TW202140464A - Curable resin composition, sealing agent for display elements, sealing agent for liquid crystal display elements, vertically conductive material, display element, adhesive for electronic components, and electronic component - Google Patents

Abstract

A purpose of the present invention is to provide a curable resin composition which exhibits excellent visible light curability and adhesiveness, while having excellently low liquid crystal contamination possibility if used in a sealing agent for liquid crystal display elements. Another purpose of the present invention is to provide: a sealing agent for display elements, a sealing agent for liquid crystal display elements, and a vertically conductive material, each of which contains this curable resin composition; and a display element which comprises a cured product of this sealing agent for display elements, a cured product of this sealing agent for liquid crystal display elements or a cured product of this vertically conductive material. Another purpose of the present invention is to provide: an adhesive for electronic components, said adhesive containing this curable resin composition; and an electronic component which is bonded by means of a cured product of this adhesive for electronic components. The present invention is a curable resin composition which contains a curable resin and a photopolymerization initiator, wherein the photopolymerization initiator contains a compound that is represented by formula (1). In formula (1), each R1 independently represents an alkyl group having from 1 to 20 carbon atoms, said alkyl group optionally having an ether bond or an amide bond, a cycloalkyl group, an aralkyl group, a heterocyclic group, or an aryl group which optionally has an ether bond or an amide bond; and the alkyl group having from 1 to 20 carbon atoms, the cycloalkyl group, the aralkyl group, the heterocyclic group and the aryl group may have a polar group. In formula (1), each R2 independently represents an alkyl group having from 1 to 20 carbon atoms, said alkyl group optionally having an ether bond or an amide bond, a cycloalkyl group, an aralkyl group, a heterocyclic group, or an aryl group which optionally has an ether bond or an amide bond; and the alkyl group having from 1 to 20 carbon atoms, the cycloalkyl group, the aralkyl group, the heterocyclic group and the aryl group may have a polar group. In formula (1), each R3 independently represents an alkyl group having from 1 to 20 carbon atoms, said alkyl group optionally having an ether bond or an amide bond, a cycloalkyl group, an aralkyl group, a heterocyclic group, or an aryl group which optionally has an ether bond or an amide bond; and the alkyl group having from 1 to 20 carbon atoms, the cycloalkyl group, the aralkyl group, the heterocyclic group and the aryl group may have a polar group. In formula (1), R4 represents a bonding hand, a structure having an arylene group or a structure having a heteroarylene group.

Description

Curable resin composition, sealant for display elements, sealant for liquid crystal display elements, vertical conduction materials, display elements, adhesives for electronic parts, and electronic parts

The present invention relates to a curable resin composition, and a sealing compound for a display element, a sealing compound for a liquid crystal display element, a vertical conduction material, a display element, an adhesive for electronic parts, and an electronic Components.

In recent years, liquid crystal display elements or organic EL display elements have been widely used as display elements with characteristics such as thinness, light weight, and low power consumption. In such display elements or other electronic devices, a curable resin composition is generally used for sealing of liquid crystals or light-emitting layers, bonding of various electronic parts, and the like. For example, in the manufacture of liquid crystal display elements, for the sake of shortening the pitch time and optimizing the amount of liquid crystal used, the liquid crystal dropping method called the dropping method is used. The method is as disclosed in Patent Document 1 and Patent Document 2. The curable resin composition is used as a sealant. In the dropping method, first, a frame-shaped sealing pattern is formed by dispensing glue on one of the two transparent substrates with electrodes. Secondly, when the sealant is not hardened, drop the tiny drops of liquid crystal into the entire frame of the transparent substrate, and immediately attach another transparent substrate to it, and irradiate the sealing part with light such as ultraviolet rays for temporary hardening. After that, heating is performed during the annealing of the liquid crystal to perform main curing, thereby fabricating a liquid crystal display element. If the substrates are bonded under reduced pressure, liquid crystal display elements can be manufactured with extremely high efficiency. At present, this dropping method has become the mainstream manufacturing method of liquid crystal display elements. Prior art literature Patent literature

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

[The problem to be solved by the invention]

Nowadays, various portable devices with LCD panels, such as mobile phones and portable game consoles, are becoming popular, and miniaturization of the devices has become the most pressing issue. As a method of miniaturization of the device, a narrow edge of the liquid crystal display can be exemplified, such as arranging the position of the sealing portion under the black matrix (hereinafter, also referred to as narrow edge design). However, in the narrow-edge design, since the sealant is arranged directly under the black matrix, when the dripping method is performed, there is a problem that the light irradiated when the sealant is hardened by light is blocked, and the light cannot reach the sealant. Insufficient hardening is caused by the inside. When the curing of the sealant is insufficient as described above, there is a problem that the uncured sealant component is eluted into the liquid crystal to cause liquid crystal contamination. In addition, as a method for photocuring the sealant, ultraviolet irradiation is usually performed. However, especially in the liquid crystal dropping method, since the sealant is cured after the liquid crystal is dropped, there is a problem of deterioration of the liquid crystal due to ultraviolet irradiation. Therefore, in order to prevent the deterioration of the liquid crystal caused by ultraviolet rays, a photopolymerization initiator having excellent reactivity to long-wavelength light is blended, and the sealant is cured by light irradiation through a cut-off filter or the like. In addition, when the sealant is irradiated with light, in order not to damage the display element, a photomask is usually covered on the element for exposure. However, in recent years, a sealant that can be cured by irradiating visible light with a small energy is required. Exposure is performed using a photomask.

On the other hand, in adhesives for electronic parts used in other electronic devices, when ultraviolet rays are irradiated to harden them, there is also a risk that the light will degrade other peripheral components. Therefore, it is being studied how to use long-wavelength light to make them harden. The electronic parts are cured with an adhesive.

The object of the present invention is to provide a curable resin composition which is excellent in visible light curability and adhesiveness, and also excellent in low liquid crystal contamination when used in a sealing compound for liquid crystal display elements. Furthermore, an object of the present invention is to provide a sealing compound for a display element, a sealing compound for a liquid crystal display element, and a vertical conduction material containing the curable resin composition, and a cured product having the sealing compound for a display element, and the liquid crystal display element A display element using a hardened material of a sealant or a hardened material of the upper and lower conductive materials. Furthermore, an object of the present invention is to provide an adhesive for electronic parts containing the curable resin composition, and an electronic part bonded by the cured product of the adhesive for electronic parts. [Technical means to solve the problem]

The curable resin composition of the present invention contains a curable resin and a photopolymerization initiator, and the photopolymerization initiator includes a compound represented by the following formula (1).

In formula (1), R ^{1 is} each independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aralkyl group, a heterocyclic group, which may have an ether bond or an amide bond, or may have an ether bond or an amide bond The aryl group of the bond, the alkyl group with 1-20 carbon atoms, the cycloalkyl group, the aralkyl group, the heterocyclic group and the aryl group may also have a polar group. In formula (1), R ^{2 is} each independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aralkyl group, a heterocyclic group which may have an ether bond or an amide bond, or may have an ether bond or an amide bond The aryl group of the bond, the alkyl group with 1-20 carbon atoms, the cycloalkyl group, the aralkyl group, the heterocyclic group and the aryl group may also have a polar group. In formula (1), R ^{3 is} each independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aralkyl group, a heterocyclic group which may have an ether bond or an amide bond, or may have an ether bond or an amide bond The aryl group of the bond, the alkyl group with 1-20 carbon atoms, the cycloalkyl group, the aralkyl group, the heterocyclic group and the aryl group may also have a polar group. In formula (1), R ⁴ is a bonding bond, a structure having an aryl group, or a structure having a heteroarylene group. The present invention will be described in detail below.

The curable resin composition used as a sealant for liquid crystal display elements is blended with a photopolymerization initiator that has excellent reactivity to long-wavelength light, and is photocured by light in the visible light region with a wavelength exceeding 420 nm In this case, there is a problem that the liquid crystal may be contaminated by the sealant. In addition, when a photopolymerization initiator with excellent reactivity to long-wavelength light is blended with an adhesive for electronic parts, it is sometimes impossible to perform photo-curing by light in the visible light region with a wavelength exceeding 420 nm. Fully obtain the problem of adherence. Therefore, the present inventors studied the use of a compound having a specific structure as a photopolymerization initiator blended in a curable resin composition. As a result, it was found that a curable resin composition which is excellent in visible light curability and adhesiveness, and also excellent in low liquid crystal contamination when used in a sealant for liquid crystal display elements, was obtained, and the present invention was completed.

The curable resin composition of the present invention contains a photopolymerization initiator. The said photopolymerization initiator contains the compound represented by the said formula (1). By using the compound represented by the above formula (1) as the photopolymerization initiator, the curable resin composition of the present invention is excellent in visible light curability and adhesiveness, and when used as a sealant for liquid crystal display elements Low liquid crystal contamination is also excellent.

In the above formula (1), R ^{1 is} each independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aralkyl group, a heterocyclic group, which may have an ether bond or an amide bond, or may have an ether bond or an amide bond. The aryl group of the amine bond, the alkyl group with 1 to 20 carbon atoms, the cycloalkyl group, the aralkyl group, the heterocyclic group and the aryl group may also have a polar group. When R ¹ is an alkyl group having 1 to 20 carbon atoms, the alkyl group is preferably a methyl group or an ethyl group. In the case where R ¹ is a cycloalkyl group, examples of the cycloalkyl group include cyclohexyl and cyclobutyl. When R ¹ is an aralkyl group, examples of the aralkyl group include phenylmethyl, 2-naphthylmethyl, and the like. In the case where R ¹ is a heterocyclic group, examples of the heterocyclic group include 2-benzofuranyl and the like. When R ¹ is an aryl group, the aryl group may, for example, be a phenyl group, a 1-naphthyl group, and the like. Among them, phenyl is preferred. As said polar group, a hydroxyl group, a carboxyl group, an amino group, etc. are mentioned, for example. Among them, when the curable resin composition of the present invention is used for bonding of electronic parts, etc., there are more cationic components in the surrounding environment. Therefore, from the viewpoint that the cationic components can be supplemented, a carboxyl group is preferred.

In the above formula (1), R ^{2 is} each independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aralkyl group, a heterocyclic group which may have an ether bond or an amide bond, or may have an ether bond or an amide bond. The aryl group of the amine bond, the alkyl group with 1 to 20 carbon atoms, the cycloalkyl group, the aralkyl group, the heterocyclic group and the aryl group may also have a polar group. When R ² is an alkyl group, examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, and 2-ethylhexyl. Among them, methyl, ethyl, propyl, butyl, and pentyl are preferred. In the case where R ² is a cycloalkyl group, the cycloalkyl group may, for example, be a cyclopentyl group or a cyclohexyl group. The above-mentioned cycloalkyl group may have an alkyl group. When the above-mentioned R ² is an aralkyl group, the aralkyl group may, for example, be phenylmethyl. When R ² is a heterocyclic group, the heterocyclic group may, for example, be 2-benzothienyl. When the above-mentioned R ² is an aryl group, the aryl group may, for example, be a phenyl group. As said polar group, a hydroxyl group, a carboxyl group, an amino group, etc. are mentioned, for example. Among them, when the curable resin composition of the present invention is used for bonding of electronic parts, etc., there are more cationic components in the surrounding environment. Therefore, from the viewpoint that the cationic components can be supplemented, a carboxyl group is preferred. In the case where R ² is an alkyl group having a polar group, examples of the alkyl group having a polar group include carboxymethyl, 2-carboxyethyl, and the like. In the case where R ² is a cycloalkyl group having a polar group, examples of the cycloalkyl group having a polar group include 2-carboxycyclohexyl, 2-carboxy-4-methylcyclohexyl, and the like.

In the above formula (1), R ^{3 is} each independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aralkyl group, a heterocyclic group which may have an ether bond or an amide bond, or may have an ether bond or an amide bond. The aryl group of the amine bond, the alkyl group with 1 to 20 carbon atoms, the cycloalkyl group, the aralkyl group, the heterocyclic group and the aryl group may also have a polar group. When R ³ is an alkyl group, examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, 2-ethylhexyl, and the like. Among them, methyl, ethyl, propyl, butyl, and pentyl are preferred. The above-mentioned alkyl group may have an aryl group. In the case where R ³ is a cycloalkyl group, the cycloalkyl group may, for example, be a cyclohexyl group. In the case where R ³ is an aralkyl group, the aralkyl group may, for example, be 2-naphthylmethyl. In the case where R ³ is a heterocyclic group, the heterocyclic group may, for example, be 2-thienyl. When the above-mentioned R ³ is an aryl group, the aryl group may, for example, be a phenyl group. As said polar group, a hydroxyl group, a carboxyl group, an amino group, etc. are mentioned, for example. Among them, when the curable resin composition of the present invention is used for bonding of electronic parts, etc., there are more cationic components in the surrounding environment. Therefore, from the viewpoint that the cationic components can be supplemented, a carboxyl group is preferred. In the case where R ³ is an alkyl group having a polar group, examples of the alkyl group having a polar group include: 1-carboxyethyl, 2-carboxyethyl, 1-carboxypropyl, 3-carboxy Propyl, 1-carboxypentyl, carboxy(phenyl)methyl, etc.

In the above formula (1), R ⁴ is a bonding bond, a structure having an aryl extension, or a structure having a heteroaryl extension. In the case where R ⁴ has a structure having an arylene group, as the arylene group, for example, 1,3-phenylene group, 1,4-phenylene group, 1,4-naphthylene group, etc. . Specific examples of the structure having an aryl group include the structures represented by the following formulas (2-1) to (2-5). In the case where R ⁴ has a structure having a heteroaryl group, the heteroaryl group may, for example, be a thienylene, furanylene, pyridylene, and the like. Among them, a thienyl group is preferred. Specific examples of the structure having the above-mentioned heteroaryl group include the structures represented by the following formulas (3-1) to (3-6).

In formulas (2-1) to (2-5), * represents the bonding position.

In formulas (3-1) to (3-6), * represents the bonding position.

As the compound represented by the above formula (1), since it is more excellent in the reactivity to visible light and low liquid crystal contamination, it is preferably the compound represented by the following formula (4) to (9), in the above formula (1) At least one of R ² and R ³ is a compound represented by the following formula (10), more preferably a compound represented by the following formula (4), R ² and R ^{3 in the above formula (1)} At least one of them is a compound of the group represented by the following formula (10).

In formula (10), R ⁵ is an alkylene, cycloalkylene, aralkylene, heterocyclic group having 1 to 20 carbon atoms which may have an ether bond or an amide bond, or may have an ether bond or an amide bond The aryl extension of the bond, * indicates the bonding position.

The compound in which ^{at least one of R 2} and R ^{3 in} the above formula (1) is a group represented by the above formula (10) is preferably a compound represented by the following formula (11).

With respect to 100 parts by weight of the curable resin, the lower limit of the content of the compound represented by the above formula (1) is preferably 0.01 parts by weight, and the upper limit is preferably 5 parts by weight. When the content of the compound represented by the above formula (1) is 0.01 parts by weight or more, the curable resin composition obtained is more excellent in visible light curability. When the content of the compound represented by the above formula (1) is 5 parts by weight or less, when the obtained curable resin composition is used in a sealing compound for liquid crystal display elements, the low liquid crystal contamination is more excellent. The lower limit of the content of the compound represented by the above formula (1) is more preferably 0.1 parts by weight, and the upper limit is more preferably 2 parts by weight.

The curable resin composition of the present invention contains a curable resin. The curable resin preferably contains a (meth)acrylic compound. As said (meth)acrylic compound, (meth)acrylate compound, epoxy (meth)acrylate, urethane (meth)acrylate (urethane (meth)acrylate) etc. are mentioned, for example. Among them, epoxy (meth)acrylate is preferred. In addition, from the viewpoint of reactivity, the (meth)acrylic compound preferably has two or more (meth)acrylic groups in one molecule. Furthermore, in this specification, the above-mentioned "(meth)acrylic acid" means acrylic acid or methacrylic acid, the above-mentioned "(meth)acrylic compound" means a compound having a (meth)acryloyl group, and the above-mentioned "(former "(Base) acryl" means acryl or methacryl. In addition, the above-mentioned "(meth)acrylate" means acrylate or methacrylate. Furthermore, the above-mentioned "epoxy (meth)acrylate" means a compound obtained by reacting all epoxy groups in an epoxy compound with (meth)acrylic acid.

As the monofunctional one of the above-mentioned (meth)acrylate compounds, for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and normal (meth)acrylate may be mentioned. Butyl ester, isobutyl (meth)acrylate, tertiary butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate Esters, isononyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, isomyristyl (meth)acrylate, stearyl (meth)acrylate, (meth) ) 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, cyclohexyl (meth)acrylate, Isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxy (meth)acrylate Ethyl, 2-butoxyethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, methoxyethylene glycol (meth)acrylate, methoxypolyethylene glycol ( Meth) acrylate, phenoxy diethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, ethyl carbitol ( (Meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, (meth)acrylate 1H, 1H, 5H -Octafluoropentyl ester, imine (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, 2-(methyl) succinate Acrylic oxyethyl ester, hexahydrophthalic acid 2-(meth) acryloxy ethyl ester, phthalic acid 2-(meth) acryloxy ethyl 2-hydroxypropyl ester, phosphoric acid 2 -(Meth)acryloxyethyl, glycidyl (meth)acrylate, etc.

In addition, examples of the bifunctional one among the above-mentioned (meth)acrylate compounds include 1,3-butanediol di(meth)acrylate and 1,4-butanediol di(meth)acrylic acid Esters, 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 addition bisphenol A di(meth)acrylate, propylene oxide addition bisphenol A di(meth)acrylate, ethylene oxide addition double Phenol F di(meth)acrylate, dimethylol dicyclopentadiene di(meth)acrylate, ethylene oxide modified isocyanuric acid di(meth)acrylate, (meth)acrylic acid 2-hydroxy-3-(meth)acryloxy propyl ester, carbonate diol di(meth)acrylate, polyether diol di(meth)acrylate, polyester diol di(meth) Acrylate, polycaprolactonediol di(meth)acrylate, polybutadienediol di(meth)acrylate, etc.

In addition, examples of the above-mentioned (meth)acrylate compounds having three or more functionalities include trimethylolpropane tri(meth)acrylate, ethylene oxide addition trimethylolpropane tri(meth) Base) acrylate, propylene oxide addition trimethylolpropane tri(meth)acrylate, caprolactone modified trimethylolpropane tri(meth)acrylate, ethylene oxide addition heterotrimerization Cyanate tri(meth)acrylate, glycerol tri(meth)acrylate, propylene oxide addition glycerol tri(meth)acrylate, neopentylerythritol tri(meth)acrylate, phosphoric acid tri(meth) ) Acrylic oxyethyl, di-trimethylolpropane tetra (meth) acrylate, neopentyl erythritol tetra (meth) acrylate, dineo pentaerythritol penta (meth) acrylate, two new Pentyleneerythritol hexa(meth)acrylate and the like.

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

As the epoxy compound used as a raw material for synthesizing the above-mentioned epoxy (meth)acrylate, for example, bisphenol A type epoxy compound, bisphenol F type epoxy compound, bisphenol S type epoxy compound, 2,2'-diallyl bisphenol A type epoxy compound, hydrogenated bisphenol type epoxy compound, propylene oxide addition bisphenol A type epoxy compound, resorcinol type epoxy compound, biphenyl type Epoxy compounds, thioether epoxy compounds, diphenyl ether epoxy compounds, dicyclopentadiene epoxy compounds, naphthalene epoxy compounds, phenol novolac epoxy compounds, o-cresol novolac epoxy compounds Compound, dicyclopentadiene novolak type epoxy compound, biphenol novolak type epoxy compound, naphthol novolak type epoxy compound, glycidamine type epoxy compound, alkyl polyol type epoxy compound, rubber modification Qualitative epoxy compounds, glycidyl ester compounds, etc.

Examples of commercially available bisphenol A epoxy compounds include jER 828EL, jER 1004 (all manufactured by Mitsubishi Chemical Corporation), EPICLON EXA-850CRP (manufactured by DIC Corporation), and the like. Examples of commercially available bisphenol F epoxy compounds include jER 806, jER 4004 (all manufactured by Mitsubishi Chemical Corporation), and the like. As a commercially available one among the above-mentioned bisphenol S-type epoxy compounds, for example, EPICLON EXA1514 (manufactured by DIC Corporation), etc. may be mentioned. As a commercially available one among the above-mentioned 2,2'-diallyl bisphenol A epoxy compounds, for example, RE-810NM (manufactured by Nippon Kayaku Co., Ltd.) can be mentioned. As a commercial item among the said hydrogenated bisphenol type epoxy compound, EPICLON EXA7015 (made by DIC Corporation) etc. are mentioned, for example. As a commercially available one among the above-mentioned propylene oxide-added bisphenol A epoxy compounds, for example, EP-4000S (manufactured by ADEKA Corporation), etc. may be mentioned. As a commercially available one among the above-mentioned resorcinol-type epoxy compounds, for example, EX-201 (manufactured by Nagase chemteX) and the like can be mentioned. As a commercially available one among the above-mentioned biphenyl type epoxy compounds, for example, jER YX-4000H (manufactured by Mitsubishi Chemical Corporation), etc. may be mentioned. As a commercially available one among the above-mentioned sulfide-type epoxy compounds, for example, YSLV-50TE (manufactured by Nippon Steel Chemical Materials Co., Ltd.) can be mentioned. As a commercially available one among the above-mentioned diphenyl ether type epoxy compounds, for example, YSLV-80DE (manufactured by Nippon Steel Chemical Materials Co., Ltd.) can be mentioned. As a commercially available one among the above-mentioned dicyclopentadiene-type epoxy compounds, for example, EP-4088S (manufactured by ADEKA Corporation) and the like can be mentioned. As a commercially available one among the above-mentioned naphthalene-type epoxy compounds, for example, EPICLON HP4032, EPICLON EXA-4700 (all manufactured by DIC Corporation), etc. can be mentioned. As a commercial item among the said phenol novolak type epoxy compound, EPICLON N-770 (made by DIC Corporation) etc. are mentioned, for example. As a commercially available one among the o-cresol novolak-type epoxy compounds mentioned above, for example, EPICLON N-670-EXP-S (manufactured by DIC Corporation) etc. can be mentioned. As a commercially available one among the above-mentioned dicyclopentadiene novolak type epoxy compounds, for example, EPICLON HP7200 (manufactured by DIC Corporation), etc. may be mentioned. As a commercially available one among the above-mentioned biphenol novolac type epoxy compounds, for example, NC-3000P (manufactured by Nippon Kayaku Co., Ltd.) can be mentioned. As a commercially available one among the above-mentioned naphthol novolak type epoxy compounds, for example, ESN-165S (manufactured by Nippon Steel Chemical Materials Co., Ltd.) and the like can be mentioned. Examples of commercially available glycidamine-type epoxy compounds include jER 630 (manufactured by Mitsubishi Chemical Corporation), EPICLON 430 (manufactured by DIC Corporation), TETRAD-X (manufactured by Mitsubishi Gas Chemical Corporation), and the like. As commercially available among the above-mentioned alkyl polyol type epoxy compounds, for example, ZX-1542 (manufactured by Nippon Steel Chemical Materials Co., Ltd.), EPICLON 726 (manufactured by DIC Co., Ltd.), Epolight 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.) ), Denacol EX-611 (manufactured by Nagase chemteX), etc. As a commercially available one among the above-mentioned rubber-modified epoxy compounds, for example, YR-450, YR-207 (all manufactured by Nippon Steel Chemical Materials Co., Ltd.); Epolead PB (manufactured by Daicel), etc. may be mentioned. As a commercially available one among the aforementioned glycidyl ester compounds, for example, Denacol EX-147 (manufactured by Nagase chemteX) and the like can be mentioned. As other commercially available ones of the above epoxy compounds, for example, YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Nippon Steel Chemical Materials Co., Ltd.); XAC4151 (manufactured by Asahi Kasei Co., Ltd.); jER 1031, jER 1032 (all manufactured by Mitsubishi Chemical Corporation); EXA-7120 (manufactured by DIC Corporation); TEPIC (manufactured by Nissan Chemical Corporation), etc.

As the commercially available epoxy (meth)acrylates mentioned above, for example, epoxy (meth)acrylate manufactured by Daicel-Allnex Corporation, epoxy (meth)acrylate manufactured by Shin Nakamura Chemical Industry Co., Ltd. Ester, epoxy (meth)acrylate manufactured by Kyoeisha Chemical Co., Ltd., epoxy (meth)acrylate manufactured by Nagase chemteX, etc. As the epoxy (meth)acrylate manufactured by Daicel-Allnex, for example, EBECRYL 860, EBECRYL 3200, EBECRYL 3201, EBECRYL 3412, EBECRYL 3600, EBECRYL 3700, EBECRYL 3701, EBECRYL 3702, EBECRYL 3703, EBECRYL 3708, EBECRYL 3800, EBECRYL 6040, EBECRYL RDX63182, etc. As the epoxy (meth)acrylate manufactured by Shinnakamura Chemical Industry Co., Ltd., for example, EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, EMA-1020, etc. can be mentioned. Examples of the epoxy (meth)acrylate produced by the above-mentioned Kyoeisha Chemical Company 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. As the epoxy (meth)acrylate manufactured by the Nagase chemteX company, for example, Denacol Acrylate DA-141, Denacol Acrylate DA-314, Denacol Acrylate DA-911, etc. may be mentioned.

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

As the above-mentioned polyfunctional isocyanate compound, for example, isophorone diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate Isocyanate, diphenylmethane-4,4'-diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, toluidine diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, thiophosphate tris(isocyanatophenyl) ester, tetramethylxylylene diisocyanate, 1,6,11- Undecane triisocyanate and so on.

In addition, as the above-mentioned polyfunctional isocyanate compound, a chain-extended polyfunctional isocyanate compound obtained by reacting a polyol with an excess of a polyfunctional isocyanate compound can also be used. Examples of the above-mentioned polyol include ethylene glycol, propylene glycol, glycerin, sorbitol, trimethylolpropane, carbonate diol, polyether diol, polyester diol, polycaprolactone diol, and the like.

Examples of the (meth)acrylic acid derivative having a hydroxyl group include: hydroxyalkyl mono(meth)acrylate, mono(meth)acrylate of dihydric alcohol, and mono(meth)acrylate of trihydric alcohol. Acrylate or di(meth)acrylate, epoxy (meth)acrylate, etc. Examples of the above-mentioned hydroxyalkyl mono(meth)acrylate include: 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate , 4-hydroxybutyl (meth)acrylate, etc. As said diol, ethylene glycol, 1, 2- propanediol, 1, 3- propanediol, 1, 3- butanediol, 1, 4- butanediol, polyethylene glycol, etc. are mentioned, for example. As said triol, trimethylolethane, trimethylolpropane, glycerol, etc. are mentioned, for example. As said epoxy (meth)acrylate, bisphenol A type epoxy acrylate etc. are mentioned, for example.

Examples of commercially available amine ester (meth)acrylates among the above-mentioned amine ester (meth)acrylates include, for example, amine ester (meth)acrylate manufactured by Toagosei Co., Ltd., amine ester (meth)acrylate manufactured by Daicel-Allnex, Urethane (meth)acrylate manufactured by Negami Industry Co., Ltd., Urethane (meth)acrylate manufactured by Shinnakamura Chemical Industry Co., Ltd., and Urethane (meth)acrylate manufactured by Kyoeisha Chemical Co., Ltd., etc. As the amine ester (meth)acrylate manufactured by the Toagosei Corporation, for example, M-1100, M-1200, M-1210, M-1600, etc. may be mentioned. Examples of the amine ester (meth)acrylate manufactured by Daicel-Allnex include: EBECRYL 210, EBECRYL 220, EBECRYL 230, EBECRYL 270, EBECRYL 1290, EBECRYL 2220, EBECRYL 4827, EBECRYL 4842, EBECRYL 4858, EBECRYL 5129, EBECRYL 6700, EBECRYL 8402, EBECRYL 8803, EBECRYL 8804, EBECRYL 8807, EBECRYL 9260, etc. As the amine ester (meth)acrylate manufactured by the above-mentioned Nekami Kogyo Co., Ltd., for example, Artresin UN-330, Artresin SH-500B, Artresin UN-1200TPK, Artresin UN-1255, Artresin UN-3320HB, Artresin UN-7100 may be mentioned. , Artresin UN-9000A, Artresin UN-9000H, etc. Examples of the urethane (meth)acrylate manufactured by Shinnakamura Chemical Industry Co., Ltd. include: U-2HA, U-2PHA, U-3HA, U-4HA, U-6H, U-6HA, U-6LPA , U-10H, U-15HA, U-108, U-108A, U-122A, U-122P, U-324A, U-340A, U-340P, U-1084A, U-2061BA, UA-340P, UA -4000, UA-4100, UA-4200, UA-4400, UA-5201P, UA-7100, UA-7200, UA-W2A, etc. Examples of the urethane (meth)acrylate produced by the above-mentioned Kyoeisha Chemical Company include: AH-600, AI-600, AT-600, UA-101I, UA-101T, UA-306H, UA-306I , UA-306T, etc.

For example, in order to improve the adhesiveness of the curable resin composition obtained, the curable resin may contain an epoxy compound. As said epoxy compound, the epoxy compound used as a raw material for synthesizing the said epoxy (meth)acrylate, or a partial (meth)acrylic-modified epoxy compound etc. are mentioned, for example. Furthermore, in this specification, the above-mentioned partial (meth)acrylic modified epoxy compound means a compound having one or more epoxy groups and one or more (meth)acryloyl groups in one molecule, and the above-mentioned compound For example, it can be obtained by reacting a part of epoxy groups of an epoxy compound having two or more epoxy groups in one molecule with (meth)acrylic acid.

When the above-mentioned (meth)acrylic compound and the above-mentioned epoxy compound are contained as the above-mentioned curable resin, or when the above-mentioned partial (meth)acrylic modified epoxy compound is contained as the above-mentioned curable resin, the above-mentioned The ratio of the (meth)acryl group in the total of the (meth)acryl group and the epoxy group in the curable resin is 30 mol% or more and 95 mol% or less. By keeping the ratio of the above-mentioned (meth)acrylic groups within this range, when the curable resin composition obtained is used in a sealing compound for liquid crystal display elements, the occurrence of liquid crystal contamination is suppressed, and the adhesiveness is improved. Excellent.

From the viewpoint of making the obtained curable resin composition more excellent in low liquid crystal contamination when used in a sealing compound for liquid crystal display elements, the curable resin preferably has an -OH group or a -NH- group , -NH ₂ groups and other hydrogen bonding units.

The said curable resin may be used individually or in combination of 2 or more types.

The curable resin composition of the present invention may contain a sensitizer, but from the viewpoint of low liquid crystal staining properties when used in a sealing compound for liquid crystal display elements, it is preferable not to contain the sensitizer. Since the curable resin composition of the present invention contains the compound represented by the above formula (1) as a photopolymerization initiator, it has excellent visible light curability even if it does not contain a sensitizer.

硫

、2,2-二甲氧基-1,2-二苯基乙烷-1-酮、二苯甲酮、2,4-二氯二苯甲酮、鄰苯甲醯基苯甲酸甲酯、4,4'-雙(二甲基胺基)二苯甲酮、4-苯甲醯基-4'-甲基二苯硫醚等。As the above-mentioned sensitizer, for example, ethyl 4-(dimethylamino)benzoate, 9,10-dibutoxyanthracene, 2,4-diethyl-9-oxygen

sulfur

, 2,2-Dimethoxy-1,2-diphenylethane-1-one, benzophenone, 2,4-dichlorobenzophenone, methyl phthalate, 4,4'-bis(dimethylamino)benzophenone, 4-benzyl-4'-methyl diphenyl sulfide, etc.

When the sensitizer is contained, relative to 100 parts by weight of the curable resin, the lower limit of the content of the sensitizer is preferably 0.01 parts by weight, and the upper limit is preferably 3 parts by weight. When the content of the sensitizer is 0.01 parts by weight or more, the sensitization effect can be further exhibited. When the content of the above-mentioned sensitizer is 3 parts by weight or less, light can be transmitted to the deep part without excessive absorption. The lower limit of the content of the sensitizer is more preferably 0.1 part by weight, and the upper limit is more preferably 1 part by weight.

The curable resin composition of the present invention may contain a thermal polymerization initiator within a range that does not hinder the purpose of the present invention. As the said thermal polymerization initiator, what consists of an azo compound, an organic peroxide, etc. can be mentioned, for example. Among them, a polymer azo initiator composed of a polymer azo compound is preferred. The above-mentioned thermal polymerization initiators may be used alone or in combination of two or more kinds. Furthermore, in this specification, the above-mentioned "polymeric azo compound" means a radical having an azo group, which is generated by heat to harden a (meth)acryloyloxy radical, and having a number average molecular weight of 300 or more Compound.

The lower limit of the number average molecular weight of the polymer azo compound is preferably 1,000, and the upper limit is preferably 300,000. When the number average molecular weight of the polymer azo compound is within this range, it can be easily mixed with the curable resin. In particular, when the obtained curable resin composition is used in a sealing compound for liquid crystal display elements, liquid crystal contamination can be suppressed, and it is easy to mix with the curable resin. The lower limit of the number average molecular weight of the polymer azo compound is more preferably 5,000, the upper limit is more preferably 100,000, the lower limit is more preferably 10,000, and the upper limit is more preferably 90,000.

Examples of the above-mentioned polymer azo compound include those having a structure in which a plurality of units such as polyalkylene oxide or polydimethylsiloxane are bonded via an azo group. The polymer azo compound having a structure in which a plurality of units such as polyalkylene oxide are bonded via an azo group is preferably one having a polyethylene oxide structure. As the above-mentioned polymer azo compound, specifically, for example, a condensation polymer of 4,4'-azobis(4-cyanovaleric acid) and polyalkylene glycol, or 4,4'- Condensation polymer of azobis(4-cyanovaleric acid) and polydimethylsiloxane having an amine group at the end, etc. Examples of commercially available high-molecular azo compounds include: VPE-0201, VPE-0401, VPE-0601, VPS-0501, VPS-1001 (all manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and the like. In addition, examples of azo compounds that are not polymers include V-65, V-501 (all manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and the like.

As said organic peroxide, for example, ketone peroxide, peroxyketal, hydrogen peroxide, dialkyl peroxide, peroxyester, diacetyl peroxide, peroxydicarbonate, etc. may be mentioned.

With respect to 100 parts by weight of the curable resin, the lower limit of the content of the thermal polymerization initiator is preferably 0.05 parts by weight, and the upper limit is preferably 10 parts by weight. When the content of the thermal polymerization initiator is 0.05 parts by weight or more, the curable resin composition of the present invention is more excellent in thermal curability. When the content of the thermal polymerization initiator is 10 parts by weight or less, the curable resin composition of the present invention is more excellent in storage stability, and when it is used in a sealing compound for liquid crystal display elements, low liquid crystal contamination is also more excellent . The lower limit of the content of the thermal polymerization initiator is more preferably 0.1 parts by weight, and the upper limit is more preferably 5 parts by weight.

The curable resin composition of the present invention may also contain a thermosetting agent. As said thermosetting agent, organic acid hydrazine, imidazole derivative, amine compound, polyphenol type compound, acid anhydride etc. are mentioned, for example. Among them, the organic acid hydrazine is suitably used. The above-mentioned thermosetting agents may be used alone or in combination of two or more kinds.

As said organic acid hydrazine, dihydrazine sebacate, dihydrazine isophthalate, dihydrazine adipate, dihydrazine malonate, etc. are mentioned, for example. As a commercially available one of the above-mentioned organic acid hydrazine, for example, organic acid hydrazine manufactured by Otsuka Chemical Co., Ltd., organic acid hydrazine manufactured by Ajinomoto Fine-Techno, etc. can be mentioned. Examples of the organic acid hydrazine manufactured by Otsuka Chemical Co., Ltd. include SDH, ADH, and the like. Examples of the organic acid hydrazine manufactured by Ajinomoto Fine-Techno include Amicure VDH, Amicure VDH-J, Amicure UDH, and Amicure UDH-J.

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 the content of the thermosetting agent is within this range, the coating properties of the curable resin composition obtained are not deteriorated, and the thermosetting properties can be made more excellent. The upper limit of the content of the thermal hardening agent is more preferably 30 parts by weight.

For example, in order to increase the viscosity, improve the adhesion due to the stress dispersion effect, and improve the linear expansion rate, the curable resin composition of the present invention preferably contains a filler.

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

With respect to 100 parts by weight of the curable resin, the lower limit of the filler content is preferably 30 parts by weight, and the upper limit is preferably 80 parts by weight. When the content of the filler is within this range, it is possible to achieve more excellent effects such as improvement in adhesiveness without deteriorating coating properties and the like. The lower limit of the filler content is more preferably 45 parts by weight, and the upper limit is more preferably 65 parts by weight.

The curable resin composition of the present invention preferably contains a silane coupling agent. The above-mentioned silane coupling agent mainly has a function as an adhesive auxiliary agent for bonding the curable resin composition to a substrate or the like well.

As the above-mentioned silane coupling agent, for example, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-isocyanate are suitably used. Propyl trimethoxysilane and so on. These excellent effects of improving adhesion to substrates, etc., when the obtained curable resin composition is used in a sealant for liquid crystal display elements, by chemically bonding with the curable resin, the curable resin can be prevented from flowing out To the liquid crystal. The above-mentioned silane coupling agent may be used alone or in combination of two or more kinds.

In 100 parts by weight of the curable resin composition of the present invention, the lower limit of the content of the silane coupling agent is preferably 0.1 parts by weight, and the upper limit is preferably 10 parts by weight. When the content of the silane coupling agent is within this range, the adhesiveness of the curable resin composition obtained is more excellent. In particular, when the obtained curable resin composition is used in a sealing compound for liquid crystal display elements, the occurrence of liquid crystal contamination is suppressed, and the adhesiveness is more excellent. The lower limit of the content of the silane coupling agent is more preferably 0.3 parts by weight, and the upper limit is more preferably 5 parts by weight.

The curable resin composition of the present invention may further contain additives such as a reactive diluent, a thixotropic agent, a spacer, a hardening accelerator, a defoamer, a leveling agent, and a polymerization inhibitor if necessary.

As a method of manufacturing the curable resin composition of the present invention, for example, a mixing machine such as a homogeneous disperser, a homomixer, a universal mixer, a planetary mixer, a kneader, or a three-roll mill is used to combine the curable resin , Method of mixing photopolymerization initiator, optionally added silane coupling agent, etc.

The curable resin composition of the present invention is suitably used as a sealing compound for display elements, and more suitably used as a sealing compound for liquid crystal display elements. Moreover, the sealing compound for display elements containing the curable resin composition of this invention, and the sealing compound for liquid crystal display elements containing the curable resin composition of this invention are also one of this invention, respectively.

The vertical conductive material can be manufactured by blending conductive fine particles with the curable resin composition of the present invention. In addition, an upper and lower conduction material containing the curable resin composition of the present invention and conductive fine particles is also one of the present invention.

As the conductive fine particles, metal balls, those having a conductive metal layer formed on the surface of the resin fine particles, or the like can be used. Among them, those with a conductive metal layer formed on the surface of the resin particles are preferred because of the excellent elasticity of the resin particles and can be electrically connected without damaging the transparent substrate or the like.

In addition, a display element having a cured product of the sealant for display elements of the present invention, a cured product of the sealant for liquid crystal display elements of the present invention, or a cured product of the top and bottom conduction material of the present invention is also one of the present invention. As the display element of the present invention, a liquid crystal display element obtained by using the sealant for a liquid crystal display element of the present invention is preferable, and a liquid crystal display element of a narrow-edge design is more preferable. Specifically, it is preferable that the width of the frame portion around the liquid crystal display portion is 2 mm or less. Moreover, when manufacturing a liquid crystal display element as the display element of this invention, the coating width of the sealing compound for liquid crystal display elements of this invention is preferably 1 mm or less.

As a method of manufacturing a liquid crystal display element as the display element of the present invention, a liquid crystal dropping method is suitably used. Specifically, for example, a method having the following steps can be exemplified. The liquid crystal display element can be obtained by the following method: first, the following steps are performed: the sealant for the liquid crystal display element of the present invention is coated on the electrode with ITO film and the like and the alignment film by screen printing, dispenser coating, etc. One of the two transparent substrates forms a frame-shaped sealing pattern. Next, the following steps are performed: in the uncured state of the sealant for liquid crystal display elements of the present invention, droplets of liquid crystal are applied to the frame of the sealing pattern of the substrate, and another transparent substrate is superimposed under vacuum. After that, the step of irradiating the sealing pattern part of the sealing compound for liquid crystal display elements of the present invention with light through a cut-off filter or the like is performed to light-harden the sealing compound. Furthermore, in addition to the above-mentioned step of photocuring the sealant, a step of heating the sealant to thermally harden it may also be performed.

The curable resin composition of the present invention is also suitable for bonding electronic parts. If the curable resin composition of the present invention is used as an adhesive for electronic parts, low-energy light can be used for photoirradiation during curing, and therefore, deterioration of other components can be suppressed. In addition, the adhesive for electronic parts containing the curable resin composition of the present invention and the electronic parts bonded by the cured product of the adhesive for electronic parts of the present invention are also one of the present invention. [Effects of the invention]

According to the present invention, it is possible to provide a curable resin composition which is excellent in visible light curability and adhesiveness, and also excellent in low liquid crystal contamination when used in a sealing compound for liquid crystal display elements. Furthermore, according to the present invention, it is possible to provide a sealing compound for a display element, a sealing compound for a liquid crystal display element, and a vertical conduction material containing the curable resin composition, and a cured product having the sealing compound for a display element, and the liquid crystal display element A display element using a hardened material of a sealant or a hardened material of the upper and lower conductive materials. Furthermore, according to the present invention, it is possible to provide an adhesive for electronic parts containing the curable resin composition, and an electronic part bonded by the cured product of the adhesive for electronic parts.

Examples are disclosed below to illustrate the present invention in more detail, but the present invention is not limited to these examples.

(Synthesis of the compound represented by formula (4)) 5 parts by weight of N-ethylcarbazole, 2.81 parts by weight of 2,5-thiophene dicarboxylic acid dichloride, and 3.76 parts by weight of aluminum chloride are added to dichloromethane 40 In mL, stir overnight at room temperature. 2.21 parts by weight of acetyl chloride and 3.76 parts by weight of aluminum chloride were added to the obtained reaction liquid, and the mixture was further stirred at room temperature for 4 hours. After pouring the obtained reaction liquid into ice water, the organic layer was extracted with ethyl acetate. After washing the extracted solution with saturated sodium bicarbonate aqueous solution and brine, it is dried and concentrated using anhydrous magnesium sulfate to obtain the product (A1). Add 3 parts by weight of the obtained product (A1), 0.76 parts by weight of hydroxylammonium chloride, and 0.86 parts by weight of pyridine to 30 mL of ethanol, and stir under reflux for 10 hours. After pouring the obtained reaction liquid into ice water, it filtered. After washing the filtrate with water, it was dissolved in ethyl acetate, dried and concentrated using anhydrous magnesium sulfate to obtain the product (B1). 1.5 parts by weight of the obtained product (B1) was dissolved in 25 parts by weight of N,N-dimethylformamide, and then 0.59 parts by weight of acetyl chloride was added. While cooling the obtained solution to 10°C or lower, 0.78 parts by weight of triethylamine was dropped and stirred at room temperature for 4 hours. After pouring the obtained reaction liquid into water, it filtered. The filtered product was purified by silica gel column chromatography using a mixed solvent of dichloromethane and hexane (dichloromethane:hexane=2:1) to obtain the compound represented by the above formula (4). Furthermore, the obtained structure of the compound represented by the above formula (4) was ^{confirmed by 1} H-NMR, ¹³ C-NMR, and FT-IR.

(Synthesis of the compound represented by formula (9)) 5 parts by weight of N-(2-ethylhexyl)carbazole, 2.81 parts by weight of 2,5-thiophene dicarboxylic acid dichloride, and 3.76 parts by weight of aluminum chloride are added To 40 mL of dichloromethane, stir overnight at room temperature. 2.21 parts by weight of acetyl chloride and 3.76 parts by weight of aluminum chloride were added to the obtained reaction liquid, and the mixture was further stirred at room temperature for 4 hours. After pouring the obtained reaction liquid into ice water, the organic layer was extracted with ethyl acetate. After washing the extracted solution with saturated sodium bicarbonate aqueous solution and brine, it is dried and concentrated using anhydrous magnesium sulfate to obtain the product (A2). Add 3 parts by weight of the obtained product (A2), 0.76 parts by weight of hydroxylammonium chloride, and 0.86 parts by weight of pyridine to 30 mL of ethanol, and stir under reflux for 10 hours. After pouring the obtained reaction liquid into ice water, it filtered. After washing the filtrate with water, it was dissolved in ethyl acetate, dried and concentrated using anhydrous magnesium sulfate to obtain the product (B2). 1.5 parts by weight of the obtained product (B2) was dissolved in 25 parts by weight of N,N-dimethylformamide, and then 0.59 parts by weight of acetyl chloride was added. While cooling the obtained solution to 10°C or lower, 0.78 parts by weight of triethylamine was dropped and stirred at room temperature for 4 hours. After pouring the obtained reaction liquid into water, it filtered. The filtered product was purified by silica gel column chromatography using a mixed solvent of dichloromethane and hexane (dichloromethane:hexane=2:1) to obtain the compound represented by the above formula (9). Furthermore, the obtained structure of the compound represented by the above formula (9) was ^{confirmed by 1} H-NMR, ¹³ C-NMR, and FT-IR.

(Synthesis of the compound represented by formula (11)) 5 parts by weight of ethyl 3-(9H-carbazol-9-yl)propionate, 2.64 parts by weight of hexanyl chloride, and 2.62 parts by weight of aluminum chloride are added to the dichloride In 80 mL of methane, stir overnight at room temperature. 1.84 parts by weight of 2,5-thiophene dicarboxylic acid dichloride and 5.24 parts by weight of aluminum chloride were added to the obtained reaction liquid, and the mixture was further stirred at room temperature for 4 hours. After pouring the obtained reaction liquid into ice water, the organic layer was extracted with ethyl acetate. After washing the extracted solution with saturated sodium bicarbonate aqueous solution and brine, it is dried and concentrated using anhydrous sodium sulfate to obtain the product (A3). Add 2.77 parts by weight of 20% sodium hydroxide aqueous solution to 4.0 parts by weight of the product (A3) in 20 mL of ethanol, and reflux for 3 hours. After the reaction, 50 mL of water was added, which was made acidic with concentrated hydrochloric acid, and then extracted with ethyl acetate. The ethyl acetate layer was washed with water and brine, and then dried and concentrated with anhydrous sodium sulfate to obtain the product (B3). 3 parts by weight of the obtained product (B3), 0.58 parts by weight of hydroxylammonium chloride, and 0.65 parts by weight of pyridine were added to 30 mL of ethanol, and stirred under reflux for 10 hours. After pouring the obtained reaction liquid into ice water, it filtered. After washing the filtrate with water, it was dissolved in ethyl acetate, dried and concentrated using anhydrous sodium sulfate to obtain the product (C3). 1.5 parts by weight of the obtained product (C3) was dissolved in 20 parts by weight of N,N-dimethylformamide, and then 0.45 parts by weight of acetyl chloride was added. While cooling the obtained solution to 10°C or lower, 0.59 parts by weight of triethylamine was dropped and stirred at room temperature for 4 hours. After pouring the obtained reaction liquid into water, it filtered. The compound is isolated by silica gel column chromatography to obtain the compound represented by the above formula (11). Furthermore, the obtained structure of the compound represented by the above formula (11) was ^{confirmed by 1} H-NMR, ¹³ C-NMR, and FT-IR.

(Examples 1 to 11 and Comparative Examples 1 to 3) According to the blending ratio described in Table 1, the materials were mixed using a planetary mixer and then mixed using a three-roll mill to prepare the curable resin compositions of Examples 1 to 11 and Comparative Examples 1 to 3 . As the planetary mixer, defoaming mixer Taro (manufactured by Thinky) was used.

＜Evaluation＞ The following evaluations were performed on each curable resin composition obtained in the examples and comparative examples. The results are shown in Table 1.

(UV curability) 1 part by weight of spacer fine particles was dispersed in 100 parts by weight of each curable resin composition obtained in the examples and comparative examples. As the spacer particles, Micropearl SI-H050 (manufactured by Sekisui Chemical Co., Ltd.) was used. Next, the sealant is filled in a dispensing syringe, and after defoaming treatment, it is coated on the glass substrate by a dispensing machine. As a dispensing syringe, PSY-10E (manufactured by Takezo High-Tech Co., Ltd.) was used, and as a dispensing machine, SHOTMASTER300 (manufactured by Takezo High-Tech Co., Ltd.) was used. A glass substrate of the same size was bonded to the substrate coated with the sealant by a vacuum bonding device under a reduced pressure of 5 Pa. Use a metal halide lamp to irradiate the sealant part of the bonded glass substrate with 100 mW/cm ² light for 10 seconds. Light irradiation is performed through a cut-off filter (340 nm cut-off filter) of light with a cut-off wavelength of 340 m or less. The FT-IR measurement of the sealant was carried out using an infrared spectrometer, and the amount of change of the peak derived from the (meth)acrylic acid group before and after light irradiation was measured. As an infrared spectrometer, FTS3000 (manufactured by BIORAD) was used. If the peaks derived from the (meth)acrylic acid group are reduced by more than 95% after irradiated with light, set to "◎", and if the peaks are reduced by more than 90% and less than 95%, set to "○", which will reduce by more than 70% And the case of less than 90% is set as "△", the case where the peak derived from the (meth)acrylic acid group is reduced by less than 70% after light irradiation is set to "×", and the UV curability is evaluated.

(Visible light curability) Disperse 1 part by weight of spacer fine particles in 100 parts by weight of each curable resin composition obtained in the examples and comparative examples. As the spacer particles, Micropearl SI-H050 (manufactured by Sekisui Chemical Co., Ltd.) was used. Next, the sealant is filled in a dispensing syringe, and after defoaming treatment, it is coated on the glass substrate by a dispensing machine. As a dispensing syringe, PSY-10E (manufactured by Takezo High-Tech Co., Ltd.) was used, and as a dispensing machine, SHOTMASTER300 (manufactured by Takezo High-Tech Co., Ltd.) was used. A glass substrate of the same size was bonded to the substrate coated with the sealant by a vacuum bonding device under a reduced pressure of 5 Pa. Use a metal halide lamp to irradiate the sealant part of the bonded glass substrate with 100 mW/cm ² light for 10 seconds. Light irradiation is performed through a cut-off filter (420 nm cut-off filter) of light with a cut-off wavelength of 420 m or less. The FT-IR measurement of the sealant was carried out using an infrared spectrometer, and the amount of change of the peak derived from the (meth)acrylic acid group before and after light irradiation was measured. As an infrared spectrometer, FTS3000 (manufactured by BIORAD) was used. If the peaks derived from the (meth)acrylic acid group are reduced by more than 95% after irradiated with light, set to "◎", and if the peaks are reduced by more than 90% and less than 95%, set to "○", which will reduce by more than 70% And the case of less than 90% is set as "△", the case where the peak derived from the (meth)acrylic acid group is reduced by less than 70% after light irradiation is set to "×", and the UV curability is evaluated.

(Low liquid crystal contamination) Put 0.5 g of liquid crystal (manufactured by Chisso, "JC-5001LA") in a sample bottle, add 0.1 g of each curable resin composition obtained in the examples and comparative examples, and shake, then shake at 120 Heat at ℃ for 1 hour and return to room temperature (25℃). By drawing a square frame, each curable resin composition obtained in the Examples and Comparative Examples was applied to a glass substrate with a transparent electrode and an alignment film (manufactured by Nissan Chemical Co., "SE7492") by a dispenser. Alignment film. Then, drop the tiny drops of liquid crystal taken out from the sample bottle onto the entire frame on the substrate, and overlap another glass substrate in a vacuum. Release the vacuum and use a metal halide lamp to irradiate 100 mW/cm ² light for 10 seconds. Light irradiation is performed through a cut-off filter (420 nm cut-off filter) of light with a cut-off wavelength of 420 m or less. Thereafter, it was heated at 120°C for 1 hour to thermally harden the sealant to obtain a liquid crystal display element. For the obtained liquid crystal display element, an AC voltage of 1.5 V was applied on one side, and the occurrence of an afterimage was confirmed visually when a DC voltage of 1 V was applied on the other side. Set the case where the afterimage is not confirmed at all as "○", the case where the afterimage is slightly confirmed as "△", and the case where the severe afterimage is confirmed as "×", and evaluate the performance of the liquid crystal display element Display performance.

(Adhesiveness) Disperse 1 part by weight of spacer particles in 100 parts by weight of each curable resin composition obtained in Examples and Comparative Examples, and drop tiny drops onto 2 glass substrates with ITO film (30×40 mm) ). As the spacer particles, Micropearl SI-H050 (manufactured by Sekisui Chemical Co., Ltd.) was used. Another glass substrate with ITO film was bonded to it in a cross shape, and then irradiated with 100 mW/cm ² light by a metal halide lamp for 30 seconds, and then heated at 120°C for 60 minutes to obtain an adhesive test piece. For the obtained adhesive test piece, a tensile test (5 mm/sec) was performed with a chuck arranged up and down. Divide the obtained measurement value (kgf) by the seal coating cross-sectional area (cm ² ), and set the value obtained when the value is 1.5 kgf/cm ² or more as "○", and when the value is less than 1.5 kgf/cm ² Set to "×", and evaluate the adhesion.

氧基)乙酸酯 （polybutylene glycol bis(9-oxy-9H-thioxanthenyloxy)acetate，IGM Resins公司製造，「Omnipol TX」） - - - - - - - - - - - - - 1 熱硬化劑 癸二酸二醯肼 （大塚化學公司製造，「SDH」） 3 3 3 3 3 3 3 3 3 3 3 3 3 3 填充劑 二氧化矽 （Admatechs公司製造，「Admafine SO-C2」） 15 15 15 15 15 15 15 15 15 15 15 15 15 15 矽烷偶合劑 3-環氧丙氧基丙基三甲氧基矽烷 （信越化學工業公司製造，「KBM-403」） 1 1 1 1 1 1 1 1 1 1 1 1 1 1 評價 UV硬化性 ○ ○ ◎ ○ ○ ◎ ○ ○ ○ ◎ ○ ○ ○ ○ 可見光硬化性 ○ ◎ ○ ○ ◎ ○ ◎ ◎ ◎ ○ ◎ × △ ○ 低液晶污染性 ○ ○ ○ △ ○ △ ○ ○ ○ ○ ○ ○ × △ 接著性 ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ × [產業上之可利用性][Table 1] Example Comparative example 1 2 3 4 5 6 7 8 9 10 11 1 2 3 Composition (parts by weight) Hardening resin Bisphenol A epoxy acrylate (manufactured by Daicel-Allnex, "EBECRYL 3700") 35 35 35 35 35 35 35 35 35 35 35 35 35 35 Caprolactone modified bisphenol A epoxy acrylate (manufactured by Daicel-Allnex, "EBECRYL 3708") 5 5 5 5 5 5 5 5 5 5 5 5 5 5 Partial acrylic modified bisphenol F epoxy compound (manufactured by Daicel-Allnex, "KRM8287") 15 15 15 15 15 15 15 15 15 15 15 15 15 15 Bisphenol A Diglycidyl Ether (manufactured by DIC Corporation, "EPICLON EXA-850") 5 5 5 5 5 5 5 5 5 5 5 5 5 5 Photopolymerization initiator The compound represented by formula (4) 1 0.3 1.2 - - - - - - - - - - - The compound represented by formula (9) - - - 1 0.3 1.2 0.1 - - - - Compound represented by formula (11) - - - - - - - 1 0.3 1.2 0.1 - - - 2,2-Dimethoxy-1,2-diphenylethane-1-one (manufactured by IGM Resins, "Omnirad 651") - - - - - - - - - - - 1 - - 1-(4-(phenylthio)phenyl)-1,2-octanedione 2-(O-benzophenoxime) (manufactured by BASF Corporation, "IRGACURE OXE01") - - - - - - - - - - - - 1 - Poly(ethylene glycol) bis(p-dimethylaminobenzoate) (manufactured by IGM Resins, "Omnipol ASA") - - - - - - - - - - - - - 1 Polybutylene glycol bis(9-oxo-9H-sulfur

Oxy)acetate (polybutylene glycol bis(9-oxy-9H-thioxanthenyloxy)acetate, manufactured by IGM Resins, "Omnipol TX") - - - - - - - - - - - - - 1 Thermal hardener Dihydrazine sebacate (manufactured by Otsuka Chemical Co., Ltd., "SDH") 3 3 3 3 3 3 3 3 3 3 3 3 3 3 Filler Silicon dioxide (manufactured by Admatechs, "Admafine SO-C2") 15 15 15 15 15 15 15 15 15 15 15 15 15 15 Silane coupling agent 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-403") 1 1 1 1 1 1 1 1 1 1 1 1 1 1 Evaluation UV curability ○ ○ ◎ ○ ○ ◎ ○ ○ ○ ◎ ○ ○ ○ ○ Visible light hardening ○ ◎ ○ ○ ◎ ○ ◎ ◎ ◎ ○ ◎ X △ ○ Low liquid crystal contamination ○ ○ ○ △ ○ △ ○ ○ ○ ○ ○ ○ X △ Continuity ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ X [Industrial availability]

According to the present invention, it is possible to provide a curable resin composition which is excellent in visible light curability and adhesiveness, and also excellent in low liquid crystal contamination when used in a sealing compound for liquid crystal display elements. Furthermore, according to the present invention, it is possible to provide a sealing compound for a display element, a sealing compound for a liquid crystal display element, and a vertical conduction material containing the curable resin composition, and a cured product having the sealing compound for a display element, and the liquid crystal display element A display element using a hardened material of a sealant or a hardened material of the upper and lower conductive materials. Furthermore, according to the present invention, it is possible to provide an adhesive for electronic parts containing the curable resin composition, and an electronic part bonded by the cured product of the adhesive for electronic parts.

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Claims (10)

A curable resin composition containing a curable resin and a photopolymerization initiator, characterized in that: the photopolymerization initiator includes a compound represented by the following formula (1);

In formula (1), R ^{1 is} each independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aralkyl group, a heterocyclic group, which may have an ether bond or an amide bond, or may have an ether bond or an amide bond The aryl group of the bond, the alkyl group with 1 to 20 carbon atoms, the cycloalkyl group, the aralkyl group, the heterocyclic group and the aryl group may also have a polar group; in formula (1), R ^{2 is} each independently It is an alkyl group, cycloalkyl group, aralkyl group, heterocyclic group which may have an ether bond or an amide bond with carbon number of 1-20, or an aryl group which may have an ether bond or an amide bond, and the carbon number is 1-20 The alkyl group, the cycloalkyl group, the aralkyl group, the heterocyclic group and the aryl group may also have a polar group; in formula (1), R ^{3 is} each independently a carbon that may have an ether bond or an amide bond Alkyl group, cycloalkyl group, aralkyl group, heterocyclic group, or aryl group which may have an ether bond or amide bond with 1-20, the alkyl group with 1-20 carbons, the cycloalkyl group, the aryl group The alkyl group, the heterocyclic group and the aryl group may also have a polar group; in formula (1), R ⁴ is a bonding bond, a structure with an aryl group, or a structure with a heteroarylene group. The curable resin composition of claim 1, wherein the photopolymerization initiator includes a compound represented by the following formula (4);

. The curable resin composition of claim 1, wherein the photopolymerization initiator includes a compound represented by the following formula (11);

. The curable resin composition of 2 or 3, wherein the content of the compound represented by the above formula (1) is 0.01 part by weight or more and 5 parts by weight or less relative to 100 parts by weight of the curable resin. A sealant for display elements, which contains the curable resin composition of claim 1, 2, 3, or 4. A sealant for liquid crystal display elements, which contains the curable resin composition of claim 1, 2, 3, or 4. An up-and-down conductive material containing the curable resin composition of claim 1, 2, 3, or 4 and conductive fine particles. A display element having a cured product of the sealant for a display element of claim 5, a cured product of the sealant for a liquid crystal display element of claim 6, or a cured product of the upper and lower conductive materials of claim 7. An adhesive for electronic parts, which contains the curable resin composition of claim 1, 2, 3, or 4. An electronic component which is bonded by the hardened substance of the adhesive for electronic components of claim 9.