower limit of the content of the sunscreen agent is 10 parts by weight, a more preferable upper limit is 70 parts by weight, a more preferable lower limit is 30 parts by weight, and a more preferable upper limit is 60 parts by weight.

As a method for producing the photocurable resin composition of the present invention, for example, the following methods are listed: using mixers such as a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, and a three-roll machine, A curable resin, the polymerizable monomer of the present invention and/or the polymer compound of the present invention, and additives such as other photopolymerization initiators, other sensitizers, and silane coupling agents are mixed as needed.

The photocurable resin composition of this invention is preferably used as a sealing compound for liquid crystal display elements.

The sealing compound for liquid crystal display elements produced using the photocurable resin composition of this invention is also one of this invention.

A vertical conduction material can be manufactured by mix|blending electroconductive fine particle with the sealing compound for liquid crystal display elements of this invention. Such a vertical conduction material containing the sealing compound for liquid crystal display elements of this invention and electroconductive fine particles is also one of this invention.

As the conductive fine particles, metal balls, fine particles having a conductive metal layer formed on the surface of resin fine particles, and the like can be used. Among them, fine particles having a conductive metal layer formed on the surface of the resin fine particles are preferable from the viewpoint of enabling conductive connection without damaging a transparent substrate or the like due to the excellent elasticity of the resin fine particles.

A liquid crystal display element manufactured using the sealing compound for liquid crystal display elements of this invention or the vertical conduction material of this invention is also one of this invention.

As a method of manufacturing the liquid crystal display element of the present invention, for example, a method having the following steps: one of two transparent substrates such as a glass substrate with an electrode such as an ITO film or a polyethylene terephthalate substrate, etc. Above, the process of forming the sealant for liquid crystal display elements of the present invention into a rectangular seal pattern by screen printing, dispenser coating, etc.; the sealant for liquid crystal display elements of the present invention is uncured. A process of applying minute droplets onto the entire surface of the frame of a transparent substrate, and then overlapping another substrate; and irradiating light such as ultraviolet rays to the sealing pattern portion of the sealant for liquid crystal display elements of the present invention to temporarily cure the sealant process; and a process of heating the temporarily cured sealant to main cure it.

The effect of the invention

According to the present invention, it is possible to provide a polymerizable monomer having low contaminating property to liquid crystal, high sensitivity to long-wavelength light, and excellent sensitization effect, and a polymer compound obtained by polymerizing the polymerizable monomer. In addition, according to the present invention, there can be provided a photocurable resin composition containing the polymerizable monomer and/or the polymer compound, a sealant for a liquid crystal display element produced using the photocurable resin composition, and a photocurable resin composition using the photocurable resin composition. The liquid crystal display element is a vertically conductive material and a liquid crystal display element manufactured by using a sealant.

Description of drawings

1 is a cross-sectional view schematically showing a liquid crystal display element produced in a state without a light-shielding portion using each sealing compound for a liquid crystal display element obtained in an Example and a comparative example.

2 is a cross-sectional view schematically showing a liquid crystal display element produced in a state having a light-shielding portion using each sealing compound for a liquid crystal display element obtained in an Example and a comparative example.

Detailed ways

Examples are given below to further describe the present invention in detail, but the present invention is not limited to these examples.

(Production of polymerizable monomer A)

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

It should be noted that the compound shown in the formula (2-1) and the R shown in the formula ( ^6-1 ) The compounding ratio of the compound shown in hydrogen is the compound shown in the formula (2-1) in molar ratio: Compound in which R ¹ represented by formula (6-1) is hydrogen = 2:1.

(Preparation of Polymer Compound A)

A polymer was obtained by reacting 10 parts by weight of the obtained polymerizable monomer A in the presence of 0.5 parts by weight of azobisisobutyronitrile as a polymerization initiator while stirring at 70°C for 7 hours while replacing nitrogen. Compound A. The number average molecular weight of the obtained polymer compound A was 14200 (polymerization degree 50).

(Production of polymerizable monomer B)

With 16.5 parts by weight of the compound shown in formula (2-2) and 5.5 parts by weight of the compound in which R shown in formula ( ^6-1 ) is hydrogen, in PS-PPH3 as a basic catalyst (manufactured by Biotage Japan, in In the presence of 0.7 parts by weight of a triphenylphosphine-supported basic catalyst) in polystyrene (PS), it was reacted while stirring at 110°C for 48 hours, thereby obtaining R ¹ represented by the formula (7-2). A compound that is hydrogen (polymerizable monomer B).

It should be noted that the compound shown in the formula (2-2) and the R shown in the formula ( ^6-1 ) The compounding ratio of the compound shown in hydrogen is the compound shown in the formula (2-2) in molar ratio: Compounds in which R ¹ represented by formula (6-1) is hydrogen = 85.3: 42.9.

(Preparation of polymer compound B)

A polymer was obtained by reacting 10 parts by weight of the obtained polymerizable monomer B in the presence of 0.5 parts by weight of azobisisobutyronitrile as a polymerization initiator while stirring at 70°C for 7 hours while substituting nitrogen. Compound B. The number average molecular weight of the obtained polymer compound B was 12900 (polymerization degree 40).

(Production of polymerizable monomer C)

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

It should be noted that the compound shown in the formula (2-3) and the R shown in the formula ( ^6-1 ) The compounding ratio of the compound shown in hydrogen is the compound shown in the formula (2-3) in molar ratio: Compounds in which R ¹ represented by formula (6-1) is hydrogen = 63.2: 32.0.

(Production of Polymer Compound C)

A polymer was obtained by reacting 10 parts by weight of the obtained polymerizable monomer C in the presence of 0.5 parts by weight of azobisisobutyronitrile as a polymerization initiator while stirring at 70°C for 7 hours while replacing nitrogen. Compound C. The number average molecular weight of the obtained polymer compound C was 10200 (polymerization degree 26).

(Production of polymerizable monomer D)

With 16.5 weight parts of compounds shown in formula (2-1) and all R shown in formula ( ^6-2 ) Be the compound 11.8 weight parts of methoxyl group, in PS-PPH3 (Biotage Japan company as basic catalyst) In the presence of 0.7 parts by weight of a triphenylphosphine-supported basic catalyst) in polystyrene (PS), the reaction was carried out while stirring at 110° C. for 48 hours, thereby obtaining the formula (7-4) The compound shown (polymerizable monomer D).

It should be noted that the compound shown in the formula (2-1) and all R shown in the formula ( ^6-2 ) The compounding ratio of the compound shown in the methoxy group is shown in the formula (2-1) in molar ratio The compound: all R shown in formula (6-2) ² are the compound=2:1 of methoxy group.

(Production of Polymer Compound D)

A polymer compound was obtained by reacting 10 parts by weight of the obtained polymerizable monomer D in the presence of 0.5 parts by weight of azobisisobutyronitrile as a polymerization initiator while stirring at 70° C. for 7 hours while substituting nitrogen. d. The number average molecular weight of the obtained polymer compound D was 8900 (polymerization degree 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 ) in which R1 is hydrogen were mixed with PS-PPH3 (manufactured by Biotage Japan Co., Ltd. In the presence of 0.7 parts by weight of triphenylphosphine-supported basic catalyst) in styrene (PS), the reaction was carried out while stirring at 110° C. for 48 hours, thereby obtaining R represented by the formula ( ^8-1 ) as Hydrogen compound (polymerizable monomer E).

It should be noted that the compound shown in the formula (5-1) and the R shown in the formula ( ^6-1 ) is the compound shown in the formula (5-1) in molar ratio in terms of the compound ratio of hydrogen: Compounds in which R ¹ represented by formula (6-1) is hydrogen = 57.63: 28.9.

(Production of Polymer Compound E)

10 parts by weight of the obtained polymerizable monomer E was reacted while stirring at 70° C. for 4 hours while flowing nitrogen 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, thereby Polymer compound E was obtained. The number average molecular weight of the obtained polymer compound E was 15200 (polymerization degree 37).

(Production of polymerizable monomer F)

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

It should be noted that the compound shown in the formula (5-2) and the R shown in the formula ( ^6-1 ) is the compound shown in the formula (5-2): Compounds in which R ¹ represented by formula (6-1) is hydrogen = 72.3: 36.7.

(Production of polymer compound F)

10 parts by weight of the obtained polymerizable monomer F was reacted while stirring at 70°C for 4 hours while nitrogen was flowing 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 gives polymer compound F. The number average molecular weight of the obtained polymer compound F was 16500 (degree of polymerization: 46).

(Production of polymerizable monomer G)

With 16.5 parts by weight of the compound shown in formula (5-1) and all R shown in formula ( ^6-2 ) Be 6.8 parts by weight of the compound of methoxy group in PS-PPH3 (Biotage Japan company manufacture) as basic catalyst , polystyrene (PS) supported triphenylphosphine basic catalyst) 0.7 parts by weight reacted while stirring at 110°C for 48 hours, thus obtaining the compound represented by formula (8-3) (polymerization sex monomer G).

It should be noted that the compound shown in the formula (5-1) and all R shown in the formula ( ^6-2 ) The compounding ratio of the compound shown in the methoxy group is shown in the formula (5-1) in molar ratio The compound: all R ² shown in formula (6-2) are the compound of methoxy group=57.6:28.8.

(Production of polymer compound G)

10 parts by weight of the obtained polymerizable monomer G was reacted while stirring at 70° C. for 4 hours while flowing nitrogen 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, thereby Polymer compound G was obtained. The number average molecular weight of the obtained polymer compound G was 7600 (polymerization degree 15).

(Examples 1 to 17, Comparative Example 1)

According to the mixing ratio recorded in Tables 1 and 2, a planetary mixer (manufactured by Thinky Co., Ltd., "あわとり Taro") After mixing each material, the sealing compound for liquid crystal display elements of Examples 1-17 and Comparative Example 1 was prepared by mixing using a three-roll machine further.

<Evaluation>

The following evaluation was performed about each sealing compound for liquid crystal display elements obtained by the Example and the comparative example. The results are shown in Tables 1 and 2.

(photocurable)

Each of the sealants for liquid crystal display elements obtained in Examples and Comparative Examples was coated on a glass substrate so that the gap after bonding the glass substrates was about 5 μm, and a glass substrate of the same size was stacked on the substrate, and then, using A metal halide lamp was irradiated with ultraviolet rays (wavelength: 365 nm) of 100 mW/cm ² for 10 seconds. Photocurability was evaluated by measuring the amount of change in the peak derived from the (meth)acryloyl group before and after light irradiation using an infrared spectrometer (manufactured by BIORAD, "FTS3000"). The case where the peak derived from the (meth)acryloyl group was reduced by 93% or more after light irradiation was regarded as "◎", and the peak derived from the (meth)acryloyl group was reduced by 85% or more and less than 93% after light irradiation The case was designated as "○", the case where the peak derived from the (meth)acryloyl group decreased by 75% or more and less than 85% after light irradiation was designated as "△", and the peak derived from the (meth)acryloyl group after light irradiation was A case where the reduction of the peak was less than 75% was rated as "x", and the photocurability was evaluated.

(LCD contamination)

1 part by weight of spacer fine particles ("Micropearl SI-H050" manufactured by Sekisui Chemical Industry Co., Ltd.) was dispersed in 100 parts by weight of each sealant for liquid crystal display elements obtained in Examples and Comparative Examples to prepare a sealant for liquid crystal display elements. The sealant was coated with a dispenser on one of the two substrates with the polished alignment film and the transparent electrode so that the line width of the sealant was 1 mm.

Next, tiny drops of liquid crystal (manufactured by Chisso Corporation, "JC-5004LA") are applied dropwise to the entire surface of the sealant inside the frame of the substrate with a transparent electrode, and then another color filter substrate with a transparent electrode is attached. The sealant part was irradiated with 100 mW/ ^cm2 of ultraviolet rays (wavelength: 365 nm) for 30 seconds using a metal halide lamp to be cured, and further heated at 120° C. for 1 hour to obtain a liquid crystal display element.

The following two types of liquid crystal display elements were produced: a liquid crystal display element (without light-shielding portion) in which the sealant was completely illuminated by light by controlling the coating position of the sealant using a dispenser; A liquid crystal display element (with a light-shielding portion) obtained by applying a sealant to overlap the black matrix. Fig. 1 is a cross-sectional view schematically showing a liquid crystal display element produced in a state without a light-shielding portion using each sealant for a liquid crystal display element obtained in an example and a comparative example, and Fig. The sealing compound for each liquid crystal display element obtained in the Example and the comparative example is the cross-sectional view of the liquid crystal display element produced in the state which has a light-shielding part. As shown in FIG. 1, the liquid crystal display element without a light-shielding portion on the sealant 1 is in a state where the sealant 1 is completely illuminated by light. On the other hand, the liquid crystal display element with a light-shielding portion on the sealant 1 is as shown in FIG. 2. The sealant 1 at the portion in contact with the liquid crystal 3 is blocked by the black matrix 2 and does not receive light at all.

After performing the operation test for 100 hours about the obtained liquid crystal display element, the disorder of the liquid crystal orientation in the sealing compound vicinity after reaching the state which applied the voltage at 80 degreeC for 1000 hours was confirmed visually.

The orientation disorder was judged by the color unevenness of the display part, and according to the degree of color unevenness, the case of no color unevenness was evaluated as "◎", the case of slight color unevenness was evaluated as "○", and the case of color unevenness was evaluated as "○". The case where there was little uniformity was evaluated as "Δ", and the case where color unevenness was considerably large was evaluated as "×", and the liquid crystal contamination property was evaluated.

In addition, the liquid crystal display element evaluated as "⊚" and "◯" was a level with no practical problem at all.

[Table 1]

[Table 2]

Industrial availability

According to the present invention, it is possible to provide a polymerizable monomer having low contaminating property to liquid crystal, high sensitivity to long-wavelength light, and excellent sensitization effect, and a polymer compound obtained by polymerizing the polymerizable monomer. In addition, according to the present invention, there can be provided a photocurable resin composition containing the polymerizable monomer and/or the polymer compound, a sealant for a liquid crystal display element produced using the photocurable resin composition, and a photocurable resin composition using the photocurable resin composition. The upper and lower conduction material and the liquid crystal display element manufactured by the sealant for the liquid crystal display element.

Symbol Description

1. Sealant

2. Black matrix

3. LCD

Claims (8)

1. a kind of sealing material for liquid crystal display device, which is characterized in that be using containing curable resin and polymerizable monomer And/or the Photocurable resin composition of high-molecular compound obtained from polymerizable monomer polymerization is manufactured, In,

The polymerizable monomer is to keep dialkyl amino yl benzoic acid based compound and epoxide with unsaturated double-bond anti- Polymerizable monomer obtained from answering makes dialkyl amino yl benzoic acid based compound and the epoxy compound with alkoxysilyl Polymerizable monomer obtained from object reaction or make with can with the thioxanthone derivates of the functional group of epoxy reaction with have Polymerizable monomer obtained from the epoxide reaction of alkoxysilyl,

It is described have can with the thioxanthone derivates of the functional group of epoxy reaction be following formula (3) compound represented,

In formula (3), X is hydrogen, group shown in hydroxyl or following formula (4), and each X can be the same or different, but at least one X For group shown in hydroxyl or following formula (4),

2. sealing material for liquid crystal display device according to claim 1, which is characterized in that dialkyl amino yl benzoic acid system Conjunction object be following formula (2-1) compound represented or formula (2-2) compound represented,

3. sealing material for liquid crystal display device according to claim 1, which is characterized in that thioxanthone derivates are following formula (5-1) or formula (5-2) compound represented,

4. sealing material for liquid crystal display device according to claim 1,2 or 3, which is characterized in that under epoxide is Formula (6-1) or formula (6-2) compound represented are stated,

In formula (6-1), R¹Indicate hydrogen or methyl, in formula (6-2), R²The alkyl or carbon number that expression carbon number is 1~10 are 1~10 Alkoxy, each R²It can be the same or different, at least one R²It is the alkoxy that carbon number is 1~10.

5. sealing material for liquid crystal display device according to claim 1,2 or 3, which is characterized in that high-molecular compound The degree of polymerization is 3 or more.

6. sealing material for liquid crystal display device according to claim 1,2 or 3, which is characterized in that light-cured resin group It closes object and contains opacifier.

7. a kind of conductive material up and down, which is characterized in that contain liquid crystal display element described in claim 1,2,3,4,5 or 6 With sealant and electrically conductive microparticle.

8. a kind of liquid crystal display element, which is characterized in that be using the member of liquid crystal display described in claim 1,2,3,4,5 or 6 Part sealant or it is as claimed in claim 7 up and down conductive material and manufacture.