TWI885211B - Compound, photopolymerization initiator, curable resin composition, display element composition, liquid crystal display element sealant, upper and lower conductive material, and liquid crystal display element - Google Patents

Abstract

The purpose of the present invention is to provide a 9-oxysulfur compound having excellent responsiveness to long-wavelength light. Compound. In addition, the present invention aims to provide a 9-oxysulfur A photopolymerization initiator composed of a compound, a curable resin composition containing the photopolymerization initiator and having excellent storage stability and light-shielding curing property, a display element composition formed using the curable resin composition, and a liquid crystal display element sealant with excellent low liquid crystal contamination property formed using the curable resin composition. Furthermore, the object of the present invention is to provide a top-bottom conductive material and a liquid crystal display element formed using the liquid crystal display element sealant. The present invention is a 9-oxysulfide represented by the following formula (1): Compound. In formula (1), X represents a structure represented by the following formula (2-1), (2-2) or (2-3), ^R1 independently represents a hydrogen atom, a methyl group, an ethyl group or a nitro group, and ^R2 independently represents a hydrogen atom, a methyl group, an ethyl group or a nitro group. In formula (2-1), (2-2) and (2-3), ^R3 represents a structure containing a heteroatom and an aromatic ring, and * represents a bonding position.

Description

9-Oxysulfur compound, photopolymerization initiator, curable resin composition, display element composition, liquid crystal display element sealant, upper and lower conductive material, and liquid crystal display element

The present invention relates to a 9-oxosulfur Compound. In addition, the present invention relates to a 9-oxysulfur The present invention relates to a photopolymerization initiator composed of a compound, a curable resin composition containing the photopolymerization initiator, a display element composition formed using the curable resin composition, and a liquid crystal display element sealant formed using the curable resin composition. Furthermore, the present invention relates to an upper and lower conductive material and a liquid crystal display element formed using the liquid crystal display element sealant.

In recent years, as a manufacturing method for liquid crystal display elements such as liquid crystal display units, from the perspective of shortening the production time and optimizing the amount of liquid crystal used, a liquid crystal dripping method called a dripping method is used, which uses a light-heat-curing curable resin composition disclosed in Patent Documents 1 and 2 as a sealant. In the dripping method, a frame-shaped sealing pattern is first formed on one of two transparent substrates with electrodes by dotting glue. Then, in the uncured state of the sealant, droplets of liquid crystal are dripped onto the entire surface of the frame of the transparent substrate, and the other transparent substrate is immediately attached, and the sealing part is irradiated with light such as ultraviolet rays for temporary curing. After that, the liquid crystal is heated during annealing, and formal curing is performed to produce a liquid crystal display element. If the substrates are bonded under reduced pressure, liquid crystal display elements can be manufactured with extremely high efficiency. Currently, the main method for manufacturing liquid crystal display elements is the dripping method.

However, nowadays, various mobile devices with LCD panels, such as mobile phones and portable game consoles, are widely used, and miniaturization of devices is the most demanded issue. As a method for miniaturization of devices, narrowing the edge of the liquid crystal display part can be cited, for example, arranging the position of the sealing part under the black matrix (hereinafter also referred to as narrow edge design). [Prior technical literature] [Patent literature]

Patent document 1: Japanese Patent Publication No. 2001-133794 Patent document 2: International Publication No. 02/092718 Patent document 3: Japanese Patent Publication No. 2017-125033 Patent document 4: International Publication No. 2017/130594

[The problem that the invention wants to solve]

Since the sealant is placed directly below the black matrix in the narrow edge design, the light irradiated when the sealant is photocured will be shielded if the dripping method is used. In the future, as narrow edge development continues or when the liquid crystal material is changed, even the sealant that was previously without any problems may have uncured sealant components dissolved into the liquid crystal and cause liquid crystal contamination. Therefore, a sealant with better low liquid crystal contamination is sought.

Furthermore, usually, as a method of photocuring the sealant, ultraviolet irradiation is performed. In particular, in the liquid crystal dropping method, since the sealant is cured after the liquid crystal is dropped, there is a problem that the liquid crystal is easily degraded by irradiation with ultraviolet rays. Therefore, in order to prevent the degradation of the liquid crystal due to ultraviolet rays, light curing is performed by using long-wavelength light in the visible light region through a cutoff filter or the like. As a method of photocuring the sealant by long-wavelength light, a method of combining a sensitizer with a high sensitivity to long-wavelength light with a photopolymerization initiator is considered. For example, Patent Documents 3 and 4 disclose a curable resin composition obtained by combining a photopolymerization initiator and a sensitizer. However, when such curable resin compositions are used as sealants for liquid crystal display devices, the total amount of photopolymerization initiator and sensitizer increases in order to fully perform photocuring by long-wavelength light, which may cause liquid crystal contamination or reduce storage stability.

The purpose of the present invention is to provide a 9-oxysulfur compound having excellent responsiveness to long-wavelength light. Compound. In addition, the present invention aims to provide a 9-oxysulfur A photopolymerization initiator composed of a compound, a curable resin composition containing the photopolymerization initiator and having excellent storage stability and light-shielding curing property, a display element composition formed using the curable resin composition, and a liquid crystal display element sealant with excellent low liquid crystal contamination property formed using the curable resin composition. Furthermore, the purpose of the present invention is to provide an upper and lower conductive material and a liquid crystal display element formed using the liquid crystal display element sealant. [Technical means for solving the problem]

The present invention is a 9-oxysulfur compound represented by the following formula (1): Compound.

In formula (1), X represents a structure represented by the following formula (2-1), (2-2) or (2-3), ^R1 independently represents a hydrogen atom, a methyl group, an ethyl group or a nitro group, and ^R2 independently represents a hydrogen atom, a methyl group, an ethyl group or a nitro group.

In formulae (2-1), (2-2) and (2-3), R ³ represents a structure containing a heteroatom and an aromatic ring, and * represents a bonding position. The present invention is described in detail below.

The inventors of the present invention have found that by mixing a photopolymerization initiator with excellent reactivity to long-wavelength light into a curable resin composition, the curability of the light-shielding portion can be improved. However, when such a photopolymerization initiator is used, the storage stability of the obtained curable resin composition may deteriorate, or when the obtained curable resin composition is used as a sealant for liquid crystal display elements, liquid crystal contamination may occur. Therefore, the inventors of the present invention have found that using 9-oxysulfide having a specific structure can improve the curability of the light-shielding portion. Compounds were studied as photopolymerization initiators. As a result, it was found that a curable resin composition with excellent storage stability, light-shielding curability, and low liquid crystal contamination when used as a sealant for liquid crystal display elements can be obtained, thereby completing the present invention. In addition, the above-mentioned "long wavelength" in this specification refers to light with a wavelength of 400 nm or more.

9-Oxosulfur The compound is represented by the above formula (1). In the above formula (1), X represents a structure represented by the above formula (2-1), (2-2) or (2-3), and in the above formula (2-1), (2-2) and (2-3), R ³ represents a structure containing a heteroatom and an aromatic ring. When the above R ³ is a structure containing a heteroatom and an aromatic ring, 9-oxysulfur The conjugation of the skeleton is expanded, thereby the 9-oxosulfur The compound has excellent responsiveness to long-wavelength light. When the compound is used as a photopolymerization initiator in a curable resin composition, the curability of the light-shielding portion of the curable resin composition becomes excellent. In particular, from the viewpoint of improving the reactivity to long-wavelength light, the above ^R3 is preferably a structure represented by the following formula (3-1), (3-2), (3-3), (3-4), (3-5), (3-6), (3-7) or (3-8). From the viewpoint of improving the electron density and improving the low liquid crystal contamination property when used as a sealant for a liquid crystal display element, it is more preferably a structure represented by the following formula (3-1), (3-2), (3-3), (3-4) or (3-5), and more preferably a structure represented by the following formula (3-1).

In formulae (3-1) to (3-8), * represents a bonding position. In formulae (3-1) to (3-8), hydrogen atoms other than hydrogen atoms contained in the OH group in formulae (3-2) and (3-3) may be substituted.

In the above formula (1), ^R1 independently represents a hydrogen atom, a methyl group, an ethyl group or a nitro group, and ^R2 independently represents a hydrogen atom, a methyl group, an ethyl group or a nitro group. From the viewpoint of solubility in the curable resin described below, it is preferred that at least one ^R1 in the formula (1) is a methyl group or an ethyl group, and at least one ^R2 in the above formula (1) is a methyl group or an ethyl group.

9-Oxosulfur The preferred lower limit of the molecular weight of the compound is 500, and the preferred upper limit is 1000. By making the molecular weight within the above range, the 9-oxosulfur When the compound is used as a photopolymerization initiator in a sealant for a liquid crystal display element, the low liquid crystal contamination property becomes more excellent. The lower limit of the molecular weight of the compound is preferably 550, and the upper limit is preferably 800. Furthermore, in this specification, the above "molecular weight" is the molecular weight obtained from the structural formula if the molecular structure of the compound is specified, and the number average molecular weight is sometimes used to express the compound with a wide distribution of polymerization degree and the compound with no specified modification site. In addition, in this specification, the above "number average molecular weight" is a value obtained by polystyrene conversion using tetrahydrofuran as a solvent and gel permeation chromatography (GPC). As a column used when measuring the number average molecular weight converted to polystyrene by GPC, for example, Shodex LF-804 (manufactured by Showa Denko K.K.) can be listed.

9-Oxosulfur The compound is suitable for use as a photopolymerization initiator. The photopolymerization initiator composed of the compound is also one of the present invention. The curable resin composition containing the curable resin and the photopolymerization initiator of the present invention is also one of the present invention.

Since the photopolymerization initiator of the present invention has excellent reactivity to long-wavelength light, when the curable resin composition of the present invention is used as a sealant for a liquid crystal display element, by reducing the content of the photopolymerization initiator of the present invention within the range that can maintain the curability of the light-shielding portion, the low liquid crystal contamination property of the sealant for the liquid crystal display element can be made more excellent. The preferred lower limit of the content of the photopolymerization initiator of the present invention in the curable resin composition of the present invention is 0.05 parts by weight, and the preferred upper limit is 3 parts by weight relative to 100 parts by weight of the curable resin. By making the content of the photopolymerization initiator of the present invention more than 0.05 parts by weight, the curability of the light-shielding portion of the obtained curable resin composition becomes more excellent. By making the content of the photopolymerization initiator of the present invention less than 3 parts by weight, the storage stability of the obtained curable resin composition becomes better, and when the curable resin composition is used as a sealant for liquid crystal display elements, the low liquid crystal contamination property becomes better. The better lower limit of the content of the photopolymerization initiator of the present invention is 0.1 parts by weight, and the better upper limit is 2 parts by weight.

The curable resin composition of the present invention may contain other photopolymerization initiators other than the photopolymerization initiator of the present invention within the scope that does not impair the purpose of the present invention. Examples of the other photopolymerization initiators include benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, oxime ester compounds, benzoin ether compounds, other 9-oxysulfur compounds other than the photopolymerization initiator of the present invention, Compounds, etc. As the other photopolymerization initiators, specifically, for example, 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1-(4- 1,2-(dimethylamino)-2-((4-methylphenyl)methyl)-1-(4-(4- 1-Butanone, 2,2-dimethoxy-1,2-diphenylethane-1-one, bis(2,4,6-trimethylbenzyl)phenylphosphine oxide, 2-methyl-1-(4-methylthiophenyl)-2- The photopolymerization initiators include 1-(4-(2-hydroxyethoxy)phenyl)-2-hydroxy-2-methyl-1-propane-1-one, 1-(4-(phenylthio)phenyl)-1,2-octanedione 2-(O-benzoyl oxime), 2,4,6-trimethylbenzoyldiphenylphosphine oxide, etc. The above other photopolymerization initiators may be used alone or in combination of two or more.

The hardening resin composition of the present invention contains a hardening resin. The hardening resin preferably contains a (meth)acrylic acid compound, and more preferably contains a (meth)acrylic acid compound and an epoxy compound. In addition, in this specification, the above-mentioned "(meth)acrylic acid" refers to acrylic acid or methacrylic acid, the above-mentioned "(meth)acrylic acid compound" refers to a compound having a (meth)acryl group, and the above-mentioned "(meth)acryl group" refers to an acryl group or a methacryl group.

As the above-mentioned (meth) acrylic acid compound, for example, (meth) acrylic acid ester compounds, epoxy (meth) acrylic acid esters, amine (meth) acrylic acid esters, etc. can be listed. Among them, epoxy (meth) acrylic acid esters are preferred. In addition, from the aspect of self-reactivity, the above-mentioned (meth) acrylic acid compound is preferably one having two or more (meth) acrylic acid groups in one molecule. Furthermore, in this specification, the above-mentioned "(meth) acrylic acid ester" refers to acrylic acid ester or methacrylic acid ester, and the above-mentioned "epoxy (meth) acrylic acid ester" refers to a compound obtained by reacting all epoxy groups in an epoxy compound with (meth) acrylic acid.

Examples of the monofunctional (meth)acrylate compounds include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, isodecyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate. Lauryl (meth)acrylate, isomyristyl (meth)acrylate, stearyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, cyclohexyl (meth)acrylate, isoborneol (meth)acrylate, dicyclopentenyl (meth)acrylate, benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxy (meth)acrylate 2-Butoxyethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, methoxyethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, ethyl carbitol (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoroethyl (meth)acrylate Propyl (meth)acrylate, 1H,1H,5H-octafluoropentyl (meth)acrylate, imide (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, 2-(meth)acryloyloxyethyl succinate, 2-(meth)acryloyloxyethyl hexahydrophthalate, 2-(meth)acryloyloxyethyl 2-hydroxypropyl phthalate, 2-(meth)acryloyloxyethyl phosphate, glycidyl (meth)acrylate, etc.

In addition, examples of the bifunctional (meth)acrylate compounds include 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 2-n-butyl-2-ethyl-1,3-propanediol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, Polypropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene oxide added bisphenol A di(meth)acrylate, propylene oxide added bisphenol A di(meth)acrylate, ethylene oxide added bisphenol F di(meth)acrylate, dihydroxymethyl dicyclopentadienyl di(meth)acrylate, ethylene oxide modified isocyanuric acid 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, polycaprolactone diol di(meth)acrylate, polybutadiene diol di(meth)acrylate, etc.

In addition, examples of the trifunctional or higher-functional (meth)acrylate compounds include trihydroxymethylpropane tri(meth)acrylate, ethylene oxide-added trihydroxymethylpropane tri(meth)acrylate, propylene oxide-added trihydroxymethylpropane tri(meth)acrylate, caprolactone-modified trihydroxymethylpropane tri(meth)acrylate, ethylene oxide-added isocyanuric acid tri(meth)acrylate, glycerol tri(meth)acrylate, propylene oxide-added glycerol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, tri(meth)acryloyloxyethyl phosphate, di-trihydroxymethylpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and the like.

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

Examples of the epoxy compounds used as raw materials for synthesizing the epoxy (meth) acrylate include bisphenol A epoxy compounds, bisphenol F epoxy compounds, bisphenol S epoxy compounds, 2,2'-diallylbisphenol A epoxy compounds, hydrogenated bisphenol epoxy compounds, propylene oxide addition bisphenol A epoxy compounds, resorcinol epoxy compounds, biphenyl epoxy compounds, thioether epoxy compounds, diisocyanate epoxy compounds, and diisocyanate epoxy compounds. Phenyl ether type epoxy compounds, dicyclopentadiene type epoxy compounds, naphthalene type epoxy compounds, phenol novolac type epoxy compounds, o-cresol novolac type epoxy compounds, dicyclopentadiene novolac type epoxy compounds, biphenyl novolac type epoxy compounds, naphthol novolac type epoxy compounds, epoxy propylamine type epoxy compounds, alkyl polyol type epoxy compounds, rubber modified epoxy compounds, epoxy propyl ester compounds, etc.

Examples of commercially available bisphenol A epoxy compounds include jER828EL, jER1004 (both manufactured by Mitsubishi Chemical Co., Ltd.), and EPICLON EXA-850CRP (manufactured by DIC Co., Ltd.). Examples of commercially available bisphenol F epoxy compounds include jER806 and jER4004 (both manufactured by Mitsubishi Chemical Co., Ltd.). Examples of commercially available bisphenol S epoxy compounds include EPICLON EXA1514 (manufactured by DIC Co., Ltd.). Examples of commercially available 2,2'-diallylbisphenol A epoxy compounds include RE-810NM (manufactured by Nippon Kayaku Co., Ltd.). As commercially available products of the above-mentioned hydrogenated bisphenol type epoxy compounds, for example, EPICLON EXA7015 (manufactured by DIC Corporation) and the like can be cited. As commercially available products of the above-mentioned propylene oxide addition bisphenol A type epoxy compounds, for example, EP-4000S (manufactured by ADEKA Corporation) and the like can be cited. As commercially available products of the above-mentioned resorcinol type epoxy compounds, for example, EX-201 (manufactured by Nagase Chemicals Co., Ltd.) and the like can be cited. As commercially available products of the above-mentioned biphenyl type epoxy compounds, for example, jER YX-4000H (manufactured by Mitsubishi Chemical Corporation) and the like can be cited. As commercially available products of the above-mentioned thioether type epoxy compounds, for example, YSLV-50TE (manufactured by Nippon Steel Chemical Materials Co., Ltd.) and the like can be cited. As commercially available products of the above-mentioned diphenyl ether type epoxy compounds, for example, YSLV-80DE (manufactured by Nippon Steel Chemical Materials Co., Ltd.) can be cited. As commercially available products of the above-mentioned dicyclopentadiene type epoxy compounds, for example, EP-4088S (manufactured by ADEKA Co., Ltd.) can be cited. As commercially available products of the above-mentioned naphthalene type epoxy compounds, for example, EPICLON HP4032 and EPICLON EXA-4700 (both manufactured by DIC Co., Ltd.) can be cited. As commercially available products of the above-mentioned phenol novolac type epoxy compounds, for example, EPICLON N-770 (manufactured by DIC Co., Ltd.) can be cited. As commercially available products of the above-mentioned o-cresol novolac type epoxy compounds, for example, EPICLON N-670-EXP-S (manufactured by DIC Corporation) and the like can be cited. As commercially available products of the above-mentioned dicyclopentadiene novolac type epoxy compounds, for example, EPICLON HP7200 (manufactured by DIC Corporation) and the like can be cited. As commercially available products of the above-mentioned biphenyl novolac type epoxy compounds, for example, NC-3000P (manufactured by Nippon Kayaku Co., Ltd.) and the like can be cited. As commercially available products of the above-mentioned naphthol novolac type epoxy compounds, for example, ESN-165S (manufactured by Nippon Steel Chemical Materials Co., Ltd.) and the like can be cited. Examples of commercially available epoxy compounds of the above-mentioned epoxy propylamine type include jER630 (manufactured by Mitsubishi Chemical), EPICLON 430 (manufactured by DIC), and TETRAD-X (manufactured by Mitsubishi Gas Chemical). Examples of commercially available epoxy compounds of the above-mentioned alkyl polyol type include ZX-1542 (manufactured by Nippon Steel Chemical Materials Co., Ltd.), EPICLON 726 (manufactured by DIC), Epolight 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.), and Denacol EX-611 (manufactured by Nagase Chemicals Co., Ltd.). Examples of the commercially available rubber-modified epoxy compounds include YR-450, YR-207 (both manufactured by Nippon Steel Chemical Materials Co., Ltd.), Epolead PB (manufactured by Daicel Co., Ltd.), etc. Examples of the commercially available glycidyl ester compounds include Denacol EX-147 (manufactured by Nagase Chemicals Co., Ltd.), etc. Other commercially available epoxy compounds include, for example, YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Nippon Steel Chemical Materials Co., Ltd.), XAC4151 (manufactured by Asahi Kasei Corporation), jER1031, jER1032 (both manufactured by Mitsubishi Chemical Co., Ltd.), EXA-7120 (manufactured by DIC Corporation), TEPIC (manufactured by Nissan Chemical Co., Ltd.), etc.

Examples of commercially available epoxy (meth)acrylates include epoxy (meth)acrylate manufactured by DAICEL-ALLNEX, epoxy (meth)acrylate manufactured by Shin-Nakamura Chemical Industry, epoxy (meth)acrylate manufactured by Kyoeisha Chemical, and epoxy (meth)acrylate manufactured by Nagase Chemicals. Examples of epoxy (meth) acrylates manufactured by the aforementioned DAICEL-ALLNEX include EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL 3700, EBECRYL3701, EBECRYL3702, EBECRYL3703, EBECRYL3708, EBECRYL3800, EBECRYL6040, and EBECRYL RDX63182. Examples of epoxy (meth) acrylates manufactured by the aforementioned Shin-Nakamura Chemical Industries include EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, and EMA-1020. Examples of epoxy (meth) acrylates manufactured by the aforementioned Kyoeisha Chemical Co., Ltd. include EPOXYESTER M-600A, EPOXYESTER 40EM, EPOXYESTER 70PA, EPOXYESTER 200PA, EPOXYESTER 80MFA, EPOXYESTER 3002M, EPOXYESTER 3002A, EPOXYESTER 1600A, EPOXYESTER 3000M, EPOXYESTER 3000A, EPOXYESTER 200EA, EPOXYESTER 400EA, etc. Examples of epoxy (meth) acrylates manufactured by the aforementioned Nagase Chemical Co., Ltd. include Denacol Acrylate DA-141, Denacol Acrylate DA-314, Denacol Acrylate DA-911, etc.

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

Examples of the isocyanate compound include isophorone diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4,4'-diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysamine diisocyanate, triphenylmethane triisocyanate, tri(isocyanatophenyl)phosphorothioate, tetramethylxylylene diisocyanate, and 1,6,11-undecane triisocyanate.

Furthermore, as the above-mentioned isocyanate compound, an extended isocyanate compound obtained by reacting a polyol with an excess of an isocyanate compound can also be used. As the above-mentioned polyol, for example, ethylene glycol, propylene glycol, glycerin, sorbitol, trihydroxymethylpropane, carbonate diol, polyether diol, polyester diol, polycaprolactone diol, etc. can be listed.

Examples of the (meth)acrylic acid derivatives having a hydroxyl group include: hydroxyalkyl mono(meth)acrylate, mono(meth)acrylate of a diol, mono(meth)acrylate or di(meth)acrylate of a triol, epoxy(meth)acrylate, etc. Examples of the hydroxyalkyl mono(meth)acrylate include: 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc. Examples of the diols include: ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, polyethylene glycol, etc. Examples of the triols include: trihydroxymethylethane, trihydroxymethylpropane, glycerol, etc. Examples of the above-mentioned epoxy (meth) acrylate include bisphenol A type epoxy acrylate, etc.

As commercially available amine (meth) acrylates, for example, amine (meth) acrylates manufactured by Toagosei Co., Ltd., amine (meth) acrylates manufactured by DAICEL-ALLNEX Co., Ltd., amine (meth) acrylates manufactured by Negami Kogyo Co., Ltd., amine (meth) acrylates manufactured by Shin-Nakamura Chemical Co., Ltd., and amine (meth) acrylates manufactured by Kyoeisha Chemical Co., Ltd., etc. As commercially available amine (meth) acrylates manufactured by Toagosei Co., Ltd., for example, M-1100, M-1200, M-1210, M-1600, etc. can be cited. Examples of amine (meth)acrylates manufactured by the above-mentioned DAICEL-ALLNEX company include EBECRYL210, EBECRYL220, EBECRYL230, EBECRYL270, EBECRYL1290, EBECRYL2220, EBECRYL4827, EBECRYL4842, EBECRYL4858, EBECRYL5129, EBECRYL6700, EBECRYL8402, EBECRYL8803, EBECRYL8804, EBECRYL8807, EBECRYL9260, etc. Examples of amine (meth)acrylates manufactured by the aforementioned Negami Industries include Artresin UN-330, Artresin SH-500B, Artresin UN-1200TPK, Artresin UN-1255, Artresin UN-3320HB, Artresin UN-7100, Artresin UN-9000A, Artresin UN-9000H, etc. Examples of amine (meth)acrylates manufactured by the aforementioned Shin-Nakamura Chemical Industry Co., Ltd. include: U-2HA, U-2PHA, U-3HA, U-4HA, U-6H, U-6HA, U-6LPA, U-10H, U-15HA, U-108, U-108A, U-122A, U-122P, U-324A, U-340A, U-340P, U-1084A, U-2061BA, UA-340P, UA-4000, UA-4100, UA-4200, UA-4400, UA-5201P, UA-7100, UA-7200, UA-W2A, etc. Examples of amine (meth)acrylates manufactured by the aforementioned Kyoeisha Chemical Company include: AH-600, AI-600, AT-600, UA-101I, UA-101T, UA-306H, UA-306I, UA-306T, etc.

Examples of the epoxy compound include: epoxy compounds used as raw materials for synthesizing the epoxy (meth)acrylate or partially (meth)acrylic acid-modified epoxy compounds. In addition, in this specification, the partially (meth)acrylic acid-modified epoxy compound refers to a compound having one or more epoxy groups and one or more (meth)acrylic acid groups in one molecule, which can be obtained by reacting a part of the epoxy groups of an epoxy compound having two or more epoxy groups in one molecule with (meth)acrylic acid.

When the curable resin contains the (meth)acrylic compound and the epoxy compound, or when the curable resin contains the partially (meth)acrylic modified epoxy compound, the ratio of the (meth)acrylic group in the total of the (meth)acrylic group and the epoxy group in the curable resin is preferably 30 mol% or more and 95 mol% or less. When the ratio of the (meth)acrylic group is within this range, the generation of liquid crystal contamination when the obtained curable resin composition is used as a sealant for liquid crystal display elements is suppressed, and the adhesion becomes more excellent.

From the viewpoint of achieving excellent low liquid crystal contamination when the obtained curable resin composition is used as a sealant for liquid crystal display devices, the curable resin preferably has a hydrogen bonding unit such as an -OH group, a -NH- group, or a _-NH2 group.

The above-mentioned curable resins may be used alone or in combination of two or more.

The curable resin composition of the present invention may contain a sensitizer. The sensitizer has the function of further improving the polymerization initiation efficiency of the photopolymerization initiator and further promoting the curing reaction of the curable resin composition of the present invention.

Examples of the sensitizer include ethyl 4-(dimethylamino)benzoate, 9,10-dibutoxyanthracene, 2,4-diethyl 9-oxysulfide, , 2,2-dimethoxy-1,2-diphenylethane-1-one, benzophenone, 2,4-dichlorobenzophenone, methyl o-benzoylbenzoate, 4,4'-bis(dimethylamino)benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, etc.

The preferred lower limit of the content of the sensitizer is 0.01 parts by weight and the preferred upper limit is 3 parts by weight relative to 100 parts by weight of the curable resin. By making the content of the sensitizer more than 0.01 parts by weight, the sensitization effect can be better exerted. By making the content of the sensitizer less than 3 parts by weight, the absorption will not be too large and the light can be transmitted to the deep part. The more preferred lower limit of the content of the sensitizer is 0.1 parts by weight and the more preferred upper limit is 1 part by weight.

The curable resin composition of the present invention may contain a thermal polymerization initiator within the scope that does not impair the purpose of the present invention. As the above-mentioned thermal polymerization initiator, for example, those composed of azo compounds or organic peroxides can be listed. Among them, from the perspective of suppressing liquid crystal contamination when the obtained curable resin composition is used as a sealant for liquid crystal display elements, an initiator composed of an azo compound (hereinafter also referred to as "azo initiator") is preferred, and an initiator composed of a polymer azo compound (hereinafter also referred to as "polymer azo initiator") is more preferred. The above-mentioned thermal polymerization initiator can be used alone or in combination of two or more. Furthermore, in this specification, the so-called "polymer azo compound" refers to a compound having an azo group, which generates free radicals that can harden the (meth)acrylic group by heat, and has a number average molecular weight of 300 or more.

The preferred lower limit of the number average molecular weight of the polymer azo compound is 1000, and the preferred upper limit is 300,000. By making the number average molecular weight of the polymer azo compound within this range, the obtained curable resin composition can be prevented from adversely affecting the liquid crystal when used as a sealant for liquid crystal display elements, and can be easily mixed in the curable resin. The more preferred lower limit of the number average molecular weight of the polymer azo compound is 5000, and the more preferred upper limit is 100,000, and the further preferred lower limit is 10,000, and the further preferred upper limit is 90,000.

As the above-mentioned high molecular weight azo compound, for example, there can be cited a structure having a plurality of units such as polyoxyalkylene or polydimethylsiloxane bonded via an azo group. As the above-mentioned high molecular weight azo compound having a structure having a plurality of units such as polyoxyalkylene bonded via an azo group, it is preferably a structure having polyethylene oxide. As the above-mentioned high molecular weight azo compound, specifically, for example, there can be cited: a condensate of 4,4'-azobis(4-cyanovaleric acid) and polyalkylene glycol, a condensate of 4,4'-azobis(4-cyanovaleric acid) and polydimethylsiloxane having a terminal amino group, etc. Examples of the commercially available polymer azo initiators include VPE-0201, VPE-0401, VPE-0601, VPS-0501, and VPS-1001 (all manufactured by FUJIFILM Wako Pure Chemical Co., Ltd.). In addition, examples of non-polymer azo initiators include V-65 and V-501 (all manufactured by FUJIFILM Wako Pure Chemical Co., Ltd.).

Examples of the organic peroxide include ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, peroxyester, diacyl peroxide, and peroxydicarbonate.

The preferred lower limit of the content of the thermal polymerization initiator is 0.01 parts by weight, and the preferred upper limit is 10 parts by weight relative to 100 parts by weight of the curable resin. By making the content of the thermal polymerization initiator within this range, liquid crystal contamination when the obtained curable resin composition is used as a sealant for liquid crystal display elements is suppressed, and the storage stability and thermal curing properties become better. The preferred lower limit of the content of the thermal polymerization initiator is 0.1 parts by weight, and the preferred upper limit is 5 parts by weight.

The curable resin composition of the present invention may also contain a thermosetting agent. Examples of the thermosetting agent include organic acid hydrazides, imidazole derivatives, amine compounds, polyphenol compounds, acid anhydrides, etc. Among them, organic acid hydrazides are preferably used. The thermosetting agents may be used alone or in combination of two or more.

Examples of the above-mentioned organic acid hydrazides include sebacic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide, malonic acid hydrazide, etc. Examples of commercially available organic acid hydrazides include organic acid hydrazide manufactured by Otsuka Chemical Co., Ltd., organic acid hydrazide manufactured by Ajinomoto Fine-Techno Co., Ltd., etc. Examples of the above-mentioned organic acid hydrazide manufactured by Otsuka Chemical Co., Ltd. include SDH, ADH, etc. Examples of the above-mentioned organic acid hydrazide manufactured by Ajinomoto Fine-Techno Co., Ltd. include Amicure VDH, Amicure VDH-J, Amicure UDH, Amicure UDH-J, etc.

The preferred lower limit of the content of the above-mentioned thermosetting agent is 1 part by weight and the preferred upper limit is 50 parts by weight relative to 100 parts by weight of the above-mentioned curable resin. By making the content of the above-mentioned thermosetting agent within this range, the thermosetting property can be made more excellent without deteriorating the coating property of the obtained curable resin composition. The more preferred upper limit of the content of the above-mentioned thermosetting agent is 30 parts by weight.

The curable resin composition of the present invention preferably contains a filler to adjust the viscosity, further improve the adhesion through the stress dispersion effect, improve the linear expansion rate, and improve the moisture resistance of the cured product.

As the above-mentioned filler, an inorganic filler or an organic filler can be used. As the above-mentioned inorganic filler, for example, there can be listed: silica, talc, glass beads, sponge, gypsum, diatomaceous earth, bentonite, bentonite, montmorillonite, sericite, activated clay, aluminum oxide, zinc oxide, iron oxide, magnesium oxide, tin oxide, titanium oxide, calcium carbonate, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, aluminum nitride, silicon nitride, barium sulfate, calcium silicate, etc. As the above-mentioned organic filler, for example, there can be listed: polyester microparticles, polyurethane microparticles, vinyl polymer microparticles, acrylic polymer microparticles, etc. The above fillers can be used alone or in combination of two or more.

In 100 parts by weight of the curable resin composition of the present invention, the preferred lower limit of the content of the filler is 10 parts by weight, and the preferred upper limit is 70 parts by weight. By making the content of the filler within this range, the effect of improving adhesion and the like is more excellent without deteriorating the coating properties and the like. The preferred lower limit of the content of the filler is 20 parts by weight, and the preferred upper limit is 60 parts by weight.

The curable resin composition of the present invention may also contain a silane coupling agent. The silane coupling agent mainly functions as a bonding aid for making the curable resin composition and the substrate or other adherends bond well.

As the above-mentioned silane coupling agent, for example, 3-aminopropyltrimethoxysilane, 3-butyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, etc. are preferably used. They are excellent in improving the adhesion with the substrate, etc., and can inhibit the curable resin from flowing into the liquid crystal when the obtained curable resin composition is used as a sealant for liquid crystal display elements by chemically bonding with the curable resin. The above-mentioned silane coupling agent can be used alone or in combination of two or more.

In 100 parts by weight of the curable resin composition of the present invention, the preferred lower limit of the content of the silane coupling agent is 0.1 parts by weight, and the preferred upper limit is 10 parts by weight. By making the content of the silane coupling agent within this range, the generation of liquid crystal contamination when the obtained curable resin composition is used as a sealant for liquid crystal display elements is suppressed, and the effect of improving adhesion becomes more excellent. The preferred lower limit of the content of the silane coupling agent is 0.3 parts by weight, and the preferred upper limit is 5 parts by weight.

The curable resin composition of the present invention may also contain a sunscreen. By containing the sunscreen, the curable resin composition of the present invention is suitable for use as a light-shielding sealant. The curable resin composition of the present invention contains the photopolymerization initiator of the present invention which has excellent reactivity to long-wavelength light, so even if it contains the sunscreen, the curability to long-wavelength light becomes excellent.

Examples of the above-mentioned light shielding agent include iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, resin-coated carbon black, etc. Among them, a substance with high insulation is preferred, and titanium black is more preferred.

The titanium black mentioned above will exert sufficient effect even if it is not surface treated, but titanium black that has been surface treated can also be used, for example: the surface is treated with organic components such as coupling agents; or the surface is coated with inorganic components such as silicon oxide, titanium oxide, germanium oxide, aluminum oxide, zirconium oxide, magnesium oxide, etc. Among them, in terms of being able to further improve the insulation, it is better to be treated with organic components. In addition, since the display element manufactured using the curable resin composition of the present invention containing the above-mentioned titanium black as a light-shielding agent has sufficient light-shielding properties, it can achieve a display element with no light leakage, high contrast, and excellent image display quality.

Examples of the titanium blacks available on the market include 12S, 13M, 13M-C, 13R-N, 14M-C (all manufactured by Mitsubishi Materials Corporation), Tilack D (manufactured by Ako Chemical Co., Ltd.), etc.

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

The preferred lower limit of the primary particle size of the above-mentioned sunscreen is 1 nm, and the preferred upper limit is 5000 nm. By making the primary particle size of the above-mentioned sunscreen within this range, the light-shielding property of the obtained curable resin composition can be made better without deteriorating the drawing property, etc. The preferred lower limit of the primary particle size of the above-mentioned sunscreen is 5 nm, and the preferred upper limit is 200 nm, and the further preferred lower limit is 10 nm, and the further preferred upper limit is 100 nm. Furthermore, the primary particle size of the above-mentioned sunscreen can be measured by dispersing the above-mentioned sunscreen in a solvent (water, organic solvent, etc.) using NICOMP 380ZLS (manufactured by PARTICLE SIZING SYSTEMS).

The preferred lower limit of the content of the above-mentioned light-shielding agent in 100 parts by weight of the curable resin composition of the present invention is 5 parts by weight, and the preferred upper limit is 80 parts by weight. By making the content of the above-mentioned light-shielding agent within this range, a more excellent light-shielding property can be exerted without reducing the adhesion of the obtained curable resin composition to the substrate or other adherends, the strength after curing, and the drawing property. The preferred lower limit of the content of the above-mentioned light-shielding agent is 10 parts by weight, and the preferred upper limit is 70 parts by weight, and the further preferred lower limit is 30 parts by weight, and the further preferred upper limit is 60 parts by weight.

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

As a method for producing the curable resin composition of the present invention, for example, there can be cited a method of mixing the curable resin, the photopolymerization initiator, and additives such as the silane coupling agent used as needed using a mixer. As the above-mentioned mixer, for example, there can be cited: a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, a three-roll grinder, etc.

The curable resin composition of the present invention is suitable for use in a display element composition, and is particularly suitable for use in a sealant for a liquid crystal display element. The display element composition and the liquid crystal display element sealant formed using the curable resin composition of the present invention are also one of the present inventions.

By mixing conductive microparticles into the sealant for liquid crystal display elements of the present invention, a vertical conductive material can be produced. The vertical conductive material containing the sealant for liquid crystal display elements of the present invention and conductive microparticles is also one of the present invention.

As the conductive particles, metal spheres, resin particles with a conductive metal layer formed on the surface, etc. can be used. Among them, resin particles with a conductive metal layer formed on the surface are preferred because they can achieve conductive connection due to the excellent elasticity of the resin particles without damaging the transparent substrate.

A liquid crystal display element made by using the sealant for liquid crystal display element of the present invention or the top-bottom conductive material of the present invention is also one of the present invention.

The sealant for liquid crystal display elements of the present invention is suitable for the manufacture of liquid crystal display elements using a liquid crystal dripping process. As a method for manufacturing the liquid crystal display element of the present invention by a liquid crystal dripping process, for example, the following methods can be listed. First, a step of applying the sealant for liquid crystal display elements of the present invention to a substrate to form a frame-shaped sealing pattern is implemented. Then, a step of applying droplets of liquid crystal to the entire surface of the frame of the sealing pattern in an uncured state of the sealant for liquid crystal display elements of the present invention and immediately overlapping with another substrate is implemented. Thereafter, a step of irradiating the sealing pattern portion with light to photocure the sealant is implemented, and a liquid crystal display element can be obtained by the above method. By making the irradiated light a long-wavelength light such as visible light, the damage caused by light irradiation to the peripheral components can be alleviated, and the sealant can be sufficiently photocured even when the sealant is arranged in the light-shielding portion. In addition to the step of photocuring the sealant, the step of heating the sealant to cure it can also be implemented. [Effects of the invention]

According to the present invention, a 9-oxysulfur having excellent responsiveness to long-wavelength light can be provided. Compound. According to the present invention, a method comprising: A photopolymerization initiator composed of a compound, a curable resin composition containing the photopolymerization initiator and having excellent storage stability and light-shielding curability, a display element composition formed using the curable resin composition, and a liquid crystal display element sealant with excellent low liquid crystal contamination property formed using the curable resin composition. Furthermore, according to the present invention, a top-bottom conductive material and a liquid crystal display element formed using the liquid crystal display element sealant can be provided.

The following disclosed embodiments further illustrate the present invention in detail, but the present invention is not limited to these embodiments.

(Preparation of Compound A) To 5.0 parts by weight of 2,5-thiophenedicarboxylic acid in 100 mL of dehydrated tetrahydrofuran was added 2-hydroxy 9-oxosulfur 20.0 parts by weight of 1,2-dimethylformamide and 0.1 parts by weight of p-toluenesulfonic acid were added, and refluxed for 12 hours. The product was then extracted with ethyl acetate. The ethyl acetate layer was washed with a saturated sodium bicarbonate aqueous solution and brine, and then dried with anhydrous magnesium sulfate to obtain 1.2 parts by weight of compound A (light yellow solid) as the photopolymerization initiator of the present invention. By ¹ H-NMR, GPC, and FT-IR analysis, it was confirmed that the obtained compound A was a compound represented by the following formula (4).

(Preparation of Compound B) Add 9-oxosulfur 5.0 parts by weight of 2,5-thiophenedicarbonyl chloride 2.7 parts by weight and aluminum chloride 3.7 parts by weight were added, and stirred overnight at room temperature. Then, the reaction mixture was poured into ice water, and the product was extracted with ethyl acetate. The ethyl acetate layer was washed with a saturated sodium bicarbonate aqueous solution and brine, and then dried with anhydrous magnesium sulfate to obtain 4.3 parts by weight of compound B (light yellow solid) as the photopolymerization initiator of the present invention. By ¹ H-NMR, GPC, and FT-IR analysis, it was confirmed that the obtained compound B was a compound represented by the following formula (5).

(Preparation of Compound C) Using 2,4-diethyl-9-sulfuryl Replace 9-oxosulfur In addition, the same method as in the above-mentioned "(Preparation of Compound B)" was used to obtain Compound C, which is a photopolymerization initiator of the present invention. By ¹ H-NMR, GPC, and FT-IR analysis, it was confirmed that the obtained Compound C was a compound represented by the following formula (6).

(Preparation of Compound D) Using 2-nitro-9-oxosulfur Replace 9-oxosulfur In addition, the same method as in the above-mentioned "(Preparation of Compound B)" was used to obtain Compound D, which is a photopolymerization initiator of the present invention. By ¹ H-NMR, GPC, and FT-IR analysis, it was confirmed that the obtained Compound D is a compound represented by the following formula (7).

(Preparation of Compound E) Add 9-oxosulfur 5.0 parts by weight of 2-trifluoromethanesulfonate, 0.1 parts by weight of PdCl ₂ (dppf), 1.0 parts by weight of K ₂ PO ₄ , and 2.7 parts by weight of 2-dithiophene-5-boric acid were added, and refluxed for 3 hours. Then, the product was extracted with ethyl acetate. The ethyl acetate layer was washed with a saturated sodium bicarbonate aqueous solution and brine, and then dried with anhydrous magnesium sulfate to obtain 1.9 parts by weight of compound E (light yellow solid) as the photopolymerization initiator of the present invention. By ¹ H-NMR, GPC, and FT-IR analysis, it was confirmed that the obtained compound E was a compound represented by the following formula (8).

(Preparation of Compound F) Compound F, which is a photopolymerization initiator of the present invention, was obtained in the same manner as in the above "(Preparation of Compound B)" except that 2,5-furandicarbonyl chloride was used instead of 2,5-thiophenedicarbonyl chloride. The obtained compound F was confirmed to be a compound represented by the following formula (9) by ¹ H-NMR, GPC, and FT-IR analysis.

(Examples 1 to 15, Comparative Examples 1 to 4) According to the blending ratios listed in Tables 1 to 3, the materials were mixed using a planetary mixer (manufactured by Thinky, "Defoaming Mixer Taro") and then mixed using a three-roll mill to prepare the curable resin compositions of Examples 1 to 15 and Comparative Examples 1 to 4.

<Evaluation> The following evaluation was performed on the curable resin compositions obtained in the Examples and Comparative Examples. The results are shown in Tables 1 to 3.

(Storage stability) For each hardening resin composition obtained in the embodiment and the comparative example, the initial viscosity immediately after production and the viscosity after storage for 24 hours in an environment of 25°C and 50%RH after production were measured. The viscosity increase ratio was set as (viscosity after storage)/(initial viscosity), and the viscosity increase ratio of less than 1.05 was evaluated as "◎", the viscosity increase ratio of 1.05 or more and less than 1.10 was evaluated as "○", the viscosity increase ratio of 1.10 or more and less than 1.15 was evaluated as "△", and the viscosity increase ratio of 1.15 or more was evaluated as "×", and the storage stability was evaluated in this way. Furthermore, the viscosity of the curable resin composition was measured using an E-type viscometer (manufactured by Brookfield, "DV-III") at 25°C and a rotation speed of 1.0 rpm.

(Photocuring) 1 part by weight of spacer microparticles ("Micropearl SI-H050" manufactured by Sekisui Chemical Industry Co., Ltd.) was dispersed in 100 parts by weight of each curable resin composition obtained in the Examples and Comparative Examples. Next, the curable resin composition was filled in a dispensing syringe ("PSY-10E" manufactured by Musashi Engineering Co., Ltd.), defoamed, and then applied to a glass substrate using a dispensing machine ("SHOTMASTER300" manufactured by Musashi Engineering Co., Ltd.). A glass substrate of the same size was bonded to the substrate using a vacuum bonding device under a reduced pressure of 5 Pa. The curable resin composition portion of the bonded glass substrate was irradiated with light of 100 mW/ ^cm2 for 10 seconds using a metal halogen lamp. Light irradiation was performed through a cutoff filter for light with a cutoff wavelength of 400 nm or less (400 nm cutoff filter). FT-IR measurement of the curable resin composition was performed using an infrared spectrometer (manufactured by BIORAD, "FTS3000") to measure the change in the peak derived from the (meth)acryloyl group before and after light irradiation. The light curing property was evaluated by evaluating the case where the peak derived from the (meth)acryloyl group decreased by 95% or more after light irradiation, "◎", the case where the decrease was 85% or more but less than 95% was evaluated as "○", the case where the decrease was 80% or more but less than 85% was evaluated as "△", and the case where the decrease in the peak derived from the (meth)acryloyl group after light irradiation was less than 80% was evaluated as "×".

(Low liquid crystal contamination) 1 part by weight of spacer particles ("Micropearl SI-H050" manufactured by Sekisui Chemical Industry Co., Ltd.) was dispersed in 100 parts by weight of each curable resin composition obtained in the embodiment and the comparative example. Then, the curable resin composition dispersed with the spacer particles was applied to the substrate with the rubbed alignment film and the transparent electrode in a line width of 1 mm using a dispenser. Then, droplets of liquid crystal ("JC-5004LA" manufactured by Chisso Corporation) were dropped and applied to the entire surface of the curable resin composition on the substrate with the transparent electrode, and the color filter substrate with the transparent electrode was immediately attached. Then, the curable resin composition was partially irradiated with 100 mW/ ^cm2 light for 30 seconds using a metal halogen lamp to cure it, and then heated at 120°C for 1 hour to obtain a liquid crystal display element. The light irradiation was performed through a cutoff filter (400 nm cutoff filter) that cuts off light with a wavelength below 400 nm. Two types of liquid crystal display elements were produced: one was a liquid crystal display element in which the curable resin composition was completely irradiated with light by controlling the coating position of the curable resin composition using a glue dispenser (without a light-shielding portion); the other was a liquid crystal display element in which the curable resin composition was coated on the black matrix of the color filter substrate in a manner that covered 50% of the line width (with a light-shielding portion). FIG. 1 is a schematic cross-sectional view of a liquid crystal display element produced by using each of the curable resin compositions obtained in the embodiment and the comparative example in a state without a light shielding portion, and FIG. 2 is a schematic cross-sectional view of a liquid crystal display element produced by using each of the curable resin compositions obtained in the embodiment and the comparative example in a state with a light shielding portion. As shown in FIG. 1, the state without a light shielding portion on the curable resin composition 1 is a state where the curable resin composition 1 is completely irradiated with light, while on the other hand, the state with a light shielding portion on the curable resin composition 1 is as shown in FIG. 2, where light is shielded by the black matrix 2 and the portion of the curable resin composition 1 in contact with the liquid crystal 3 is hardly irradiated. The obtained liquid crystal display elements were visually checked for disordered liquid crystal alignment (uneven display) after a 100-hour operation test and a 1000-hour voltage application at 80°C. The liquid crystal display element was rated as "◎" when no uneven display was found, "○" when a little uneven display was found near the curable resin composition of the liquid crystal display element (peripheral part), "△" when obvious uneven display was found in the peripheral part, and "×" when not only obvious uneven display was found in the peripheral part but also spread to the central part, thereby evaluating low liquid crystal contamination. Furthermore, liquid crystal display components rated as "◎" and "○" are of a level that has no practical problems, liquid crystal display components rated as "△" are of a level that may cause problems depending on the display design, and liquid crystal display components rated as "×" are of a level that cannot be actually used.

[Table 1] Embodiment 1 2 3 4 5 Composition (parts by weight) Hardening resin Bisphenol A epoxy acrylate (manufactured by DAICEL-ALLNEX, "EBECRYL 3700") 50 50 50 50 50 Partially acrylic modified bisphenol F type epoxy compound (manufactured by DAICEL-ALLNEX, "KRM8287") 40 40 40 40 40 Bisphenol A epoxy resin (manufactured by DIC Corporation, "EPICLON EXA-850CRP") 10 10 10 10 10 Photopolymerization initiator Photopolymerization initiator of the present invention Compound A 2 1 0.5 0.1 1 Compound B - - - - - Compound C - - - - - Compound D - - - - - Compound E - - - - - Compound F - - - - - other Polybutylene glycol bis(9-oxo-9H-sulfur Oxyacetic acid) ester (manufactured by iGM, "Omnipol TX") - - - - - Sensitizer Ethyl 4-(dimethylamino)benzoate (manufactured by iGM, "Omnirad EDB") 1 1 1 1 - Heat hardener Sebacate dihydrazide (manufactured by Otsuka Chemical Co., Ltd., "SDH") 5 5 5 5 5 Filler Silicon dioxide (Admafine SO-C2, manufactured by Admatechs) 35 35 35 35 35 Silane coupling agent 3-Glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-403") 1 1 1 1 1 Reviews Preserve stability ○ ○ ○ ◎ ○ Light curing ◎ ◎ ◎ ○ ○ Low liquid crystal contamination No shading part ◎ ◎ ◎ ◎ ◎ With shading part ○ ○ ○ ◎ ○

[Table 2] Embodiment 6 7 8 9 10 11 12 13 14 15 Composition (parts by weight) Hardening resin Bisphenol A epoxy acrylate (manufactured by DAICEL-ALLNEX, "EBECRYL 3700") 50 50 50 50 50 50 50 50 50 50 Partially acrylic modified bisphenol F type epoxy compound (manufactured by DAICEL-ALLNEX, "KRM8287") 40 40 40 40 40 40 40 40 40 40 Bisphenol A epoxy resin (manufactured by DIC Corporation, "EPICLON EXA-850CRP") 10 10 10 10 10 10 10 10 10 10 Photopolymerization initiator Photopolymerization initiator of the present invention Compound A - - - - - - - - - - Compound B 1 0.1 - - - - - - - - Compound C - - 1 0.1 - - - - - - Compound D - - - - 1 0.1 - - - - Compound E - - - - - - 1 0.1 - - Compound F - - - - - - - - 0.1 0.5 other Polybutylene glycol bis(9-oxo-9H-sulfur Oxyacetic acid) ester (manufactured by iGM, "Omnipol TX") - - - - - - - - - - Sensitizer Ethyl 4-(dimethylamino)benzoate (manufactured by iGM, "Omnirad EDB") 1 1 1 1 1 1 1 1 1 1 Heat hardener Sebacate dihydrazide (manufactured by Otsuka Chemical Co., Ltd., "SDH") 5 5 5 5 5 5 5 5 5 5 Filler Silicon dioxide (Admafine SO-C2, manufactured by Admatechs) 35 35 35 35 35 35 35 35 35 35 Silane coupling agent 3-Glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-403") 1 1 1 1 1 1 1 1 1 1 Reviews Preserve stability ○ ◎ ○ ◎ ○ ◎ ○ ◎ ○ ◎ Light curing ◎ ○ ◎ ○ ◎ ○ ◎ ○ ◎ ○ Low liquid crystal contamination No shading part ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ With shading part ○ ◎ ○ ◎ ○ ◎ ○ ◎ ○ ◎

[Table 3] Comparative example 1 2 3 4 Composition (parts by weight) Hardening resin Bisphenol A epoxy acrylate (manufactured by DAICEL-ALLNEX, "EBECRYL 3700") 50 50 50 50 Partially acrylic modified bisphenol F type epoxy compound (manufactured by DAICEL-ALLNEX, "KRM8287") 40 40 40 40 Bisphenol A epoxy resin (manufactured by DIC Corporation, "EPICLON EXA-850CRP") 10 10 10 10 Photopolymerization initiator Photopolymerization initiator of the present invention Compound A - - - - Compound B - - - - Compound C - - - - Compound D - - - - Compound E - - - - Compound F - - - - other Polybutylene glycol bis(9-oxo-9H-sulfur Oxyacetic acid) ester (manufactured by iGM, "Omnipol TX") 2 1 - - 2,4-Diethyl sulfide -9-Keto (manufactured by FUJIFILM Wako Pure Chemical Co., Ltd., "DETX") - - 2 1 Sensitizer Ethyl 4-(dimethylamino)benzoate (manufactured by iGM, "Omnirad EDB") 1 1 1 1 Heat hardener Sebacate dihydrazide (manufactured by Otsuka Chemical Co., Ltd., "SDH") 5 5 5 5 Filler Silicon dioxide (Admafine SO-C2, manufactured by Admatechs) 35 35 35 35 Silane coupling agent 3-Glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-403") 1 1 1 1 Reviews Preserve stability × ○ × ○ Light curing ○ × ○ × Low liquid crystal contamination No shading part △ ○ △ ○ With shading part × △ × △

[Industrial Applicability] According to the present invention, a 9-oxysulfur compound having excellent responsiveness to long-wavelength light can be provided. Compound. According to the present invention, a method comprising: A photopolymerization initiator composed of a compound, a curable resin composition containing the photopolymerization initiator and having excellent storage stability and light-shielding curability, a display element composition formed using the curable resin composition, and a liquid crystal display element sealant with excellent low liquid crystal contamination property formed using the curable resin composition. Furthermore, according to the present invention, a top-bottom conductive material and a liquid crystal display element formed using the liquid crystal display element sealant can be provided.

1: Curable resin composition 2: Black matrix 3: Liquid crystal

[Figure 1] is a schematic cross-sectional view of a liquid crystal display element produced by using each curable resin composition obtained in the embodiment and the comparative example without a light shielding portion. [Figure 2] is a schematic cross-sectional view of a liquid crystal display element produced by using each curable resin composition obtained in the embodiment and the comparative example with a light shielding portion.

Claims (9)

A 9-oxysulfur

A compound represented by the following formula (1):

In formula (1), X represents a structure represented by the following formula (2-1), (2-2) or (2-3), ^R1 independently represents a hydrogen atom, a methyl group, an ethyl group or a nitro group, and ^R2 independently represents a hydrogen atom, a methyl group, an ethyl group or a nitro group;

In formula (2-1), (2-2) and (2-3), R ³ represents a structure represented by the following formula (3-1), (3-2), (3-3), (3-4), (3-5), (3-6), (3-7) or (3-8), and * represents a bonding position;

In formulas (3-1) to (3-8), * represents a bonding position; in formulas (3-1) to (3-8), hydrogen atoms other than the hydrogen atoms contained in the OH groups of formulas (3-2) and (3-3) may be substituted. As requested in item 1, 9-oxysulfur

The compound, wherein the above R ³ is a structure represented by the above formula (3-1). If the 9-oxysulfur

The compound, wherein at least one R ¹ in the above formula (1) is a methyl group or an ethyl group, and at least one R ² in the above formula (1) is a methyl group or an ethyl group. A photopolymerization initiator, which is composed of 9-oxysulfide of claim 1, 2 or 3

Compound composition. A curable resin composition, which contains a curable resin and the photopolymerization initiator of claim 4. A display element composition, which is made using the hardening resin composition of claim 5. A sealant for a liquid crystal display element, which is made using the curable resin composition of claim 5. A vertical conductive material, which contains the sealant for liquid crystal display elements of claim 7 and conductive microparticles. A liquid crystal display element is formed by using the sealant for liquid crystal display element of claim 7 or the upper and lower conductive material of claim 8.