JP2005060651A - Curable resin composition, liquid crystal display element sealing agent, liquid crystal display element sealing agent, liquid crystal display element vertical conduction material, and liquid crystal display element - Google Patents

Abstract

In particular, in the production of a liquid crystal display element by a dropping method, when used as at least one of a sealing agent for a liquid crystal display element, a sealing agent for a liquid crystal display element, and a vertical conduction material for a liquid crystal display element, irradiation is performed when curing. Curable resin composition, liquid crystal display element sealing agent, liquid crystal display element sealing agent, liquid crystal display element capable of realizing high display quality and high reliability of liquid crystal display element without deterioration of liquid crystal due to ultraviolet rays The present invention provides a vertical conducting material for use, and a liquid crystal display element using these materials.
A curable resin composition comprising a radical polymerization initiator having a radical polymerization initiating group and a hydrogen-bonding functional group in one molecule that generate active radicals upon irradiation with light, and a curable resin. The radical polymerization initiator is a curable resin composition having a molar extinction coefficient at 350 nm measured in acetonitrile of 200 to 10,000 M ⁻¹ · cm ⁻¹ .
[Selection figure] None

Description

  The present invention relates to an ultraviolet ray irradiated during curing, particularly when used as at least one of a sealing agent for liquid crystal display elements, a sealing agent for liquid crystal display elements, and a vertical conduction material for liquid crystal display elements in the production of liquid crystal display elements by a dropping method. The present invention relates to a curable resin composition, a liquid crystal display element sealing agent, a liquid crystal display element sealing agent, a liquid crystal display element vertical conduction material, and a liquid crystal display element using these.

Conventionally, a liquid crystal display element such as a liquid crystal display cell is formed by forming a cell by facing two transparent substrates with electrodes facing each other at a predetermined interval and sealing the periphery with a sealing agent. The liquid crystal was injected into the cell from the liquid crystal injection port, and the liquid crystal injection port was sealed using a sealing agent or a sealing agent.
In this method, first, a seal pattern provided with a liquid crystal injection port using a thermosetting sealant is formed on one of two transparent substrates with electrodes by screen printing, and prebaked at 60 to 100 ° C. Dry the solvent in the sealant. Next, alignment is performed with the two substrates facing each other with a spacer interposed therebetween, and the gap in the vicinity of the seal is adjusted by performing hot pressing at 110 to 220 ° C. for 10 to 90 minutes, and then at 110 to 220 ° C. in an oven. Heat for 10 to 120 minutes to fully cure the sealant. Next, liquid crystal was injected from the liquid crystal injection port, and finally, the liquid crystal injection port was sealed using a sealing agent to produce a liquid crystal display element.

  However, according to this manufacturing method, positional displacement, gap variation, and decrease in adhesion between the sealant and the substrate occur due to thermal strain; residual solvent thermally expands to generate bubbles, resulting in gap variation and seal path. The seal curing time is long; the prebaking process is complicated; the usable time of the sealant is short due to the volatilization of the solvent; and it takes time to inject liquid crystal. In particular, in a large liquid crystal display device in recent years, it takes a very long time to inject liquid crystal.

  On the other hand, a manufacturing method of a liquid crystal display element called a dripping method using a sealing agent made of a curable resin composition has been studied. In the dropping method, first, a rectangular seal pattern is formed on one of the two transparent substrates with electrodes by screen printing. Next, fine droplets of liquid crystal are dropped and applied to the entire surface of the transparent substrate frame in an uncured state of the sealant, and the other transparent substrate is immediately overlaid, and the seal portion is irradiated with ultraviolet rays for temporary curing. Then, if necessary, it is heated at the time of liquid crystal annealing and further cured to produce a liquid crystal display element. If the substrates are bonded together under reduced pressure, a liquid crystal display element can be manufactured with extremely high efficiency. In the future, this dripping method is expected to become the mainstream of liquid crystal display manufacturing methods.

  As a sealing agent used in a conventional construction method, for example, Patent Document 1 discloses an adhesive mainly composed of a partial (meth) acrylate of a bisphenol A type epoxy resin. Other similar sealing agents are disclosed in Patent Document 2, Patent Document 3, or Patent Document 4, and the like. Patent Document 5 discloses a liquid crystal sealant mainly composed of (meth) acrylate.

Conventionally, when a liquid crystal display element is produced by a dropping method using these sealing agents, it has been necessary to irradiate ultraviolet rays having a high energy with a wavelength of less than 350 nm in order to sufficiently cure the sealing agent.
However, in the manufacture of liquid crystal display elements by the dripping method, since the ultraviolet rays irradiated to cure the sealing agent are also irradiated to the liquid crystal, when the sealing agent is cured with ultraviolet rays having a short wavelength and high energy, the liquid crystal is simultaneously emitted. There is also a problem that the display quality of the liquid crystal display element is remarkably lowered and the reliability is lowered. In addition, when the curable resin composition similar to that of the sealing agent is used as the vertical conduction material, there is a problem similar to that of the sealing agent.
Japanese Patent Laid-Open No. 6-160872 JP-A-1-243029 JP 7-13173 A Japanese Patent Laid-Open No. 7-13175 Japanese Patent Laid-Open No. 7-13174

  In view of the above-mentioned present situation, the present invention, particularly when used as at least one of a liquid crystal display element sealing agent, a liquid crystal display element sealing agent and a liquid crystal display element vertical conduction material in the production of a liquid crystal display element by a dropping method, A curable resin composition capable of realizing high display quality and high reliability of a liquid crystal display element, liquid crystal display element sealant, and liquid crystal display element use liquid crystal display device without deterioration of liquid crystal due to ultraviolet rays irradiated upon curing. It is an object of the present invention to provide a sealing agent, a vertical conducting material for a liquid crystal display element, and a liquid crystal display element using these.

The present invention relates to a curable resin composition comprising a radical polymerization initiator having a radical polymerization initiating group and a hydrogen bonding functional group that generate active radicals when irradiated with light in one molecule, and a curable resin. The radical polymerization initiator is a curable resin composition having a molar extinction coefficient at 350 nm measured in acetonitrile of 200 to 10,000 M ⁻¹ · cm ⁻¹ .
The present invention is described in detail below.

The curable resin composition of the present invention contains a radical polymerization initiator and a curable resin.
The radical polymerization initiator has a lower limit of the molar extinction coefficient at 350 nm measured in acetonitrile of 200 M ⁻¹ · cm ⁻¹ and an upper limit of 10,000 M ⁻¹ · cm ⁻¹ . 200M is less than ^-1 · cm ^-1, for a liquid crystal display element sealant, when used as a vertically conducting material for a sealing agent or a liquid crystal display device liquid crystal display device, rapidly by irradiating ultraviolet rays having a wavelength of about 350nm And when it cannot be cured sufficiently and exceeds 10,000 M ⁻¹ · cm ⁻¹ , when used as a liquid crystal display element sealing agent, a liquid crystal display element sealing agent or a liquid crystal display element vertical conduction material, When the ultraviolet rays having a wavelength of about 350 nm are irradiated, only the surface is cured first, and the inside cannot be sufficiently cured. A preferred lower limit is 300 M ⁻¹ · cm ⁻¹ , and a preferred upper limit is 3000 M ⁻¹ · cm ⁻¹ .

In the present specification, the molar extinction coefficient is ε (M ⁻¹ · cm ⁻¹ ) defined by the Lambert-Beer formula for the acetonitrile solution containing the radical polymerization initiator shown in the following formula (1). Means the value of

In the above formula (1), I represents the intensity of transmitted light, I _o represents the intensity of transmitted light of the acetonitrile pure solvent, c represents the molar concentration (M), d represents the thickness (cm) of the solution layer, and log ( I _o / I) represents the absorbance.

The radical polymerization initiator preferably has a molar extinction coefficient at 430 nm measured in acetonitrile of 100 M ⁻¹ · cm ⁻¹ or less. When it exceeds 100 M ⁻¹ · cm ⁻¹ , active radicals are generated by light having a wavelength in the visible light range, and handling is very poor.

The radical polymerization initiator has in one molecule a radical polymerization initiating group that generates an active radical when irradiated with light and a hydrogen bonding functional group.
Examples of the radical polymerization initiating group include a carbonyl group, a sulfur-containing group, an azo group, and an organic peroxide-containing group. Among these, the structures represented by the following general formulas (1) to (4) are exemplified. Suitable groups are preferred.

In the general formulas (1) to (4), R ¹ , R ² and R ³ are each independently an alkyl group having 1 to 6 carbon atoms, a hydrogen atom, a hydroxyl group, or an alkoxyl group having 1 to 6 carbon atoms. , (Meth) acrylic group, phenyl group,

  Represents an aromatic ring which may have an alkyl group having 1 to 6 carbon atoms or a halogen group.

  Of these, a group having a structure represented by the general formula (1) is more preferable from the viewpoint of the generation efficiency of active radicals.

  Moreover, it is preferable that the (meth) acryl group (conversion rate of an acrylic group) consumed by the active radical generated from the radical polymerization initiator is 90% or more. When it is less than 90%, when the curable resin composition of the present invention is used as a sealing agent for liquid crystal display elements, a sealing agent for liquid crystal display elements, or a vertical conduction material for liquid crystal display elements, it cures by heating during liquid crystal realignment. The unpolymerized or uncrosslinked component in the curable resin composition may elute into the liquid crystal, impairing the alignment of the liquid crystal, and may be one cause of color unevenness.

The hydrogen bonding functional group is not particularly limited as long as it is a functional group or a residue having hydrogen bonding properties, for example, OH group, NH ₂ group, NHR group (R is an aromatic or aliphatic hydrocarbon) And COOH groups, CONH ₂ groups, NHOH groups, and the like, and groups having residues such as NHCO bonds, NH bonds, CONHCO bonds, and NH—NH bonds in the molecule.
When the radical polymerization initiator has such a hydrogen bonding functional group, the radical polymerization initiator is less likely to elute even when the uncured curable resin composition of the present invention is in contact with the liquid crystal. Liquid crystal contamination is less likely to occur.

The radical polymerization initiator preferably further has a reactive functional group capable of reacting with and binding to the curable resin described later.
The reactive functional group is not particularly limited as long as it is a functional group that can be bonded to the curable resin by a polymerization reaction, and examples thereof include cyclic ether groups such as epoxy groups and oxetanyl groups, (meth) acrylic groups, styryl groups, and the like. Can be mentioned. Of these, a (meth) acryl group or an epoxy group is preferred.
By having such a reactive functional group in the molecule, the radical polymerization initiator itself is fixed by forming a copolymer with the curable resin. Is not eluted into the liquid crystal, and is not outgassed by heating during liquid crystal realignment.

  In addition, in a radical polymerization initiator that generates two active radicals by dissociating radical polymerization initiating groups when irradiated with light, the generated active radicals are added to radical polymerizable functional groups such as (meth) acrylic groups. If the active radicals are deactivated by hydrogen abstraction or the like, elution into the liquid crystal may occur, or outgassing may occur after curing. Therefore, the radical polymerization initiator preferably has at least one hydrogen-bonding functional group and a reactive functional group, respectively, when the radical polymerization initiating group absorbs light and dissociates into two active radicals. That is, the reactive functional group is reactive with at least one hydrogen bonding functional group when the radical polymerization initiating group is dissociated by irradiation with light to generate two active radicals. It is preferable to arrange | position in a molecule | numerator so that it may have a functional group. Thereby, since all the generated active radicals are fixed by forming a copolymer with the curable resin, the residue of the radical polymerization initiator does not elute into the liquid crystal even after the completion of the polymerization, Since the residue of the radical polymerization initiator is taken into the cured product after curing, it is not outgassed by heating during liquid crystal realignment.

  The lower limit of the number average molecular weight of the radical polymerization initiator is preferably 300. If it is less than 300, the radical polymerization initiator component may elute into the liquid crystal, and the orientation of the liquid crystal may be easily disturbed. A preferable upper limit is 3000. If it exceeds 3000, it may be difficult to adjust the viscosity of the curable resin composition of the present invention.

  It does not specifically limit as a manufacturing method of the said radical polymerization initiator, A conventionally well-known method can be used, for example, the said radical is contained in 1 molecule using (meth) acrylic acid or (meth) acrylic acid chloride. (Meth) acrylic esterification of an alcohol derivative having a polymerization initiating group and a hydroxyl group; a compound having the above radical polymerization initiating group and a hydroxyl group or an amino group in one molecule, and two epoxy groups in the molecule A method of reacting one of the epoxy groups of the compound having one or more of the above: a compound having two or more radical polymerization initiating groups and a hydroxyl group or an amino group in the molecule, and one of the compounds having two or more epoxy groups in the molecule Reacting with an epoxy group, and further, the remaining epoxy group is a (meth) acrylic acid or (meth) acrylic acid ester monomer having an active hydrogen group, A method of reacting with a tylene monomer or the like; reacting a compound having two or more radical polymerization initiating groups and a hydroxyl group or an amino group in the molecule with a cyclic ester compound or a carboxylic acid compound having a hydroxyl group; A urethane derivative from a compound having two or more radical polymerization initiating groups and a hydroxyl group or an amino group in the molecule, and a bifunctional isocyanate derivative; Examples thereof include a method of reacting isocyanate with (meth) acrylic acid, glycidol, a (meth) acrylic acid ester monomer having a hydroxyl group, a styrene monomer, and the like.

Examples of the compound having two or more epoxy groups in the molecule include a bifunctional epoxy resin compound.
The bifunctional epoxy resin compound is not particularly limited. For example, a bisphenol A type epoxy compound, a bisphenol F type epoxy resin, a bisphenol AD type epoxy resin, an epoxy resin obtained by adding these to water, a novolac type epoxy resin, a urethane-modified epoxy Examples thereof include a resin, a nitrogen-containing epoxy resin obtained by epoxidizing meta-xylenediamine and the like, a rubber-modified epoxy resin containing polybutadiene or nitrile butadiene rubber (NBR), and the like. These bifunctional epoxy resin compounds may be solid or liquid.

  The (meth) acrylic acid ester monomer having a hydroxyl group is not particularly limited, and examples thereof include ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and polyethylene glycol. And mono (meth) acrylates of trivalent alcohols such as mono (meth) acrylates of trihydric alcohols, trimethylolethane, trimethylolpropane and glycerin, and di (meth) acrylates. These may be used independently and 2 or more types may be used together.

Examples of the bifunctional isocyanate derivative include diphenylmethane diisocyanate (MDI), tolylene diisocyanate (TDI), xylene diisocyanate (XDI), isophorone diisocyanate (IPDI), naphthylene diisocyanate (NDI), tolidine diisocyanate (TPDI), hexamethylene. Examples include diisocyanate (HDI), dicyclohexylmethane diisocyanate (HMDI), trimethylhexamethylene diisocyanate (TMHDI), and the like.
In the curable resin composition of the present invention, the above radical polymerization initiators may be used alone or in combination of two or more.

  A preferable lower limit of the blending amount of the radical polymerization initiator in the curable resin composition of the present invention is 0.1 part by weight with respect to 100 parts by weight of the curable resin described later, and a preferable upper limit is 15 parts by weight. If it is less than 0.1 part by weight, the curable resin composition of the present invention may not be sufficiently cured, and if it exceeds 15 parts by weight, the storage stability may be lowered. A more preferred lower limit is 1 part by weight, and a more preferred upper limit is 7 parts by weight.

The curable resin composition of the present invention contains a curable resin.
The curable resin has a radical polymerizable functional group and is polymerized and cured by irradiation with light such as ultraviolet rays. In addition, the said radical polymerizable functional group means the photoreactive functional group which can superpose | polymerize with an ultraviolet-ray, and the upper limit with the preferable number of the said photoreactive functional groups in 1 molecule of the said curable resin is six. When it is more than 6, curing shrinkage increases, which may cause a decrease in adhesive strength.
In addition, when the curable resin composition of the present invention is used as a sealing agent for a liquid crystal display element, a sealing agent for a liquid crystal display element, or a vertical conduction material for a liquid crystal display element, from the viewpoint of reducing elution of the resin component into the liquid crystal The curable resin preferably has a hydrogen-bonding functional group in the molecule, and more preferably has a hydroxyl group or a urethane bond.
Moreover, it is preferable to have two or more addition-reactive functional groups in one molecule so as not to leave as much unreacted resin as possible after curing. By being in this range, after the polymerization or crosslinking reaction, the remaining unreacted compound is extremely reduced, and the curable resin composition of the present invention is used as a sealing agent for liquid crystal display elements, a sealing agent for liquid crystal display elements, or a liquid crystal display element. When used as a vertical conduction material, the liquid crystal is not contaminated.

  Examples of such curable resins include (meth) acrylic acid esters, ethylene derivatives, styrene derivatives, and the like. Among these, a (meth) acrylic acid ester is preferable from the viewpoint that polymerization or crosslinking proceeds rapidly with active radicals generated by irradiation with ultraviolet rays.

  Examples of the (meth) acrylic acid ester include urethane (meth) acrylate having a urethane bond, and epoxy (meth) acrylate obtained by modifying a compound having a glycidyl group with (meth) acrylic acid.

  Examples of the urethane (meth) acrylate include a derivative of a diisocyanate such as isophorone diisocyanate and a reactive compound that undergoes an addition reaction with an isocyanate such as acrylic acid or hydroxyethyl acrylate. These derivatives may be chain-extended with caprolactone or polyol. Examples of commercially available products include U-122P, U-340P, U-4HA, U-1084A (all manufactured by Shin-Nakamura Chemical Co., Ltd.), KRM7595, KRM7610, KRM7619 (all manufactured by Daicel UCB). Can be mentioned.

  Examples of the epoxy (meth) acrylate include epoxy (meth) acrylate derived from an epoxy resin such as bisphenol A type epoxy resin or propylene glycol diglycidyl ether and (meth) acrylic acid. Examples of commercially available products include EA-1020, EA-6320, EA-5520 (all manufactured by Shin-Nakamura Chemical Co., Ltd.), epoxy ester 70PA, epoxy ester 3002A (all manufactured by Kyoeisha Chemical Co., Ltd.), and the like. .

  In addition to the radically polymerizable functional group such as the (meth) acrylic acid ester, the curable resin further has a thermally reactive functional group such as a cyclic ether group such as an epoxy group or an oxetane group in one molecule. It may be. In the case of having such a functional group, the curable resin composition of the present invention is a combination type of a photo-curing type and a thermo-curing type. After being fastened, it can be completely cured by heat curing, and more accurate and easy work can be performed, and contamination of the liquid crystal can also be prevented.

  The resin having a radically polymerizable functional group and a thermally reactive functional group in one molecule is not particularly limited, and examples thereof include a partial (meth) acrylic acid-modified epoxy resin and a urethane-modified (meth) acrylic epoxy resin. .

  Examples of the partial (meth) acrylic acid-modified epoxy resin include novolak type epoxy resin, bisphenol type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, tris (hydroxyphenyl) alkyl type epoxy resin, and tetrakis (hydroxyphenyl). Examples include alkyl (epoxy) resins, cycloaliphatic epoxy resins and the like partially (meth) acrylated.

  Examples of the raw material epoxy resin of such a partial (meth) acrylic acid-modified epoxy resin include novolak type, phenol novolak type, cresol novolak type, biphenyl novolak type, trisphenol novolak type, dicyclopentadiene novolak type and the like. Examples of the bisphenol type include bisphenol A type, bisphenol F type, 2,2′-diallyl bisphenol A type, hydrogenated bisphenol type, polyoxypropylene bisphenol A type cyclic aliphatic epoxy, and the like.

As a commercial item of the said phenol novolak-type epoxy resin, for example, Epicron N-740, N-770, N-775 (all manufactured by Dainippon Ink & Chemicals), Epicoat 152, Epicoat 154 (all manufactured by Japan Epoxy Resin Co., Ltd.) ) And the like.
As a commercial item of the said cresol novolak type epoxy resin, for example, Epicron N-660, N-665, N-670, N-673, N-680, N-695, N-665-EXP, N-672-EXP (Dainippon Ink Chemical Co., Ltd.).

  Commercially available products of the bisphenol A type epoxy resin include, for example, Epicoat 828, Epicoat 834, Epicoat 1001, Epicoat 1004 (all manufactured by Japan Epoxy Resin Co., Ltd.), Epicron 850, Epicron 860, and Epicron 4055 (all Dainippon Ink Chemical Co., Ltd.) Manufactured by Kogyo Co., Ltd.).

  As a commercial item of the said bisphenol F-type epoxy resin, Epikote 807 (made by Japan Epoxy Resin Co., Ltd.), Epicron 830 (made by Dainippon Ink & Chemicals, Inc.), etc. are mentioned, for example.

  As a commercial item of the said cycloaliphatic epoxy resin, Celoxide 2021, Celoxide 2080, Celoxide 3000 (all are Daicel UCB Co., Ltd.) etc. are mentioned, for example.

The partially (meth) acrylated product of the epoxy resin can be obtained, for example, by reacting the epoxy resin and (meth) acrylic acid in the presence of a basic catalyst according to a conventional method.
An epoxy resin having a desired acrylate ratio can be obtained by appropriately changing the blending amount of the epoxy resin and (meth) acrylic acid. As a compounding quantity of the said epoxy resin and (meth) acrylic acid, Preferably, the minimum of carboxylic acid is 0.1 equivalent with respect to 1 equivalent of epoxy groups, and an upper limit is 0.5 equivalent, More preferably, epoxy The lower limit of the carboxylic acid is 0.2 equivalent and the upper limit is 0.4 equivalent with respect to 1 equivalent of the group.

The urethane-modified (meth) acrylic epoxy resin is obtained by the following method, for example.
A method of reacting a polyol with a bifunctional or higher functional isocyanate and further reacting a hydroxyl group-containing (meth) acrylic monomer and glycidol; It can be obtained by a method of reacting glycidol.
The urethane-modified (meth) acrylic epoxy resin can also be obtained by a method in which glycidol is reacted with a (meth) acrylate monomer having an isocyanate group. Specifically, for example, first, 1 mol of trimethylolpropane and 3 mol of isophorone diisocyanate are reacted under a tin-based catalyst. Examples thereof include a method of reacting hydroxyethyl acrylate which is an acrylic monomer having an isocyanate group and a hydroxyl group remaining in the obtained compound and glycidol which is an epoxy having a hydroxyl group.

  It does not specifically limit as said polyol, For example, ethylene glycol, glycerol, sorbitol, a trimethylol propane, (poly) propylene glycol etc. are mentioned.

  The isocyanate is not particularly limited as long as it is bifunctional or higher. For example, diphenylmethane diisocyanate (MDI), tolylene diisocyanate (TDI), xylene diisocyanate (XDI), isophorone diisocyanate (IPDI), naphthylene diisocyanate (NDI), Examples include tolidine diisocyanate (TPDI), hexamethylene diisocyanate (HDI), dicyclohexylmethane diisocyanate (HMDI), and trimethylhexamethylene diisocyanate (TMHDI).

  The (meth) acrylic acid ester monomer having a hydroxyl group is not particularly limited, and examples thereof include ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and polyethylene glycol. Mono (meth) acrylates of dihydric alcohols such as mono (meth) acrylates or di (meth) acrylates of trivalent alcohols such as trimethylolethane, trimethylolpropane and glycerin, epoxy acrylates such as bisphenol A-modified epoxy acrylate, etc. Is mentioned. These may be used independently and 2 or more types may be used together.

  The curable resin composition of the present invention may further contain a thermosetting resin in order to further improve the adhesiveness. It does not specifically limit as said thermosetting resin, For example, an epoxy resin, an oxetane resin, etc. are mentioned.

  Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type resin, cresol novolac type resin, biphenyl type epoxy resin, naphthalene type epoxy resin, and catechol type epoxy resin.

When the curable resin contains a cyclic ether group and has thermosetting properties, or when the curable resin contains the thermosetting resin, the curable resin composition of the present invention may further contain a curing agent. . The said hardening | curing agent can improve the adhesiveness and moisture resistance of hardened | cured material.
As the curing agent, a latent curing agent having a melting point of 100 ° C. or higher is preferably used. When a curing agent having a melting point of less than 100 ° C. is used, the storage stability may be remarkably deteriorated. Examples of such a curing agent include hydrazide compounds such as 1,3-bis [hydrazinocarbonoethyl-5-isopropylhydantoin], dicyandiamide, guanidine derivatives, 1-cyanoethyl-2-phenylimidazole, N- [2 -(2-Methyl-1-imidazolyl) ethyl] urea, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, N, N'-bis (2- Methyl-1-imidazolylethyl) urea, N, N ′-(2-methyl-1-imidazolylethyl) -adipamide, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-dihydroxy Imidazole derivatives such as methylimidazole, modified aliphatic polyamines, tetrahydrophthalic anhydride, ethylene glycol -Acid anhydrides such as bis (anhydrotrimellitate), addition products of various amines and epoxy resins, and the like. Further, as the curing agent, a coating curing agent in which the surface of the solid curing agent particles is coated with fine particles may be used.

  The preferable lower limit of the amount of the curing agent is 1 part by weight with respect to 100 parts by weight of the curable resin, and the preferable upper limit is 60 parts by weight. If it is out of this range, the adhesiveness of the cured product is lowered, and the liquid crystal characteristic deterioration in the high temperature and high humidity operation test may be accelerated. A more preferred lower limit is 5 parts by weight, and a more preferred upper limit is 50 parts by weight.

The curable resin composition of the present invention may further contain a silane coupling agent. The silane coupling agent has a role as an adhesion aid that improves adhesion to a glass substrate or the like.
Although it does not specifically limit as said silane coupling agent, Since it is excellent in the adhesive improvement effect with a glass substrate etc., and it can prevent the outflow in a liquid crystal by chemically bonding with curable resin, for example, (gamma) -amino Propyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-isocyanatopropyltrimethoxysilane, etc., and a structure in which the imidazole skeleton and alkoxysilyl group are bonded via a spacer group What consists of the imidazole silane compound which has is used suitably. These silane coupling agents may be used alone or in combination of two or more.

  The curable resin composition of the present invention may contain a filler for the purpose of improving the adhesiveness due to the stress dispersion effect and improving the linear expansion coefficient. The filler is not particularly limited, and examples thereof include silica particles, alumina, talc and the like.

  The curable resin composition of the present invention further includes a reactive diluent for adjusting viscosity, a thixotropic agent for adjusting thixotropy, a spacer such as polymer beads for adjusting panel gap, It may contain a curing accelerator such as P-chlorophenyl-1,1-dimethylurea, an antifoaming agent, a leveling agent, a polymerization inhibitor, and other additives.

In the curable resin composition of the present invention, the upper limit of the molar extinction coefficient at 350 nm measured in acetonitrile as a component other than the radical polymerization initiator is preferably 100 M ⁻¹ · cm ⁻¹ . When it exceeds 100 M ⁻¹ · cm ⁻¹ , the amount of the radical polymerization initiator absorbed in the ultraviolet rays irradiated to the curable resin composition of the present invention decreases, and the radical polymerization initiator dissociates and is curable. It may be difficult to fully polymerize the resin.

  For the value obtained by multiplying the molar extinction coefficient at 350 nm measured in acetonitrile of the radical polymerization initiator by the blending amount (% by weight) of the radical polymerization initiator at 350 nm measured in acetonitrile of components other than the radical polymerization initiator. The value obtained by multiplying the molar extinction coefficient by the blending amount (% by weight) other than the radical polymerization initiator is preferably 50 or less. When it exceeds 50, the blending amount of components other than the radical polymerization initiator is too large, and among the ultraviolet rays irradiated to the curable resin composition of the present invention, the amount absorbed by the radical polymerization initiator is too small, The radical polymerization initiator may dissociate and it may be difficult to sufficiently polymerize the curable resin.

The curable resin composition of the present invention preferably has an adhesive strength of 150 N / cm ² or more when the glass substrate is bonded and cured. If it is less than 150 N / cm ² , the strength of the obtained liquid crystal display element may be insufficient.
In addition, the said adhesive strength can be calculated | required from the tensile strength required, for example, after adhering and hardening two glass substrates using the curable resin composition of this invention, and peeling two glass substrates. it can.

The curable resin composition of the present invention preferably has a volume resistivity of 1 × 10 ¹³ Ω · cm and a dielectric constant of 3 or more at 100 kHz. When the volume resistance value is less than 1 × 10 ¹³ Ω · cm, it means that the curable resin composition of the present invention contains an ionic impurity, and the liquid crystal display element sealant and the liquid crystal display element use When used as a sealing agent or a vertical conduction material for a liquid crystal display element, ionic impurities are eluted into the liquid crystal when energized, which affects the liquid crystal driving voltage and may cause display unevenness. In addition, the dielectric constant of the liquid crystal is usually about ε // (parallel) is about 10 and ε⊥ (vertical) is about 3.5. Therefore, when the dielectric constant is less than 3, the curable resin composition is in the liquid crystal. May affect the liquid crystal driving voltage and cause display unevenness.

  The method for producing the curable resin composition of the present invention is not particularly limited. For example, the curable resin, the radical polymerization initiator, and additives that are blended as necessary are mixed by a conventionally known method. Methods and the like. At this time, in order to remove ionic impurities, it may be brought into contact with an ion-adsorbing solid such as a layered silicate mineral.

Since the curable resin composition of the present invention contains a radical polymerization initiator having both radical polymerization initiator groups that generate active radicals upon irradiation with light and hydrogen-bonding functional groups in one molecule, liquid crystal When used as a sealant for display elements, a sealing agent for liquid crystal display elements, or a vertical conduction material for liquid crystal display elements, the polymerization initiator will flow into the liquid crystal even if it is touched in an uncured state in the dropping method. And no contamination. The radical polymerization initiator has a molar extinction coefficient at 350 nm in acetonitrile of 200 to 10,000 M ⁻¹ · cm ⁻¹ in acetonitrile. Therefore, the liquid crystal display element sealing agent, the liquid crystal display element sealing agent, or the liquid crystal display element use When used as a vertical conduction material, the wavelength of ultraviolet rays irradiated when these are cured can be set to a low energy of 350 nm or more, and the liquid crystal is not deteriorated.
Therefore, a liquid crystal display element obtained by using at least one of a sealing agent for liquid crystal display elements, a sealing agent for liquid crystal display elements, and a vertical conduction material for liquid crystal display elements comprising the curable resin composition of the present invention is reliable. Therefore, it can be suitably used as a display panel for characters and symbols of office equipment, home appliances, automobile meters and the like.
The sealing agent for liquid crystal display elements or the sealing agent for liquid crystal display elements comprising the curable resin composition of the present invention is also one aspect of the present invention.

Further, in the liquid crystal display element, in general, a vertical conduction material is used in order to make vertical conduction between opposing electrodes on two transparent substrates. The vertical conduction material is usually configured by containing conductive fine particles in a curable resin composition.
The vertical conduction material for a liquid crystal display element comprising the curable resin composition of the present invention and conductive fine particles is also one aspect of the present invention.

  The conductive fine particles are not particularly limited. For example, metal fine particles; those obtained by subjecting resin substrate fine particles to metal plating (hereinafter referred to as metal plating fine particles); Those coated (hereinafter referred to as coated metal plated fine particles); and those metal fine particles, metal plated fine particles, and coated metal plated fine particles having protrusions on the surface. Especially, since it is excellent in the uniform dispersibility in a resin composition and electroconductivity, the metal plating fine particle and covering metal plating fine particle which gave gold plating are preferable.

  The minimum with the preferable compounding quantity with respect to 100 weight part of the said curable resin composition of the said electroconductive fine particles is 0.2 weight part, and a preferable upper limit is 5 weight part.

  The method for producing the vertical conduction material for a liquid crystal display element of the present invention is not particularly limited. For example, the curable resin composition, the conductive fine particles and the like are blended so as to have a predetermined blending amount, and a vacuum planetary type is used. The method of mixing with a stirring apparatus etc. is mentioned.

The method for producing a liquid crystal display element using at least one of the sealing agent for liquid crystal display elements of the present invention, the sealing agent for liquid crystal display elements of the present invention, and the vertical conduction material for liquid crystal display elements of the present invention is particularly limited. For example, it can be manufactured by the following method.
First, the sealing agent for liquid crystal display elements of the present invention is applied to one of two transparent substrates with electrodes such as an ITO thin film so as to have a predetermined pattern in which the liquid crystal inlet is released. Examples of the application method include screen printing and dispenser application. Furthermore, the vertical conduction material for a liquid crystal display element of the present invention is applied onto a predetermined electrode on the other transparent substrate. Examples of the application method include screen printing and dispenser application. Instead of using a vertical conduction material, it is possible to incorporate conductive fine particles in the sealant to achieve vertical conduction. Next, the two transparent substrates are opposed to each other via a spacer, and are overlapped while aligning. Thereafter, the seal portion and the vertical conduction material portion of the transparent substrate are cured by irradiation with ultraviolet rays of 350 nm or more. When the sealing agent for liquid crystal display elements of the present invention and the vertical conduction material for liquid crystal display elements of the present invention have thermosetting properties, they are further cured by heating in an oven at 100 to 200 ° C. for 1 hour to complete the curing. Finally, liquid crystal is injected from the liquid crystal injection port, and the injection port is closed using the sealing agent for liquid crystal display element of the present invention to produce a liquid crystal display element.

  Moreover, as a manufacturing method of the liquid crystal display element by a dripping method, for example, the liquid crystal display element sealant of the present invention is formed into a rectangular shape on one of two transparent substrates with electrodes such as an ITO thin film by screen printing, dispenser application, or the like. The seal pattern is formed. Further, a vertical conduction pattern is formed on a predetermined electrode on the other transparent substrate by screen printing, dispenser application or the like of the vertical conduction material for a liquid crystal display element of the present invention. Instead of using a vertical conduction material, it is possible to incorporate conductive fine particles in the sealant to achieve vertical conduction. Next, a liquid crystal micro-droplet is dropped onto the entire surface of the transparent substrate frame in an uncured state of the sealant, and the other transparent substrate is immediately overlapped in an uncured state of the vertically conductive material, and the seal portion and the vertically conductive material portion Are cured by irradiating them with ultraviolet rays of 350 nm or more. When the sealing agent for liquid crystal display elements of the present invention and the vertical conduction material for liquid crystal display elements of the present invention have thermosetting properties, the curing is further completed by heating and curing in an oven at 100 to 200 ° C. for 1 hour, A liquid crystal display element is produced.

  The liquid crystal display element using at least one of the sealing agent for liquid crystal display elements of the present invention, the sealing agent for liquid crystal display elements of the present invention, and the vertical conduction material for liquid crystal display elements of the present invention is also one aspect of the present invention. It is.

  The liquid crystal display element of the present invention preferably has a liquid crystal resistivity holding ratio of 10% or more. If it is less than 10%, the alignment of the liquid crystal is disturbed, which may be one of the causes of color unevenness. More preferably, it is 50% or more. The liquid crystal specific resistance can be measured by using a known liquid crystal specific resistance measuring device or the like, and the retention ratio of the liquid crystal specific resistance can be obtained by the following equation.

  The liquid crystal display element of the present invention preferably has a nematic-isotropic liquid transition point (NI point) change of 3 ° C. or less. If it exceeds 3 ° C., the alignment of the liquid crystal is disturbed, which may be one of the causes of color unevenness. The nematic-isotropic liquid transition point (NI point) can be measured by using a known thermal analyzer or the like, and the nematic-isotropic liquid transition point (NI point). The change can be obtained by the following equation.

The curable resin composition of the present invention contains a radical polymerization initiator having a radical polymerization initiating group and a hydrogen bonding functional group that generate active radicals when irradiated with light in one molecule, and a curable resin. Therefore, when used as a sealing agent for a liquid crystal display element, a sealing agent for a liquid crystal display element, or a vertical conduction material for a liquid crystal display element, the polymerization initiator can be used even when touching the liquid crystal in an uncured state in a dropping method or the like. It does not flow out into the liquid crystal and become contaminated. The radical polymerization initiator has a molar extinction coefficient at 350 nm in acetonitrile of 200 to 10,000 M ⁻¹ · cm ⁻¹ in acetonitrile. Therefore, the liquid crystal display element sealing agent, the liquid crystal display element sealing agent, or the liquid crystal display element use When used as a vertical conduction material, the wavelength of ultraviolet rays irradiated when curing them can be made to have a low energy of 350 nm or more, and the liquid crystal is not deteriorated.
Therefore, a liquid crystal display element obtained by using at least one of a sealing agent for liquid crystal display elements, a sealing agent for liquid crystal display elements, and a vertical conduction material for liquid crystal display elements comprising the curable resin composition of the present invention is reliable. Therefore, it can be suitably used as a display panel for characters and symbols of office equipment, home appliances, automobile meters and the like.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.

Synthesis of Compound (1) Phenyl sulfide (10 mol), aluminum chloride (10 mol), and carbon disulfide (2 L) were put into a three-necked flask equipped with a dropping funnel, a mechanical stirrer, and a hydrogen chloride gas trap, and stirred at 0 ° C. Isobutyryl chloride (10 mol) was slowly added dropwise to the reaction solution so that the reaction solution did not exceed 10 ° C., and the mixture was further stirred at room temperature for 24 hours. Ice water was added to the reaction solution to stop the reaction, and the organic layer was extracted with chloroform. The organic layer was washed with ion-exchanged water and then dried over anhydrous magnesium sulfate. The solution was concentrated and purified under reduced pressure to obtain a compound (1) having a structure represented by the following formula (5).

Synthesis of Compound (2) Compound (1) (5 mol), aluminum chloride (5 mol) and carbon disulfide (1 L) are placed in a three-necked flask equipped with a dropping funnel, a mechanical stirrer, and a hydrogen chloride gas trap, and stirred at 0 ° C. did. Benzoyl chloride (5 mol) was slowly added dropwise to the reaction solution so that the reaction solution did not exceed 10 ° C., and the mixture was further stirred at room temperature for 24 hours. Ice water was added to the reaction solution to stop the reaction, and the organic layer was extracted with chloroform. The organic layer was washed with ion-exchanged water and then dried over anhydrous magnesium sulfate. The solution was concentrated and purified under reduced pressure to obtain a compound (2) having a structure represented by the following formula (6).

Synthesis of radical polymerization initiator A Compound (2) (2 mol) and dimethyl sulfoxide (2 L) were placed in a flask under nitrogen, and a methanol solution of potassium hydroxide (potassium hydroxide: 2 mol / ethanol: 100 mL) was further added. Stir at room temperature. Paraformaldehyde (2 mol as an aldehyde unit) was added to the solution and stirred at room temperature for 5 hours. The solution was neutralized by adding hydrochloric acid, and the organic layer was extracted with ethyl acetate. The organic layer was washed with ion-exchanged water and then dried over anhydrous magnesium sulfate. The solution was concentrated and purified under reduced pressure to obtain radical polymerization initiator A having a structure represented by the following formula (7).

Synthesis of radical polymerization initiator B Compound (2) (1 mol) was placed in a reaction flask and dissolved by heating in a dry air atmosphere. Into this, 0.001 mol of dibutyltin dilaurate and 1 mol of 2-methacryloxyethylene isocyanate (manufactured by Showa Denko KK) are slowly added dropwise, and after completion of the addition, no isocyanate group remains by infrared absorption spectrum analysis at 90 ° C. And then purified at a temperature of 90 ° C. to obtain radical polymerization initiator B having a structure represented by the following formula (8).

Synthesis of radical polymerization initiator C Compound (2) (1 mol) was placed in a reaction flask and dissolved by heating in a dry air atmosphere. Dibutyltin dilaurate (0.001 mol), 2,2,4- and 2,4,4-trimethylhexamethylene diisocyanate (manufactured by Degussa, 0.5 mol) are slowly added so that the reaction temperature does not exceed 90 ° C. 2-hydroxyethyl acrylate (0.5 mol) was added after the addition was completed, and the reaction temperature was slowly added dropwise so that the reaction temperature did not exceed 90 ° C., until 90 isocyanate groups remained by infrared absorption spectrum analysis. The reaction was carried out at 0 ° C., followed by purification to obtain radical polymerization initiator C having a structure represented by the following formula (9).

  However, A in Formula (9) represents 2,2,4- and 2,4,4-trimethylhexamethylene groups.

Synthesis of Radical Polymerization Initiator D 2-Carboxymethoxythioxan-9-one (1 mol) was placed in a reaction flask and dissolved by heating in a dry air atmosphere. Into this, 0.001 mol of dibutyltin dilaurate and 1 mol of 2-methacryloxyethylene isocyanate (manufactured by Showa Denko KK) are slowly added dropwise, and after completion of the addition, no isocyanate group remains by infrared absorption spectrum analysis at 90 ° C. And then purified at a temperature of 90 ° C. to obtain radical polymerization initiator D having a structure represented by the following formula (10).

(Example 1)
2 parts by weight of radical polymerization initiator A, 40 parts by weight of partially acrylated epoxy resin (Daicel UCB, UVAC 1561), 20 parts by weight of bisphenol A epoxy acrylate resin (Daicel UCB, EB3700) Was heated to 70 ° C. to dissolve the radical polymerization initiator A, and then stirred using a planetary stirrer to obtain a mixture.
As a filler in this mixture, spherical silica (manufactured by Admatechs, SO-C1) 15 parts by weight, epoxy thermosetting agent (manufactured by Otsuka Chemical Co., ADH) 5 parts by weight, coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., KBM403) 1 After blending parts by weight and stirring with a planetary stirrer, the mixture was dispersed with three ceramic rolls to obtain a curable resin composition.

One part by weight of spacer fine particles (Micropearl SP-2055, manufactured by Sekisui Chemical Co., Ltd.) is dispersed in 100 parts by weight of the obtained curable resin composition, and two rubbed alignment films and a sealing agent for a liquid crystal display element are obtained. It applied with the dispenser to one side of the glass substrate with a transparent electrode.
Subsequently, a fine drop of liquid crystal (manufactured by Chisso Corporation, JC-5004LA) is dropped onto the entire surface of the sealant frame of the glass substrate with a transparent electrode, and the other glass substrate with a transparent electrode is immediately bonded together, and the sealant part Then, using a high pressure mercury lamp with a filter that cuts light of 350 nm or less, it was irradiated and cured at 50 mW / cm ² for 20 seconds to obtain a liquid crystal display element.

(Example 2)
A curable resin composition was obtained in the same manner as in Example 1 except that the radical polymerization initiator B was used instead of the radical polymerization initiator A in Example 1.
Then, the liquid crystal display element was obtained like Example 1 using the obtained curable resin composition.

(Example 3)
A curable resin composition was obtained in the same manner as in Example 1 except that the radical polymerization initiator C was used in place of the radical polymerization initiator A in Example 1.
Then, the liquid crystal display element was obtained like Example 1 using the obtained curable resin composition.

Example 4
A curable resin composition was obtained in the same manner as in Example 1 except that the radical polymerization initiator D was used in place of the radical polymerization initiator A in Example 1.
Then, the liquid crystal display element was obtained like Example 1 using the obtained curable resin composition.

(Comparative Example 1)
A curable resin composition was obtained in the same manner as in Example 1 except that Irgacure 2959 (manufactured by Nagase Sangyo Co., Ltd.) was used instead of the radical polymerization initiator A of Example 1.
Then, the liquid crystal display element was obtained like Example 1 using the obtained curable resin composition.

(Comparative Example 2)
A curable resin composition was obtained in the same manner as in Example 1 except that Irgacure 651 (manufactured by Nagase Sangyo Co., Ltd.) was used instead of the radical polymerization initiator A of Example 1.
Then, the liquid crystal display element was obtained like Example 1 using the obtained curable resin composition.

  The radical polymerization initiators, curable resin compositions and liquid crystal display devices obtained in Examples 1 to 4 and Comparative Examples 1 and 2 were evaluated by the following methods, and the results are shown in Table 1 below.

(Measurement of molar extinction coefficient)
A radical polymerization initiator solution was prepared using acetonitrile for ultraviolet absorption spectrum (manufactured by Dojin Chemical Co., Ltd.) so that the sample concentration was 1.0 × 10 ⁻⁴ M, and placed in a quartz cell with an optical path length (1 cm). Absorbance was measured using a spectrophotometer (UV-2450, manufactured by Shimadzu Corporation). The molar extinction coefficient was a value obtained by dividing the measured absorbance by the molar concentration (M) of the solution and the thickness (cm) of the cell.

(Measurement of liquid crystal specific resistance retention)
In an ampoule bottle (inner diameter: 10.0 mm), 0.5 g of the curable resin composition was added, and 0.5 g of liquid crystal was added. The bottle was put into an oven at 120 ° C. for 1 hour, and after returning to room temperature (25 ° C.), the liquid crystal part was measured for a liquid crystal resistivity measuring device (KEITHLEY Instruments, 6517A), and the electrode for liquid (manufactured by Ando Electric Co., Ltd., LE-21 type), and the liquid crystal specific resistance was measured in a standard temperature and humidity state (20 ° C., 65% RH). In addition, the liquid crystal specific resistance retention was calculated | required by the following formula.

(Nematic-isotropic liquid transition point (NI point) change measurement)
In an ampoule bottle (inner diameter: 10.0 mm), 0.5 g of the curable resin composition was added, and 0.5 g of liquid crystal was added. The bottle was put into an oven at 120 ° C. for 1 hour, and after returning to room temperature (25 ° C.), the liquid crystal portion was put into an aluminum pan and measured at a temperature rising rate of 10 ° C./min to measure the peak temperature. In addition, MDSC (made by TA Instruments) was used as a thermal analyzer. The change in nematic-isotropic liquid transition point was determined by the following formula.

(Measurement of acrylic group conversion)
In 100 parts by weight of the obtained curable resin composition, 1 part by weight of spacer fine particles (manufactured by Sekisui Chemical Co., Ltd., Micropearl SP-2055) is dispersed, and taken at the center of glass (Corning 1737), and another glass (Corning). 1737) was overlaid thereon to spread the curable resin composition to make the thickness uniform, thereby preparing a test piece.
The produced test piece was irradiated with a high pressure mercury lamp with a filter for cutting light of 350 nm or less at 50 mW / cm ² for 20 seconds. Thereafter, one glass of the test piece was peeled off, and measurement was performed using an infrared spectrophotometer (EXCALIBUR FTS3000MX, manufactured by BIO RAD). By comparing the peak area of the acrylate groups prior to curing was measured separately (815~800cm ^-1) and the peak area of the acrylate groups after curing (815~800cm ^-1) as the reference peak area (845~820cm ^-1) Conversion was calculated. The conversion rate of the acrylic group was calculated from the following formula.

  Conversion rate of acrylic group = {1- (peak area of acrylic group after curing / reference peak area after curing) / (peak area of acrylic group before curing / reference peak area before curing)} × 100

(Adhesion evaluation)
1 part by weight of spacer fine particles (manufactured by Sekisui Chemical Co., Ltd., Micropearl SP-2055) is dispersed in 100 parts by weight of the curable resin composition, taken at the center of the slide glass, and another slide glass is overlaid thereon. The curable resin composition was spread out to have a uniform thickness, and was irradiated at 50 mW / cm ² for 20 seconds using a high-pressure mercury lamp with a filter that cuts light of 350 nm or less. Thereafter, heating was performed at 120 ° C. for 1 hour to obtain an adhesion test piece. The adhesive strength of this test piece was measured using a tension gauge.

(Liquid crystal display panel evaluation (color unevenness evaluation))
About the obtained liquid crystal display element, the liquid crystal alignment disorder in the vicinity of the sealant was evaluated by visual observation according to the following criteria immediately after production and after an operation test for 1000 hours under the condition of 65 ° C. and 95% RH. The number of samples was 6.
◎: No color unevenness ○: Color unevenness is slightly △: Color unevenness is slightly ×: Color unevenness is considerable

(Example 5)
After thoroughly mixing the curable resin composition obtained in the same manner as in Example 1 using three rolls so as to form a uniform liquid, the conductive fine particles are used with respect to 100 parts by weight of the curable resin composition. 2 parts by weight of gold-plated metal plating fine particles (manufactured by Sekisui Chemical Co., Ltd., Micropearl AU-206) were mixed and mixed with a vacuum planetary stirrer to prepare a vertical conduction material for a liquid crystal display element.

  A liquid crystal display device was produced in the same manner as in Example 1 except that the vertical conduction pattern was formed on the electrode for vertical conduction by applying the obtained vertical conduction material on the transparent substrate by a dispenser.

  About the obtained liquid crystal display element, liquid crystal display panel evaluation (color unevenness evaluation) was performed similarly, and when the liquid crystal orientation disorder near vertical conduction material was observed visually, there was no color unevenness at all. Also, the conductivity was good.

According to the present invention, particularly when used as at least one of a sealing agent for a liquid crystal display element, a sealing agent for a liquid crystal display element, and a vertical conduction material for a liquid crystal display element in the production of a liquid crystal display element by a dropping method, Curable resin composition, liquid crystal display element sealing agent, liquid crystal display element sealing agent, which can realize high display quality and high reliability of the liquid crystal display element without deterioration of the liquid crystal due to ultraviolet rays applied to A vertically conductive material for a liquid crystal display element and a liquid crystal display element using these can be provided.

Claims (12)

A curable resin composition comprising a radical polymerization initiator having a radical polymerization initiating group that generates active radicals upon irradiation with light and a hydrogen bonding functional group in one molecule, and a curable resin,
The radical polymerization initiator has a molar extinction coefficient at 350 nm measured in acetonitrile of 200 to 10,000 M ⁻¹ · cm ⁻¹ . The curable resin composition according to claim 1, wherein the radical polymerization initiator has a molar extinction coefficient at 430 nm measured in acetonitrile of 100 M ⁻¹ · cm ⁻¹ or less.   The curable resin composition according to claim 1 or 2, wherein the curable resin has a hydrogen bonding functional group in one molecule.   The curable resin composition according to claim 1, wherein the hydrogen bonding functional group is a urethane group and / or a hydroxyl group.   The curable resin composition according to claim 1, 2, 3, or 4, wherein the radical polymerization initiator has a reactive functional group capable of reacting with and binding to the curable resin.   6. The curable resin composition according to claim 5, wherein at least one reactive functional group capable of reacting with and binding to the curable resin is a (meth) acryl group and / or an epoxy group.   Any of the active radicals generated by irradiating the radical polymerization initiator with light has at least one hydrogen-bonding functional group and a reactive functional group capable of reacting with and binding to the curable resin. The curable resin composition according to claim 5, wherein the curable resin composition is a curable resin composition.   The curable resin composition according to claim 1, 2, 3, 4, 5, 6, or 7, wherein the radical polymerization initiator has a number average molecular weight of 300 or more.   A sealing agent for liquid crystal display elements, comprising the curable resin composition according to claim 1, 2, 3, 4, 5, 6, 7 or 8.   A sealing agent for liquid crystal display elements, comprising the curable resin composition according to claim 1, 2, 3, 4, 5, 6, 7 or 8.   A vertical conducting material for a liquid crystal display element, comprising the curable resin composition according to claim 1, 2, 3, 4, 6, 7, or 8 and conductive fine particles. A sealing agent for a liquid crystal display element according to claim 9, a sealing agent for a liquid crystal display element according to claim 10, and a vertical conduction material for a liquid crystal display element according to claim 11 are used. Liquid crystal display element.