KR20220149651A - Curable resin composition, sealing compound for display elements, sealing compound for liquid crystal display elements, vertical conduction material, display element, adhesive for electronic components, and electronic component - Google Patents

Abstract

식 (1) 중, R¹ 은, 각각 독립적으로, 에테르 결합 혹은 아미드 결합을 갖고 있어도 되는 탄소수 1 ∼ 20 의 알킬기, 시클로알킬기, 아르알킬기, 복소 고리기, 또는, 에테르 결합 혹은 아미드 결합을 갖고 있어도 되는 아릴기이고, 그 탄소수 1 ∼ 20 의 알킬기, 그 시클로알킬기, 그 아르알킬기, 그 복소 고리기, 및, 그 아릴기는, 극성기를 갖고 있어도 된다. 식 (1) 중, R² 는, 각각 독립적으로, 에테르 결합 혹은 아미드 결합을 갖고 있어도 되는 탄소수 1 ∼ 20 의 알킬기, 시클로알킬기, 아르알킬기, 복소 고리기, 또는, 에테르 결합 혹은 아미드 결합을 갖고 있어도 되는 아릴기이고, 그 탄소수 1 ∼ 20 의 알킬기, 그 시클로알킬기, 그 아르알킬기, 그 복소 고리기, 및, 그 아릴기는, 극성기를 갖고 있어도 된다. 식 (1) 중, R³ 은, 각각 독립적으로, 에테르 결합 혹은 아미드 결합을 갖고 있어도 되는 탄소수 1 ∼ 20 의 알킬기, 시클로알킬기, 아르알킬기, 복소 고리기, 또는, 에테르 결합 혹은 아미드 결합을 갖고 있어도 되는 아릴기이고, 그 탄소수 1 ∼ 20 의 알킬기, 그 시클로알킬기, 그 아르알킬기, 그 복소 고리기, 및, 그 아릴기는, 극성기를 갖고 있어도 된다. 식 (1) 중, R⁴ 는, 결합손, 아릴렌기를 갖는 구조, 또는, 헤테로아릴렌기를 갖는 구조이다.It is excellent in visible light sclerosis|hardenability and adhesiveness, and, when it uses for the sealing compound for liquid crystal display elements, an object of this invention is to provide the curable resin composition excellent also in low-liquid-crystal contamination property. Moreover, this invention contains the sealing compound for display elements containing this curable resin composition, the sealing compound for liquid crystal display elements, and the up-and-down conduction material, and the hardened|cured material of this sealing compound for display elements, and this seal|sticker for liquid crystal display elements It aims at providing the display element which has the hardened|cured material of this, or the hardened|cured material of the vertical conduction material. Moreover, an object of this invention is to provide the adhesive agent for electronic components containing this curable resin composition, and the electronic component adhere|attached by the hardened|cured material of this adhesive agent for electronic components.
This invention is curable resin composition containing curable resin and a photoinitiator, The said photoinitiator is curable resin composition containing the compound represented by following formula (1).

In formula (1), R ¹ is each independently an alkyl group having 1 to 20 carbon atoms which may have an ether bond or an amide bond, a cycloalkyl group, an aralkyl group, a heterocyclic group, or an ether bond or an amide bond. It is an aryl group used, and the alkyl group having 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), R ² is each independently an alkyl group having 1 to 20 carbon atoms which may have an ether bond or an amide bond, a cycloalkyl group, an aralkyl group, a heterocyclic group, or an ether bond or an amide bond. It is an aryl group used, and the alkyl group having 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), R ³ is each independently an alkyl group having 1 to 20 carbon atoms which may have an ether bond or an amide bond, a cycloalkyl group, an aralkyl group, a heterocyclic group, or an ether bond or an amide bond. It is an aryl group used, and the alkyl group having 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), R< ⁴ > is a structure which has a bond, a structure which has an arylene group, or a heteroarylene group.

Description

Curable resin composition, sealing compound for display elements, sealing compound for liquid crystal display elements, vertical conduction material, display element, adhesive for electronic components, and electronic component

This invention relates to curable resin composition, and the sealing compound for display elements which use this curable resin composition, the sealing compound for liquid crystal display elements, a vertical conduction material, a display element, the adhesive agent for electronic components, and an electronic component.

In recent years, a liquid crystal display element, an organic electroluminescent display element, etc. are widely used as a display element which has characteristics, such as thin shape, light weight, and low power consumption. In such a display element and another electronic device, curable resin composition is normally used for sealing of a liquid crystal and a light emitting layer, adhesion|attachment of various electronic components, etc.

For example, in manufacture of a liquid crystal display element, the liquid crystal called the dripping method using the curable resin composition currently disclosed by patent document 1 and patent document 2 as a sealing agent from viewpoints of shortening of a tact time, optimization of the amount of liquid crystal used, etc. The drop method is used.

In the dripping construction method, first, a frame-like seal pattern is formed by dispensing in one of the transparent substrates with an electrode of 2 sheets. Next, in the state in which a sealing compound is not hardened, the microdroplet of a liquid crystal is dripped at the whole surface in the frame of a transparent substrate, the other transparent substrate is bonded together immediately, and light, such as an ultraviolet-ray, is irradiated to a sealing part, and temporary hardening is performed. Then, main hardening is performed by heating at the time of liquid crystal annealing, and a liquid crystal display element is produced. When bonding of a board|substrate is performed under reduced pressure, a liquid crystal display element can be manufactured with very high efficiency, and this dripping construction method becomes the mainstream of the manufacturing method of a liquid crystal display element now.

Japanese Patent Laid-Open No. 2001-133794 International Publication No. 02/092718

In the present age in which various types of mobile devices with liquid crystal panels, such as mobile phones and portable game machines, are prevalent, miniaturization of devices is the most demanded subject. As a method of reducing the size of the device, a frame narrowing of the liquid crystal display unit is exemplified, for example, arranging the position of the seal unit under a black matrix (hereinafter also referred to as frame narrow design).

However, in a narrow frame design, since the sealing compound is arrange|positioned just below the black matrix, when the dripping method is performed, the light irradiated when photocuring the sealing compound is blocked, and the light does not reach the inside of the sealing compound, and hardening is insufficient. There was a problem with it being done. Thus, when hardening of a sealing compound became inadequate, the non-hardened sealing compound component eluted in a liquid crystal, and there existed a problem that a liquid-crystal contamination generate|occur|produced.

Moreover, although irradiation of an ultraviolet-ray is normally performed as a method of photocuring a sealing compound, especially in the liquid crystal dropping method, in order to harden a sealing compound after dripping a liquid crystal, there was a problem that a liquid crystal deteriorated by irradiating an ultraviolet-ray. . Then, in order to prevent deterioration of the liquid crystal by an ultraviolet-ray, the photoinitiator excellent in the reactivity with respect to long-wavelength light is mix|blended, and hardening of a sealing compound by light irradiation through a cut filter etc. is performed. Moreover, when irradiating light to a sealing compound, in order not to damage a display element, exposure is normally performed by covering an element with a mask, In recent years, so that exposure can be performed without a mask, by irradiating visible light with low energy, The sealing compound which can be hardened is calculated|required.

On the other hand, also in adhesives for electronic components used in other electronic devices, when curing by irradiating ultraviolet rays, there is a risk of causing deterioration due to light in other surrounding members. Hardening has been considered.

It is excellent in visible light sclerosis|hardenability and adhesiveness, and, when it uses for the sealing compound for liquid crystal display elements, an object of this invention is to provide the curable resin composition excellent also in low liquid-crystal contamination property. Moreover, this invention contains the sealing compound for display elements containing this curable resin composition, the sealing compound for liquid crystal display elements, and the up-and-down conduction material, and the hardened|cured material of this sealing compound for display elements, and this seal|sticker for liquid crystal display elements It aims at providing the display element which has the hardened|cured material of this, or the hardened|cured material of the vertical conduction material. Moreover, an object of this invention is to provide the adhesive agent for electronic components containing this curable resin composition, and the electronic component adhere|attached by the hardened|cured material of this adhesive agent for electronic components.

This invention is curable resin composition containing curable resin and a photoinitiator, The said photoinitiator is curable resin composition containing the compound represented by following formula (1).

[Formula 1]

In formula (1), R ¹ is each independently an alkyl group having 1 to 20 carbon atoms which may have an ether bond or an amide bond, a cycloalkyl group, an aralkyl group, a heterocyclic group, or an ether bond or an amide bond. It is an aryl group used, and the alkyl group having 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), R ² is each independently an alkyl group having 1 to 20 carbon atoms which may have an ether bond or an amide bond, a cycloalkyl group, an aralkyl group, a heterocyclic group, or an ether bond or an amide bond. It is an aryl group used, and the alkyl group having 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), R ³ is each independently an alkyl group having 1 to 20 carbon atoms which may have an ether bond or an amide bond, a cycloalkyl group, an aralkyl group, a heterocyclic group, or an ether bond or an amide bond. It is an aryl group used, and the alkyl group having 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), R ⁴ is a structure having a bond, an arylene group, or a heteroarylene group.

Hereinafter, the present invention will be described in detail.

When a photoinitiator excellent in reactivity with respect to long-wavelength light is mix|blended with curable resin composition used as a sealing compound for liquid crystal display elements, and photocured by the light of the visible region exceeding wavelength 420nm, liquid crystal with a sealing compound There was a problem that this may be contaminated. In addition, when a photopolymerization initiator excellent in reactivity to long-wavelength light is blended with an adhesive for electronic components and photocured by light in the visible light region exceeding a wavelength of 420 nm, sufficient adhesion may not be obtained. there was

Then, this inventor examined using the compound which has a specific structure as a photoinitiator mix|blended with curable resin composition. As a result, it was excellent in visible light sclerosis|hardenability and adhesiveness, and when it used for the sealing compound for liquid crystal display elements, it discovered that the curable resin composition excellent also in low liquid-crystal contamination property could be obtained, and came to complete this invention.

Curable resin composition of this invention contains a photoinitiator.

The said photoinitiator contains the compound represented by the said Formula (1). By using the compound represented by the said Formula (1) as said photoinitiator, curable resin composition of this invention is excellent in visible light sclerosis|hardenability and adhesiveness, and when it uses for the sealing compound for liquid crystal display elements, low-liquid-crystal contamination Saints will be excellent.

In the formula (1), R ¹ each independently represents an alkyl group having 1 to 20 carbon atoms which may have an ether bond or an amide bond, a cycloalkyl group, an aralkyl group, a heterocyclic group, or an ether bond or an amide bond It is an aryl group which may be present, and the alkyl group having 1 to 20 carbon atoms, the cycloalkyl group, the aralkyl group, the heterocyclic group, and the aryl group may have a polar group.

When said R< ¹ > is a C1-C20 alkyl group, a methyl group and an ethyl group are preferable as this alkyl group.

When said R< ¹ > is a cycloalkyl group, as the cycloalkyl group, a cyclohexyl group, a cyclobutyl group, etc. are mentioned, for example.

When said R< ¹ > is an aralkyl group, as the aralkyl group, a phenylmethyl group, 2-naphthylmethyl group, etc. are mentioned, for example.

When said R< ¹ > is a heterocyclic group, as this heterocyclic group, a 2-benzofuranyl group etc. are mentioned, for example.

When said R< ¹ > is an aryl group, as the aryl group, a phenyl group, 1-naphthyl group, etc. are mentioned, for example. Especially, a phenyl group is preferable.

As said polar group, a hydroxyl group, a carboxyl group, an amino group, etc. are mentioned, for example. Especially, when using the curable resin composition of this invention for adhesion|attachment of an electronic component, etc., a carboxyl group is preferable from a point which a cation component increases in a surrounding environment, and a viewpoint that the replenishment of the cation component is possible.

In the formula (1), R ² each independently represents an alkyl group having 1 to 20 carbon atoms which may have an ether bond or an amide bond, a cycloalkyl group, an aralkyl group, a heterocyclic group, or an ether bond or an amide bond, It is an aryl group which may be present, and the alkyl group having 1 to 20 carbon atoms, the cycloalkyl group, the aralkyl group, the heterocyclic group, and the aryl group may have a polar group.

When said R< ² > is an alkyl group, as the alkyl group, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, 2-ethylhexyl group, etc. are mentioned, for example. Especially, a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group are preferable.

When said R< ² > is a cycloalkyl group, a cyclopentyl group, a cyclohexyl group, etc. are mentioned as this cycloalkyl group. The cycloalkyl group may have an alkyl group.

When said R< ² > is an aralkyl group, as the aralkyl group, a phenylmethyl group etc. are mentioned, for example.

When said R< ² > is a heterocyclic group, as this heterocyclic group, a 2-benzothiophenyl group etc. are mentioned, for example.

When said R< ² > is an aryl group, a phenyl group etc. are mentioned as the aryl group.

As said polar group, a hydroxyl group, a carboxyl group, an amino group, etc. are mentioned, for example. Especially, when using the curable resin composition of this invention for adhesion|attachment of an electronic component, etc., a carboxyl group is preferable from a point which a cation component increases in a surrounding environment, and a viewpoint that the replenishment of the cation component is possible.

When said R< ² > is an alkyl group which has a polar group, as an alkyl group which has the polar group, a carboxymethyl group, 2-carboxyethyl group, etc. are mentioned, for example.

When said R< ² > is a cycloalkyl group which has a polar group, as a cycloalkyl group which has the polar group, a 2-carboxycyclohexyl group, 2-carboxy-4-methylcyclohexyl group, etc. are mentioned, for example.

In said formula (1), R< ³ > has each independently a C1-C20 alkyl group which may have an ether bond or an amide bond, a cycloalkyl group, an aralkyl group, a heterocyclic group, or an ether bond or an amide bond, It is an aryl group which may be present, and the alkyl group having 1 to 20 carbon atoms, the cycloalkyl group, the aralkyl group, the heterocyclic group, and the aryl group may have a polar group.

When said R ³ is an alkyl group, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a 2-ethylhexyl group. Especially, a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group are preferable. The said alkyl group may have an aryl group.

When said R< ³ > is a cycloalkyl group, a cyclohexyl group etc. are mentioned as this cycloalkyl group.

When said R ³ is an aralkyl group, examples of the aralkyl group include a 2-naphthylmethyl group.

When said R ³ is a heterocyclic group, examples of the heterocyclic group include a 2-thienyl group.

When said R< ³ > is an aryl group, a phenyl group etc. are mentioned as the aryl group. As said polar group, a hydroxyl group, a carboxyl group, an amino group, etc. are mentioned, for example. Especially, when using the curable resin composition of this invention for adhesion|attachment of an electronic component, etc., a carboxyl group is preferable from a point which a cation component increases in a surrounding environment, and a viewpoint that the replenishment of the cation component is possible.

When R ³ is an alkyl group having a polar group, examples of the alkyl group having a polar group include 1-carboxyethyl group, 2-carboxyethyl group, 1-carboxypropyl group, 3-carboxypropyl group, 1-carboxypentyl group. , a carboxy (phenyl) methyl group, and the like.

In said Formula (1), R< ⁴ > is a structure which has a bond, an arylene group, or a structure which has a hetero arylene group.

When R ⁴ has a structure having an arylene group, examples of the arylene group include a 1,3-phenylene group, a 1,4-phenylene group, and a 1,4-naphthylene group. As a structure which has the said arylene group, the structure etc. which are specifically, shown by following formula (2-1) - (2-5) are mentioned, for example.

When R ⁴ has a structure having a heteroarylene group, examples of the heteroarylene group include a thienylene group, a furanylene group, and a pyridylene group. Especially, a thienylene group is preferable. As a structure which has the said hetero arylene group, the structure etc. which are specifically, shown by following formula (3-1) - (3-6) are mentioned, for example.

[Formula 2]

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

[Formula 3]

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

As the compound represented by the formula (1), among the compounds represented by the following formulas (4) to (9) and R ² and R ³ in the formula (1), from the viewpoint of more excellent reactivity to visible light and low liquid crystal contamination properties. A compound in which at least one is a group represented by the following formula (10) is preferable, a compound represented by the following formula (4), and a compound in which at least one of R ² and R ³ in the formula (1) is a group represented by the following formula (10) more preferably.

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

In formula (10), R ⁵ is an alkylene group having 1 to 20 carbon atoms which may have an ether bond or an amide bond, a cycloalkylene group, an aralkylene group, a heterocyclic group, or an ether bond or an amide bond It is an arylene group, and * represents a bonding position.

As the compound in which at least one of R ² and R ³ in the formula (1) is a group represented by the formula (10), a compound represented by the following formula (11) is preferable.

[Formula 11]

As for content of the compound represented by said Formula (1), with respect to 100 weight part of curable resin, a preferable minimum is 0.01 weight part, and a preferable upper limit is 5 weight part. When content of the compound represented by said Formula (1) is 0.01 weight part or more, the curable resin composition obtained becomes the thing excellent in visible light sclerosis|hardenability. When content of the compound represented by said Formula (1) is 5 weight part or less and curable resin composition obtained uses it for the sealing compound for liquid crystal display elements, it becomes the thing excellent in low-liquid-crystal contamination property. The minimum with more preferable content of the compound represented by the said Formula (1) is 0.1 weight part, and a more preferable upper limit is 2 weight part.

Curable resin composition of this invention contains curable resin.

It is preferable that the said curable resin contains a (meth)acrylic compound.

As said (meth)acrylic compound, a (meth)acrylic acid ester compound, an epoxy (meth)acrylate, urethane (meth)acrylate, etc. are mentioned, for example. Especially, epoxy (meth)acrylate is preferable. Moreover, it is preferable that the said (meth)acryl compound has two or more (meth)acryloyl groups in 1 molecule from a reactive viewpoint.

In addition, in this specification, the said "(meth)acryl" means acryl or methacryl, and the said "(meth)acryl compound" means a compound having a (meth)acryloyl group, and the "( Meth)acryloyl" means acryloyl or methacryloyl. In addition, the said "(meth)acrylate" means an acrylate or a methacrylate. In addition, the said "epoxy (meth)acrylate" shows that it is a compound which made all the epoxy groups in an epoxy compound react with (meth)acrylic acid.

Among the (meth)acrylic acid ester compounds, monofunctional ones include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, Isodecyl (meth) acrylate, lauryl (meth) acrylate, isomyristyl (meth) acrylate, stearyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl ( Meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, bicyclopentenyl (meth) ) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, 2-phenoxyethyl ( Meth) acrylate, methoxyethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, phenoxydiethylene 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, 1H, 1H,5H-octafluoropentyl (meth)acrylate, imide (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, 2- (meth)acryloyloxy Ethyl succinic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl 2-hydroxypropyl phthalate, 2- (meth) acryloyloxyethyl phosphate, glycidyl ( meth)acrylate and the like.

Moreover, as a bifunctional thing among the said (meth)acrylic acid ester compound, 1, 3- butanediol di (meth) acrylate, 1, 4- butanediol di (meth) acrylate, and 1, 6- hexanediol are, for example. Di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylic rate, 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 ) 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 bisphenol F di(meth)acrylate, dimethyloldicyclopentadienyldi(meth)acrylate, ethylene oxide-modified isocyanuric acid di(meth)acrylate, 2-hydroxy- 3- (meth) acryloyloxypropyl (meth) acrylate, carbonate diol di (meth) acrylate, polyether diol di (meth) acrylate, polyester diol di (meth) acrylate, polycaprolactone diol di (meth)acrylate, polybutadienediol di(meth)acrylate, etc. are mentioned.

Moreover, as a trifunctional or more than trifunctional thing among the said (meth)acrylic acid ester compound, trimethylol propane tri(meth)acrylate, ethylene oxide addition trimethylol propane tri(meth)acrylate, propylene oxide addition trimethylol propane tri (meth)acrylate, caprolactone-modified trimethylolpropane tri(meth)acrylate, ethylene oxide-added isocyanuric acid tri(meth)acrylate, glycerin tri(meth)acrylate, propylene oxide-added glycerin tri(meth)acrylic Rate, pentaerythritol tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta ( Meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. are mentioned.

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

As an epoxy compound used as a raw material for synthesizing the said epoxy (meth)acrylate, For example, a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a bisphenol S type epoxy compound, and 2,2'- diallylbisphenol A Epoxy compound, hydrogenated bisphenol type epoxy compound, propylene oxide added bisphenol A type epoxy compound, resorcinol type epoxy compound, biphenyl type epoxy compound, sulfide type epoxy compound, diphenyl ether type epoxy compound, dicyclopentadiene type Epoxy compound, naphthalene type epoxy compound, phenol novolak type epoxy compound, orthocresol novolak type epoxy compound, dicyclopentadiene novolak type epoxy compound, biphenyl novolak type epoxy compound, naphthalenephenol novolak type epoxy compound, gly A cydylamine type epoxy compound, an alkyl polyol type epoxy compound, a rubber-modified type epoxy compound, a glycidyl ester compound, etc. are mentioned.

As what is marketed among the said bisphenol A epoxy compounds, jER828EL, jER1004 (all are made by Mitsubishi Chemical Corporation), EPICLON EXA-850CRP (made by DIC Corporation), etc. are mentioned, for example.

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

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

As what is marketed among the said 2,2'- diallylbisphenol A epoxy compound, RE-810NM (made by Nippon Kayaku Co., Ltd.) etc. are mentioned, for example.

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

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

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

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

As what is marketed among the said sulfide-type epoxy compounds, YSLV-50TE (made by Nittetsu Chemical & Materials) etc. is mentioned, for example.

As what is marketed among the said diphenyl ether type epoxy compounds, YSLV-80DE (made by Nittetsu Chemical & Materials) etc. is mentioned, for example.

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

As what is marketed among the said naphthalene type epoxy compounds, EPICLON HP4032, EPICLON EXA-4700 (all are made by DIC Corporation), etc. are mentioned, for example.

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

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

As what is marketed among the said dicyclopentadiene novolak-type epoxy compounds, EPICLON HP7200 (made by DIC Corporation) etc. are mentioned, for example.

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

As what is marketed among the said naphthalenephenol novolak-type epoxy compounds, ESN-165S (made by Nittetsu Chemical & Materials) etc. is mentioned, for example.

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

As what is marketed among the said alkyl polyol type epoxy compound, For example, ZX-1542 (made by Nittetsu Chemical & Materials), EPICLON 726 (made by DIC), Eporite 80MFA (made by Kyoeisha Chemicals), Denacol EX-611 (manufactured by Nagase Chemtex Co., Ltd.); and the like.

As what is marketed among the said rubber-modified epoxy compounds, YR-450, YR-207 (all are made by Nittetsu Chemicals & Materials), Epolide PB (made by Daicel), etc. are mentioned, for example.

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

Other commercially available epoxy compounds include, for example, YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Nittetsu Chemical & Materials), XAC4151 (manufactured by Asahi Chemical Corporation), jER1031, jER1032. (all are manufactured by Mitsubishi Chemical Corporation), EXA-7120 (made by DIC Corporation), TEPIC (made by Nissan Chemical Corporation), etc. are mentioned.

As what is marketed among the said epoxy (meth)acrylates, For example, the epoxy (meth)acrylate by the Daicel Allnex company, the epoxy (meth)acrylate by the Shin-Nakamura Chemical Industries, Ltd., Kyoeisha Chemical Co., Ltd. Manufactured epoxy (meth)acrylate, the epoxy (meth)acrylate by the Nagase Chemtex company, etc. are mentioned.

As said Daicel Allnex epoxy (meth)acrylate, For example, EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, DX can be heard

As said Shin-Nakamura Chemical Industry Co., Ltd. epoxy (meth)acrylate, EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, EMA-1020 etc. are mentioned, for example.

As the epoxy (meth)acrylate manufactured by Kyoeisha Chemical, for example, epoxy ester M-600A, epoxy ester 40EM, epoxy ester 70PA, epoxy ester 200PA, epoxy ester 80MFA, epoxy ester 3002M, epoxy ester 3002A, Epoxy ester 1600A, epoxy ester 3000M, epoxy ester 3000A, epoxy ester 200EA, epoxy ester 400EA, etc. are mentioned.

As said Nagase Chemtex company make epoxy (meth)acrylate, denacol acrylate DA-141, denacol acrylate DA-314, denacol acrylate DA-911 etc. are mentioned, for example.

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

Examples of the polyfunctional isocyanate compound include isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene 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, lysine diisocyanate, Triphenylmethane triisocyanate, tris (isocyanate phenyl) thiophosphate, tetramethyl xylylene diisocyanate, 1,6,11- undecane triisocyanate, etc. are mentioned.

Moreover, as said polyfunctional isocyanate compound, the chain extension polyfunctional isocyanate compound obtained by reaction of a polyol and an excess polyfunctional isocyanate compound can also be used.

Examples of the polyol include ethylene glycol, propylene glycol, glycerin, sorbitol, trimethylolpropane, carbonate diol, polyetherdiol, polyesterdiol, and polycaprolactonediol.

As the (meth)acrylic acid derivative having a hydroxyl group, for example, hydroxyalkyl mono(meth)acrylate, dihydric alcohol mono(meth)acrylate, trihydric alcohol mono(meth)acrylate or di( Meth)acrylate, epoxy (meth)acrylate, etc. are mentioned.

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. are mentioned.

As said dihydric alcohol, ethylene glycol, propylene glycol, 1, 3- propanediol, 1, 3- butanediol, 1, 4- butanediol, polyethylene glycol etc. are mentioned, for example.

As said trihydric alcohol, trimethylolethane, a trimethylol propane, glycerol etc. are mentioned, for example.

As said epoxy (meth)acrylate, bisphenol A epoxy acrylate etc. are mentioned, for example.

As what is marketed among the said urethane (meth)acrylates, For example, the urethane (meth)acrylate manufactured by Toa Synthetic Co., Ltd., the urethane (meth)acrylate manufactured by Daicel Allnex, and the urethane manufactured by Negami Kogyo Co., Ltd. (meth)acrylate, the urethane (meth)acrylate by a Shin-Nakamura Chemical Industry company, the urethane (meth)acrylate by the Kyoeisha Chemical company, etc. are mentioned.

Examples of the urethane (meth)acrylate manufactured by Toa Synthesis Co., Ltd. include M-1100, M-1200, M-1210, M-1600, and the like.

As said Daicel Allnex urethane (meth)acrylate, For example, EBECRYL210, EBECRYL220, EBECRYL230, EBECRYL270, EBECRYL1290, EBECRYL2220, EBECRYL4827, EBECRYL4842, EBECRYL4858, EBECRYL4858, EBECRYL880, EBECRYL482 EBECRYL8807, EBECRYL9260, etc. are mentioned.

Examples of the urethane (meth)acrylate manufactured by Negami Kogyo Co., Ltd. include art resin UN-330, art resin SH-500B, art resin UN-1200TPK, art resin UN-1255, art resin UN-3320HB, art resin UN-3320HB. Resin UN-7100, Art resin UN-9000A, Art resin UN-9000H, etc. are mentioned.

As the urethane (meth)acrylate manufactured by Shin-Nakamura Chemical Industries, Ltd., for example, 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. are mentioned.

As the urethane (meth)acrylate manufactured by Kyoeisha Chemical, for example, AH-600, AI-600, AT-600, UA-101I, UA-101T, UA-306H, UA-306I, UA- 306T etc. are mentioned.

The said curable resin may contain an epoxy compound for the purpose of improving the adhesiveness of the curable resin composition obtained, etc. As said epoxy compound, the epoxy compound used as a raw material for synthesizing the above-mentioned epoxy (meth)acrylate, a partial (meth)acryl modified|denatured epoxy compound, etc. are mentioned, for example.

In addition, in this specification, the said partially (meth)acrylic-modified epoxy compound is obtained by, for example, reacting a part of an epoxy group of an epoxy compound having two or more epoxy groups in one molecule with (meth)acrylic acid. , means a compound having one or more epoxy groups and (meth)acryloyl groups in one molecule, respectively.

When the said (meth)acrylic compound and the said epoxy compound are contained as said curable resin, or when the said partial (meth)acryl modified epoxy compound is contained, the sum total of the (meth)acryloyl group and the epoxy group in the said curable resin. It is preferable to make the ratio of the (meth)acryloyl group in the inside into 30 mol% or more and 95 mol% or less. When the ratio of the said (meth)acryloyl group is this range, adhesiveness becomes more excellent, suppressing generation|occurrence|production of the liquid-crystal contamination when curable resin composition obtained uses it for the sealing compound for liquid crystal display elements.

The said curable resin is hydrogen bonding property, such as -OH group, -NH- group, -NH2 group, from a viewpoint _of making the low liquid-crystal contamination property at the time of using the curable resin composition obtained for the sealing compound for liquid crystal display elements more excellent. It is desirable to have a unit.

The said curable resin may be used independently and may be used in combination of 2 or more type.

Although curable resin composition of this invention may contain a sensitizer, it is preferable not to contain the said sensitizer from viewpoints, such as low liquid-crystal contamination property at the time of using for the sealing compound for liquid crystal display elements. When curable resin composition of this invention contains the compound represented by said Formula (1) as a photoinitiator, even if it does not contain a sensitizer, it becomes the thing excellent in visible light sclerosis|hardenability.

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

As for content of the said sensitizer in the case of containing the said sensitizer, with respect to 100 weight part of said curable resin, a preferable minimum is 0.01 weight part, and a preferable upper limit is 3 weight part. When content of the said sensitizer is 0.01 weight part or more, a sensitizing effect is exhibited more. When content of the said sensitizer is 3 weight part or less, absorption does not become large too much, and light can be transmitted to a deep part. A more preferable minimum of content of the said sensitizer is 0.1 weight part, and a more preferable upper limit is 1 weight part.

Curable resin composition of this invention may contain a thermal-polymerization initiator in the range which does not impair the objective of this invention.

As said thermal polymerization initiator, what consists of an azo compound, an organic peroxide, etc. is mentioned, for example. Especially, the polymeric azo initiator which consists of a polymeric azo compound is preferable.

The said thermal-polymerization initiator may be used independently and may be used in combination of 2 or more type.

In addition, in this specification, the said "polymer azo compound" means a compound having an azo group and generating a radical capable of curing a (meth)acryloyloxy group by heat and having a number average molecular weight of 300 or more.

The preferable minimum of the number average molecular weight of the said polymeric azo compound is 1000, and a preferable upper limit is 300,000. When the number average molecular weight of the said high molecular weight azo compound is this range, it can mix easily with curable resin. When the curable resin composition obtained especially is used for the sealing compound for liquid crystal display elements, curable resin and curable resin can be mixed easily, suppressing a liquid-crystal contamination. A more preferable minimum of the number average molecular weight of the said polymeric azo compound is 5000, a more preferable upper limit is 100,000, a more preferable minimum is 10,000, and a more preferable upper limit is 90,000.

Examples of the high molecular weight azo compound include those having a structure in which a plurality of units such as polyalkylene oxide and polydimethylsiloxane are bonded via an azo group.

As the high molecular weight azo compound having a structure in which a plurality of units such as polyalkylene oxide are bonded via the azo group, it is preferable to have a polyethylene oxide structure.

Specific examples of the polymer azo compound include a polycondensate of 4,4'-azobis(4-cyanopentanoic acid) and polyalkylene glycol, and 4,4'-azobis(4-cyanophene). carbonic acid) and polydimethylsiloxane having a terminal amino group; and the like.

As what is marketed among the said polymeric azo compounds, VPE-0201, VPE-0401, VPE-0601, VPS-0501, VPS-1001 (all are the Fujifilm Wako Pure Pharmaceutical Co., Ltd. make) etc. are mentioned, for example.

Moreover, as an azo compound which is not polymer|macromolecule, V-65, V-501 (all are the Fujifilm Wako Pure Pharmaceutical Co., Ltd. make) etc. are mentioned, for example.

Examples of the organic peroxide include ketone peroxide, peroxyketal, hydroperoxide, dialkylperoxide, peroxyester, diacylperoxide, and peroxydicarbonate.

As for content of the said thermal-polymerization initiator, with respect to 100 weight part of said curable resin, a preferable minimum is 0.05 weight part, and a preferable upper limit is 10 weight part. When content of the said thermal-polymerization initiator is 0.05 weight part or more, the curable resin composition of this invention becomes a thing excellent in thermosetting property. When content of the said thermal-polymerization initiator is 10 weight part or less, curable resin composition of this invention becomes the thing more excellent in storage stability, and when it uses for the sealing compound for liquid crystal display elements, it becomes the thing excellent also in low-liquid-crystal contamination property. A more preferable lower limit of the content of the thermal polymerization initiator is 0.1 parts by weight, and a more preferable upper limit thereof is 5 parts by weight.

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

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

The said thermosetting agent may be used independently and may be used in combination of 2 or more type.

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

As what is marketed among the said organic acid hydrazide, the organic acid hydrazide by the Otsuka Chemical company, the organic acid hydrazide by the Ajinomoto Fine Techno company, etc. are mentioned, for example.

As said organic acid hydrazide by the Otsuka Chemical company, SDH, ADH, etc. are mentioned, for example.

As said organic acid hydrazide by the said Ajinomoto Fine Techno company, Amicure VDH, Amicure VDH-J, Amicure UDH, Amicure UDH-J etc. are mentioned, for example.

As for content of the said thermosetting agent, with respect to 100 weight part of said curable resins, a preferable minimum is 1 weight part, and a preferable upper limit is 50 weight part. When content of the said thermosetting agent is this range, it can be made into the thing more excellent in thermosetting property, without deteriorating the applicability|paintability etc. of the curable resin composition obtained. A more preferable upper limit of the content of the thermosetting agent is 30 parts by weight.

It is preferable that curable resin composition of this invention contains a filler for the purpose of the improvement of a viscosity, the adhesive improvement by the stress dispersion effect, the improvement of a linear expansion coefficient, etc.

As the filler, an inorganic filler or an organic filler can be used.

Examples of the inorganic filler include silica, talc, glass beads, asbestos, gypsum, diatomaceous earth, smectite, bentonite, montmorillonite, sericite, activated clay, alumina, 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, and the like.

As said organic filler, polyester microparticles|fine-particles, polyurethane microparticles|fine-particles, vinyl polymer microparticles|fine-particles, acrylic polymer microparticles|fine-particles, etc. are mentioned, for example.

The said filler may be used independently and may be used in combination of 2 or more type.

As for content of the said filler, with respect to 100 weight part of said curable resin, a preferable minimum is 30 weight part, and a preferable upper limit is 80 weight part. When content of the said filler is this range, it becomes a thing excellent in the effect, such as an adhesive improvement, without worsening applicability|paintability etc. A more preferable lower limit of the content of the filler is 45 parts by weight, and a more preferable upper limit thereof is 65 parts by weight.

It is preferable that curable resin composition of this invention contains a silane coupling agent. The said silane coupling agent mainly has a role as an adhesion auxiliary agent for adhering a curable resin composition, a board|substrate, etc. favorably.

Examples of the silane coupling agent include 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanatepropyltrimethoxysilane, and the like. This is preferably used. These are excellent in the effect of improving the adhesiveness with a board|substrate etc., and when the curable resin composition obtained is used for the sealing compound for liquid crystal display elements, it can suppress the outflow of curable resin into a liquid crystal by chemically bonding with curable resin. have.

The said silane coupling agent may be used independently and may be used in combination of 2 or more type.

The minimum with preferable content of the said silane coupling agent in 100 weight part of curable resin composition of this invention is 0.1 weight part, and a preferable upper limit is 10 weight part. When content of the said silane coupling agent is this range, the curable resin composition obtained becomes more excellent in adhesiveness. When the curable resin composition obtained especially is used for the sealing compound for liquid crystal display elements, adhesiveness becomes more excellent, suppressing generation|occurrence|production of a liquid-crystal contamination. A more preferable lower limit of content of the said silane coupling agent is 0.3 weight part, and a more preferable upper limit is 5 weight part.

The curable resin composition of this invention may contain additives, such as a reactive diluent, a thixotropic agent, a spacer, a hardening accelerator, an antifoamer, a leveling agent, and a polymerization inhibitor, further as needed.

As a method of manufacturing the curable resin composition of this invention, using mixers, such as a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, 3 rolls, curable resin and a photoinitiator, for example, and the method of mixing the silane coupling agent etc. which are added as needed, etc. are mentioned.

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

By mix|blending electroconductive microparticles|fine-particles with curable resin composition of this invention, a vertical conduction material can be manufactured. The vertical conduction material containing the curable resin composition of this invention and electroconductive fine particles is also one of this invention.

As the conductive fine particles, a metal ball or one in which a conductive metal layer is formed on the surface of the resin fine particles, etc. can be used. Among them, the one in which the conductive metal layer is formed on the surface of the resin fine particles is preferable because of the excellent elasticity of the resin fine particles, the conductive connection is possible without damaging the transparent substrate or the like.

The display element which has the hardened|cured material of the sealing compound for display elements of this invention, the hardened|cured material of the sealing compound for liquid crystal display elements of this invention, or the top and bottom conduction material of this invention is also one of this invention.

As a display element of this invention, the liquid crystal display element formed using the sealing compound for liquid crystal display elements of this invention is preferable, and the liquid crystal display element of a frame narrow 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, it is preferable that the application width|variety of the sealing compound for liquid crystal display elements of this invention at the time of manufacturing a liquid crystal display element as a display element of this invention is 1 mm or less.

As a method of manufacturing a liquid crystal display element as a display element of this invention, the liquid-crystal dropping method is used preferably, and, specifically, the method etc. which have the following each process are mentioned, for example.

First, the sealing compound for liquid crystal display elements of this invention is apply|coated by screen printing, dispenser application|coating, etc. to one of two transparent substrates which have electrodes, such as an ITO thin film, and an orientation film, The process of forming a frame-shaped sealing pattern is performed. Next, in a non-hardened state, the sealing compound for liquid crystal display elements of this invention drip apply|coats the microdroplet of a liquid crystal in the frame of the sealing pattern of a board|substrate, and performs the process of superimposing the other transparent substrate under vacuum. Then, a liquid crystal display element can be obtained by the method of performing the process of photocuring a sealing compound by irradiating light to the sealing pattern part of the sealing compound for liquid crystal display elements of this invention through a cut filter etc. Moreover, in addition to the process of photocuring the said sealing compound, you may perform the process of heating and thermosetting a sealing compound.

The curable resin composition of this invention is used suitably also for adhesion|attachment of an electronic component. When the curable resin composition of this invention is used as an adhesive agent for electronic components, since low-energy light can be used for light irradiation at the time of hardening, deterioration of another member, etc. can be suppressed.

The adhesive for electronic components containing the curable resin composition of the present invention, and the electronic component adhered to the cured product of the adhesive for electronic components of the present invention are also each one of the present invention.

ADVANTAGE OF THE INVENTION According to this invention, when it is excellent in visible light sclerosis|hardenability and adhesiveness, and also uses for the sealing compound for liquid crystal display elements, the curable resin composition excellent also in low liquid-crystal contamination property can be provided. Moreover, according to this invention, the sealing compound for display elements containing this curable resin composition, the sealing compound for liquid crystal display elements, and the vertical conduction material, and the hardened|cured material of the sealing compound for display elements, the object for liquid crystal display elements The display element which has the hardened|cured material of the sealing compound or the hardened|cured material of this vertical conduction|electrical_connection can be provided. Moreover, according to this invention, the adhesive agent for electronic components containing this curable resin composition, and the electronic component adhere|attached by the hardened|cured material of this adhesive agent for electronic components can be provided.

The present invention will be described in more detail below with reference to Examples, but the present invention is not limited only to these Examples.

(Synthesis of compound represented by formula (4))

5 parts by weight of N-ethylcarbazole, 2.81 parts by weight of 2,5-thiophenedicarboxylic acid dichloride and 3.76 parts by weight of aluminum chloride were added to 40 mL of dichloromethane, followed by stirring at room temperature overnight. To the obtained reaction solution, 2.21 parts by weight of acetyl chloride and 3.76 parts by weight of aluminum chloride were added, followed by stirring at room temperature for further 4 hours. After pouring the obtained reaction solution into ice water, the organic layer was extracted with ethyl acetate. The extracted solution was washed with a saturated aqueous sodium hydrogen carbonate solution and brine, dried over anhydrous magnesium sulfate, and concentrated to obtain a product (A1).

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 were added to 30 mL of ethanol, followed by stirring under reflux for 10 hours. The obtained reaction solution was poured into ice water and then filtered. The filtrate was washed with water, dissolved in ethyl acetate, dried over anhydrous magnesium sulfate, and concentrated to obtain a product (B1).

After dissolving 1.5 parts by weight of the obtained product (B1) in 25 parts by weight of N,N-dimethylformamide, 0.59 parts by weight of acetyl chloride was added. 0.78 parts by weight of triethylamine was added dropwise to the obtained solution while cooling to 10°C or lower, followed by stirring at room temperature for 4 hours. The obtained reaction solution was poured with water and then filtered. The filtrate was purified by silica gel column chromatography using a mixed solvent of dichloromethane and hexane (dichloromethane: hexane = 2:1) to obtain a compound represented by the above formula (4).

In addition, the structure of the obtained compound represented by said Formula (4) was confirmed by ¹ H-NMR, ¹³ C-NMR, and FT-IR.

(Synthesis of compound represented by formula (9))

5 parts by weight of N-(2-ethylhexyl)carbazole, 2.81 parts by weight of 2,5-thiophenedicarboxylic acid dichloride, and 3.76 parts by weight of aluminum chloride were added to 40 mL of dichloromethane, followed by stirring at room temperature overnight. To the obtained reaction solution, 2.21 parts by weight of acetyl chloride and 3.76 parts by weight of aluminum chloride were added, followed by stirring at room temperature for further 4 hours. After pouring the obtained reaction solution into ice water, the organic layer was extracted with ethyl acetate. The extracted solution was washed with a saturated aqueous sodium hydrogencarbonate solution and brine, dried over anhydrous magnesium sulfate, and concentrated to obtain a product (A2).

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 were added to 30 mL of ethanol, followed by stirring under reflux for 10 hours. The obtained reaction solution was poured into ice water and then filtered. The filtrate was washed with water, dissolved in ethyl acetate, dried over anhydrous magnesium sulfate, and concentrated to obtain a product (B2).

After dissolving 1.5 parts by weight of the obtained product (B2) in 25 parts by weight of N,N-dimethylformamide, 0.59 parts by weight of acetyl chloride was added. 0.78 parts by weight of triethylamine was added dropwise to the obtained solution while cooling to 10°C or lower, followed by stirring at room temperature for 4 hours. The obtained reaction solution was poured with water and then filtered. The filtrate was purified by silica gel column chromatography using a mixed solvent of dichloromethane and hexane (dichloromethane:hexane = 2:1) to obtain a compound represented by the above formula (9).

In addition, the structure of the obtained compound represented by said Formula (9) was confirmed by ¹ H-NMR, ¹³ C-NMR, and FT-IR.

(Synthesis of compound represented by formula (11))

5 parts by weight of ethyl 3-(9H-carbazol-9-yl)propionate, 2.64 parts by weight of hexanoyl chloride, and 2.62 parts by weight of aluminum chloride were added to 80 mL of dichloromethane, followed by stirring at room temperature overnight. To the obtained reaction solution, 1.84 parts by weight of 2,5-thiophenedicarboxylic acid dichloride and 5.24 parts by weight of aluminum chloride were added, followed by stirring at room temperature for further 4 hours. After pouring the obtained reaction solution into ice water, the organic layer was extracted with ethyl acetate. The extracted solution was washed with a saturated aqueous sodium hydrogen carbonate solution and brine, dried over anhydrous sodium sulfate, and concentrated to obtain a product (A3).

To 4.0 parts by weight of the product (A3) in 20 mL of ethanol, 2.77 parts by weight of a 20% aqueous sodium hydroxide solution was added, and the mixture was refluxed for 3 hours. After completion of the reaction, 50 mL of water was added and acidified with concentrated hydrochloric acid, followed by extraction with ethyl acetate. The ethyl acetate layer was washed with water and brine, and then dried over anhydrous sodium sulfate and concentrated to obtain a 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, followed by stirring under reflux for 10 hours. The obtained reaction solution was poured into ice water and then filtered. The filtrate was washed with water, dissolved in ethyl acetate, dried over anhydrous sodium sulfate, and concentrated to obtain a product (C3).

After dissolving 1.5 parts by weight of the obtained product (C3) in 20 parts by weight of N,N-dimethylformamide, 0.45 parts by weight of acetyl chloride was added. 0.59 parts by weight of triethylamine was added dropwise to the obtained solution while cooling to 10°C or lower, followed by stirring at room temperature for 4 hours. The obtained reaction solution was poured with water and then filtered. The compound represented by the above formula (11) was obtained by isolating the compound by silica gel column chromatography.

In addition, the structure of the obtained compound represented by said 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 compounding ratio of Table 1, after mixing each material using a planetary stirrer, Examples 1-11 and the curable resin composition of Comparative Examples 1-3 were prepared by mixing using 3 rolls further. As the planetary stirrer, Awatori Rentaro (manufactured by Shinki Corporation) was used.

<Evaluation>

The following evaluation was performed about each curable resin composition obtained by the Example and the comparative example. The results are shown in Table 1.

(UV curable)

1 part by weight of spacer fine particles was dispersed in 100 parts by weight of each curable resin composition obtained in Examples and Comparative Examples. As the spacer fine particles, Micropearl SI-H050 (manufactured by Sekisui Chemical Industry Co., Ltd.) was used. Next, after filling the syringe for dispensing with a sealing compound and performing a defoaming process, it apply|coated on the glass substrate with the dispenser. As a syringe for dispensing, PSY-10E (manufactured by Musashi Engineering) was used, and as a dispenser, SHOTMASTER300 (manufactured by Musashi Engineering) was used. The glass substrate of the same size was bonded to the board|substrate to which the sealing compound was apply|coated under the pressure_reduction|reduced_pressure of 5 Pa with the vacuum bonding apparatus. The light of 100 mW/cm<2> was irradiated for 10 second using the metal halide lamp to the sealing compound part of the bonded glass substrate. Light irradiation was performed through a cut filter (340 nm cut filter) that cuts light having a wavelength of 340 m or less.

FT-IR measurement of the sealing compound was performed using the infrared spectroscopy apparatus, and the change amount before and behind light irradiation of the peak derived from (meth)acryloyl group was measured. As the infrared spectrometer, FTS3000 (manufactured by BIORAD) was used. After light irradiation, the case where the peak derived from the (meth)acryloyl group decreased by 95% or more was “◎”, the case where it was decreased by 90% or more and less than 95% was “○”, and the case where it was decreased by 70% or more and less than 90% was “△” ", the case where the reduction|decrease of the peak derived from the (meth)acryloyl group after light irradiation was less than 70 % was made into "x", and UV curability was evaluated.

(Visible light curability)

1 part by weight of spacer fine particles was dispersed in 100 parts by weight of each curable resin composition obtained in Examples and Comparative Examples. As the spacer fine particles, Micropearl SI-H050 (manufactured by Sekisui Chemical Industry Co., Ltd.) was used. Next, after filling the syringe for dispensing with a sealing compound and performing a defoaming process, it apply|coated on the glass substrate with the dispenser. As a syringe for dispensing, PSY-10E (manufactured by Musashi Engineering) was used, and as a dispenser, SHOTMASTER300 (manufactured by Musashi Engineering) was used. The glass substrate of the same size was bonded to the board|substrate to which the sealing compound was apply|coated under the pressure_reduction|reduced_pressure of 5 Pa with the vacuum bonding apparatus. The light of 100 mW/cm<2> was irradiated for 10 second using the metal halide lamp to the sealing compound part of the bonded glass substrate. Light irradiation was performed through a cut filter (420 nm cut filter) that cuts light having a wavelength of 420 m or less.

FT-IR measurement of the sealing compound was performed using the infrared spectroscopy apparatus, and the change amount before and behind light irradiation of the peak derived from (meth)acryloyl group was measured. As the infrared spectrometer, FTS3000 (manufactured by BIORAD) was used. After light irradiation, the case where the peak derived from the (meth)acryloyl group decreased by 95% or more was “◎”, the case where it was decreased by 90% or more and less than 95% was “○”, and the case where it was decreased by 70% or more and less than 90% was “△” ", the case where the reduction|decrease of the peak derived from the (meth)acryloyl group after light irradiation was less than 70 % was made into "x", and UV curability was evaluated.

(Low liquid crystal contamination)

0.5 g of liquid crystal (manufactured by Chisso, "JC-5001LA") was placed in a sample bottle, 0.1 g of each curable resin composition obtained in Examples and Comparative Examples was added and shaken, then heated at 120° C. for 1 hour, and room temperature ( 25°C). On the alignment film of a glass substrate having a transparent electrode and an alignment film (manufactured by Nissan Chemical Co., Ltd., "SE7492"), each curable resin composition obtained in Examples and Comparative Examples was applied with a dispenser as if drawing a square frame. Then, the liquid crystal micro-droplets taken out from the said sample bottle were drip-coated on the whole surface in the frame on a board|substrate, and the other glass substrate was superposed|stacked in vacuum. The vacuum was released and 100 mW/cm 2 light was irradiated for 10 seconds using a metal halide lamp. Light irradiation was performed through a cut filter (420 nm cut filter) that cuts light having a wavelength of 420 m or less. Then, the sealing compound was thermosetted by heating at 120 degreeC for 1 hour, and the liquid crystal display element was obtained. About the obtained liquid crystal display element, the generation|occurrence|production degree of the residual image at the time of applying a DC voltage of 1V was confirmed visually, applying an alternating voltage of 1.5V. As a result, the display performance of the liquid crystal display element was evaluated as "○" when no afterimage was observed at all, "Δ" when slight afterimage was confirmed, and "x" when severe afterimage was confirmed.

(Adhesive)

1 weight part of spacer microparticles|fine-particles were disperse|distributed to 100 weight part of each curable resin composition obtained by the Example and the comparative example, and it was microdropped at one of the glass substrates (30x40mm) with ITO thin film of 2 sheets. As the spacer fine particles, Micropearl SI-H050 (manufactured by Sekisui Chemical Industry Co., Ltd.) was used. Another glass substrate with an ITO thin film was bonded to this crosswise, and after irradiating 100 mW/cm<2> light for 30 second with a metal halide lamp, the adhesive test piece was obtained by heating at 120 degreeC for 60 minutes.

The obtained adhesion test piece was subjected to a tensile test (5 mm/sec) with a chuck placed up and down. When the obtained measured value (kgf) divided by the seal application cross-sectional area (cm 2 ) was 1.5 kgf/cm 2 or more, "○", and less than 1.5 kgf/cm 2 "x", and the adhesiveness was evaluated.

ADVANTAGE OF THE INVENTION According to this invention, when it is excellent in visible light sclerosis|hardenability and adhesiveness, and also uses for the sealing compound for liquid crystal display elements, the curable resin composition excellent also in low liquid-crystal contamination property can be provided. Moreover, according to this invention, the sealing compound for display elements containing this curable resin composition, the sealing compound for liquid crystal display elements, and the vertical conduction material, and the hardened|cured material of the sealing compound for display elements, the object for liquid crystal display elements The display element which has the hardened|cured material of the sealing compound or the hardened|cured material of this vertical conduction|electrical_connection can be provided. Moreover, according to this invention, the adhesive agent for electronic components containing this curable resin composition, and the electronic component adhere|attached by the hardened|cured material of this adhesive agent for electronic components can be provided.

Claims (10)

A curable resin composition comprising a curable resin and a photoinitiator, comprising:
The said photoinitiator contains the compound represented by following formula (1), Curable resin composition characterized by the above-mentioned.

In formula (1), R ¹ is each independently an alkyl group having 1 to 20 carbon atoms which may have an ether bond or an amide bond, a cycloalkyl group, an aralkyl group, a heterocyclic group, or an ether bond or an amide bond. It is an aryl group used, and the alkyl group having 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), R ² is each independently an alkyl group having 1 to 20 carbon atoms which may have an ether bond or an amide bond, a cycloalkyl group, an aralkyl group, a heterocyclic group, or an ether bond or an amide bond. It is an aryl group used, and the alkyl group having 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), R ³ is each independently an alkyl group having 1 to 20 carbon atoms which may have an ether bond or an amide bond, a cycloalkyl group, an aralkyl group, a heterocyclic group, or an ether bond or an amide bond. It is an aryl group used, and the alkyl group having 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), R ⁴ is a structure having a bond, an arylene group, or a heteroarylene group. The method of claim 1,
Curable resin composition in which the said photoinitiator contains the compound represented by following formula (4).

The method of claim 1,
Curable resin composition in which the said photoinitiator contains the compound represented by following formula (11).

4. The method of claim 1, 2 or 3,
Curable resin composition whose content of the compound represented by said Formula (1) is 0.01 weight part or more and 5 weight part or less with respect to 100 weight part of said curable resins. The sealing compound for display elements containing curable resin composition of Claim 1, 2, 3, or 4. The sealing compound for liquid crystal display elements containing curable resin composition of Claim 1, 2, 3, or 4. A vertical conduction material comprising the curable resin composition according to claim 1, 2, 3, or 4, and conductive fine particles. The display element which has hardened|cured material of the sealing compound for display elements of Claim 5, the hardened|cured material of the sealing compound for liquid crystal display elements of Claim 6, or the hardened|cured material of the vertical conduction material of Claim 7. The adhesive for electronic components containing the curable resin composition of Claim 1, 2, 3, or 4. The electronic component adhere|attached with the hardened|cured material of the adhesive agent for electronic components of Claim 9.