JP5564028B2 - Sealant for liquid crystal dropping method, vertical conduction material, and liquid crystal display element - Google Patents

Description

In the production of a liquid crystal display element by the dropping method, the present invention can be sufficiently cured even if there is a portion where light is not directly irradiated, and the liquid crystal is not deteriorated by ultraviolet rays irradiated when it is cured, The present invention relates to a liquid crystal dropping method sealing agent capable of realizing high display quality and high reliability of a liquid crystal display element, a 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, the positional displacement, gap variation, decrease in adhesion between the sealing agent and the substrate, etc. occur due to thermal strain; residual solvent thermally expands to generate bubbles, resulting in cap 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. In addition, similar sealing agents are disclosed in Patent Document 2, Patent Document 3, Patent Document 4, or Patent Document 5, and the like. Patent Document 6 discloses a liquid crystal sealant mainly composed of (meth) acrylate.

However, in the production of the liquid crystal display element by such a dripping method, since the uncured sealant directly contacts the liquid crystal, there is a problem that the sealant component is eluted into the liquid crystal and contaminates the liquid crystal.
In particular, in recent years, with the narrowing of the frame of the liquid crystal display part for the purpose of miniaturization of devices accompanying the widespread use of mobile devices with various liquid crystal panels such as mobile phones and portable game machines, the sealant pattern formed on the substrate is Although it has become a position that overlaps with the black matrix (BM) etc. in the thickness direction of the liquid crystal cell, the sealing agent formed at such a position overlapping with the BM etc. is irradiated with light such as ultraviolet rays. However, since the uncured portion remains, there is a problem in that the sealant component is eluted from the uncured portion into the liquid crystal to further contaminate the liquid crystal.

To solve such a problem, for example, a method of irradiating light from the back surface of the substrate, that is, the array side is conceivable. However, since metal wiring, transistors, and the like are also present on the array substrate, a portion that does not receive light on the sealant is formed, and a portion that does not harden after irradiation with light remains. In particular, if the part not exposed to light is 50 μm or more, a part where the sealant does not harden is likely to be formed, and if this part comes into contact with the liquid crystal, the liquid crystal is contaminated and liquid crystal display unevenness is likely to occur. It was.

On the other hand, when a liquid crystal display element is manufactured by a dropping method using a conventional sealing agent, it is necessary to irradiate ultraviolet rays having a short wavelength and high energy 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.

Japanese Patent Laid-Open No. 6-160872 JP-A-1-243029 JP 7-13173 A Japanese Patent Laid-Open No. 7-13174 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 can be sufficiently cured even when there is a portion where light is not directly irradiated on the sealing agent for liquid crystal dropping method in the production of a liquid crystal display element by the dropping method, Liquid crystal is not deteriorated by the irradiated ultraviolet rays, and a liquid crystal display element sealing agent capable of realizing a high display quality and high reliability of the liquid crystal display element, a vertical conduction material, and a liquid crystal display element using the same The purpose is to provide.

The present invention is a liquid crystal dropping method sealing agent containing a radical initiator that generates active radicals upon irradiation with light, a curable resin, and a solid organic acid hydrazide, wherein the radical initiator is in acetonitrile. molar absorption coefficient at the measured 350nm is 100 to 100,000 ^{M -1} · ^cm -1, more 60 mol% of the reactive functional groups contained in the curing resin (meth) liquid crystal dropping process for sealing an acryloyl group It is an agent.
The present invention is described in detail below.

As a result of intensive studies, the present inventors have found that when the sealing agent for liquid crystal dropping method has a property of being cured by ultraviolet rays having a long wavelength of about 350 nm, the black matrix (BM) ) Etc., even if it is a part where the irradiation of ultraviolet rays is shielded, it was found that it can be cured sufficiently and that the liquid crystal is not deteriorated because the energy of ultraviolet rays is low, and the present invention was completed. .

The sealing agent for liquid crystal dropping method of the present invention (hereinafter also referred to as the sealing agent of the present invention) contains a radical polymerization initiator, a curable resin, and a solid organic acid hydrazide.
The radical polymerization initiator has a lower limit of the molar extinction coefficient at 350 nm measured in acetonitrile of 100 M ⁻¹ · cm ⁻¹ and an upper limit of 100,000 M ⁻¹ · cm ⁻¹ . When it is less than 100 M ⁻¹ · cm ⁻¹ , there are a portion where the sealing agent of the present invention is directly irradiated with ultraviolet rays having a wavelength of about 350 nm, and a portion where ultraviolet irradiation is blocked by a black matrix (BM) or the like. None of the shielding parts in the case can be cured quickly and sufficiently. When it exceeds 100,000 M ⁻¹ · cm ⁻¹ , the surface of the portion directly irradiated when the sealing agent of the present invention is irradiated with ultraviolet rays having a wavelength of about 350 nm is cured first, and the inside is sufficiently cured. In addition, the portion where the ultraviolet rays are shielded by BM or the like cannot be sufficiently cured.
The preferred lower limit is 200 M ⁻¹ · cm ⁻¹ , the preferred upper limit is 10,000 M ⁻¹ · cm ⁻¹ , the more preferred lower limit is 300 M ⁻¹ · cm ⁻¹ , and the more preferred upper limit is 3000 M ⁻¹ · cm ⁻¹ . is there.

The radical polymerization initiator preferably has a molar extinction coefficient at 450 nm measured in acetonitrile of 100 M ⁻¹ · cm ⁻¹ or less. If it exceeds 100 M ⁻¹ · cm ⁻¹ , active radicals are generated by light having a wavelength in the visible light range, and handling becomes very poor.

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 is the intensity of transmitted light, Io is the intensity of transmitted light of the acetonitrile pure solvent, c is the molar concentration (M), d is the thickness (cm) of the solution layer, and log (Io / I ) Represents absorbance.

As described above, the radical polymerization initiator has a high molar extinction coefficient in long-wavelength ultraviolet light having a wavelength of about 350 nm, and sufficiently cures the sealing agent of the present invention when irradiated with long-wavelength ultraviolet light having a wavelength of about 350 nm. be able to. Further, even when such a long wavelength ultraviolet ray having a wavelength of about 350 nm is present on the sealing agent of the present invention, there is a shielding material that obstructs the transmission of black matrix (BM) or the like. Since the sealing agent of the present invention is shielded by a shielding material such as BM and is not directly irradiated with ultraviolet rays, the sealing agent of the present invention is irradiated with ultraviolet rays having a wavelength of about 350 nm. It can be cured sufficiently. Therefore, the sealing agent of the present invention can be particularly suitably used when manufacturing a liquid crystal display element by a dropping method with a narrow frame design.
Furthermore, since the sealing agent of the present invention can be sufficiently cured with ultraviolet rays having a wavelength of about 350 nm and low energy, even when it is used for manufacturing a liquid crystal display device by a dropping method, the ultraviolet rays are directly irradiated. Therefore, the liquid crystal is not deteriorated.

The radical polymerization initiator is not particularly limited as long as it satisfies the molar extinction coefficient. For example, the radical polymerization initiator has a radical polymerization initiation group such as a carbonyl group, a sulfur-containing group, an azo group, or an organic peroxide-containing group. Among them, groups having structures represented by the following general formulas (1) to (4) are preferable.

は、炭素原子数１〜６のアルキル基又はハロゲン基を有してもよい芳香環を表わす。 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 a liquid crystal display element is produced using the sealant of the present invention, unpolymerized or uncrosslinked components in the sealant are eluted into the liquid crystal due to heating during liquid crystal realignment, and the liquid crystal Orientation may be hindered, which may be one of the causes of color unevenness.

The radical polymerization initiator preferably contains a hydrogen bonding functional group.
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.
By having such a hydrogen bonding functional group, even when the uncured sealing agent of the present invention is in contact with the liquid crystal, the radical polymerization initiator is less likely to elute and 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 sealant 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), Examples include hexamethylene diisocyanate (HDI), dicyclohexylmethane diisocyanate (HMDI), and trimethylhexamethylene diisocyanate (TMHDI).
In the sealing agent of the present invention, the above radical polymerization initiators may be used alone or in combination of two or more.

Moreover, in the sealing agent of this invention, the said radical polymerization initiator can also use what is marketed. Examples of the radical polymerization initiators that are commercially available include Irgacure 907, Irgacure 819, Irgacure 651, Irgacure 369 (all of which are manufactured by Ciba Specialty Chemicals), benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl. Examples include ether and lucillin TPO (manufactured by BASF Japan). Among these, Irgacure 907, Irgacure 651, BIPE and Lucilin TPO are preferable because the molar extinction coefficient at 450 nm measured in acetonitrile is 100 M ⁻¹ · cm ⁻¹ .

The preferable lower limit of the blending amount of the radical polymerization initiator in the sealant of the present invention is 0.5 parts by weight with respect to 100 parts by weight of the curable resin described later, and the preferable upper limit is 10 parts by weight. If the amount is less than 0.5 parts by weight, the sealing agent of the present invention may not be sufficiently cured. If the amount exceeds 10 parts by weight, when the sealing agent of the present invention is irradiated with light, If the surface is hardened first, the inside cannot be hardened sufficiently, and if there is a part shielded by BM or the like, the part may not be hardened sufficiently. Moreover, the curing storage stability may be reduced.

The sealing agent of the present invention contains a curable resin.
The curable resin has a (meth) acryloyl group in its molecule, and in the sealing agent of the present invention, 60 mol% or more of the reactive functional group contained in the curable resin is a (meth) acryloyl group. is there.
In the present specification, the “reactive functional group” means a (meth) acryloyl group, a cyclic ether such as an epoxy group or an oxetanyl group, a styryl group, or the like.

When the (meth) acryloyl group is less than 60 mol% of the reactive functional group contained in the curable resin, the resin is not sufficiently cured by light irradiation and liquid crystal contamination occurs. A preferred lower limit is 75 mol%. In the present specification, the (meth) acryloyl group means an acryloyl group or a methacryloyl group.

Moreover, the preferable upper limit of the number of (meth) acryloyl groups in one molecule of the curable resin is 6. When it is more than 6, curing shrinkage increases, which may cause a decrease in adhesive strength.

In the sealing agent of the present invention, 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 one molecule, and more preferably has a hydroxyl group or a urethane bond. It is what you have.
Furthermore, the sealing agent of the present invention preferably has two or more addition-reactive functional groups in one molecule of the curable resin so as not to leave as much unreacted resin as possible after curing. By being in this range, the remaining unreacted compound is extremely reduced after polymerization or crosslinking reaction, and the liquid crystal is not contaminated when the liquid crystal display element is produced using the sealing agent of the present invention.

In the sealing agent of the present invention, the curable resin in which 60 mol% or more of the reactive functional group included is a (meth) acryloyl group is not particularly limited. For example, (meth) acrylic acid ester and reactive Examples thereof include those having a (meth) acryloyl group in the molecule by modifying the functional group. Of these, (meth) acrylic acid esters are preferred from the viewpoint of rapid polymerization or crosslinking by active radicals generated by irradiation with ultraviolet rays. In the present specification, (meth) acrylic acid means acrylic acid or methacrylic acid.

Examples of the (meth) acrylic acid ester include an ester compound obtained by reacting a compound having a hydroxyl group with (meth) acrylic acid, and an epoxy obtained by reacting (meth) acrylic acid with an epoxy compound ( Examples thereof include urethane (meth) acrylates obtained by reacting (meth) acrylates and isocyanates with (meth) acrylic acid derivatives having a hydroxyl group.

The ester compound obtained by reacting the above (meth) acrylic acid with a compound having a hydroxyl group is not particularly limited. Examples of monofunctional compounds include 2-hydroxyethyl acrylate and 2-hydroxypropyl (meth) acrylate. 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate , Isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, methoxyethylene glycol (meth) acrylate, 2-ethoxyethyl (meth) acrylate, tet Hydrofurfuryl (meth) acrylate, benzyl (meth) acrylate, ethyl carbitol (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) Acrylate, 2,2,2, -trifluoroethyl (meth) acrylate, 2,2,3,3, -tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H, -octafluoropentyl (meth) acrylate, imide (Meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, Rohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isononyl (meth) acrylate, isomyristyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) ) Acrylate, bicyclopentenyl (meth) acrylate, isodecyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyl Roxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl 2-hydroxypropyl phthalate, glycidyl (meth) acrylate, 2- (meth) acryloyloxyethyl phosphate, etc. It is done.

Examples of the bifunctional compound include 1,4-butanediol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and 1,9. -Nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate 2-n-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, dipropylene glycol di (meth) acrylate , Tripropylene glycol di (meth) acrylate, polypropylene glycol (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, Pyrene oxide-added bisphenol A di (meth) acrylate, ethylene oxide-added bisphenol A di (meth) acrylate, ethylene oxide-added bisphenol F di (meth) acrylate, dimethylol dicyclopentadiene didi (meth) acrylate, 1,3-butylene glycol di ( (Meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide modified isocyanuric acid di (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, carbonate diol di (meth) acrylate, poly Ether diol di (meth) acrylate, polyester diol di (meth) acrylate, polycaprolactone diol di (meth) acrylate, polybutadiene geo Distearate (meth) acrylate.

Examples of the tri- or higher functional group include pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, propylene oxide-added trimethylolpropane tri (meth) acrylate, and ethylene oxide-added trimethylolpropane tri (meth). Acrylate, caprolactone-modified trimethylolpropane tri (meth) acrylate, ethylene oxide-added isocyanuric acid tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, Pentaerythritol tetra (meth) acrylate, glycerin tri (meth) acrylate, propylene oxide-added glycerin Li (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, and the like.

The epoxy (meth) acrylate obtained by reacting the (meth) acrylic acid with an epoxy compound is not particularly limited. For example, an epoxy resin and (meth) acrylic acid are present in the presence of a basic catalyst according to a conventional method. What is obtained by reacting under is mentioned.

The epoxy compound as a raw material for synthesizing the epoxy (meth) acrylate is not particularly limited, and examples of commercially available products include bisphenols such as Epicoat 828EL and Epicoat 1004 (both manufactured by Japan Epoxy Resin Co., Ltd.). A type epoxy resin; Bisphenol F type epoxy resin such as Epicoat 806 and Epicoat 4004 (both manufactured by Japan Epoxy Resin Co.); Bisphenol S type epoxy resin such as Epicron EXA1514 (Dainippon Ink Co.); RE-810NM (Nipponization) 2,2'-diallyl bisphenol A type epoxy resin such as Yakuhin Co., Ltd .; Hydrogenated bisphenol type epoxy resin such as Epicron EXA7015 (Dainippon Ink Co., Ltd.); Propylene oxide addition such as EP-4000S (Asahi Denka Co., Ltd.) Bisf Knoll A type epoxy resin; Resorcinol type epoxy resin such as EX-201 (manufactured by Nagase ChemteX); Biphenyl type epoxy resin such as Epicoat YX-4000H (manufactured by Japan Epoxy Resin); YSLV-50TE (manufactured by Tohto Kasei Co., Ltd.) Sulfide type epoxy resins such as YSLV-80DE (manufactured by Tohto Kasei Co., Ltd.); Dicyclopentadiene type epoxy resins such as EP-4088S (manufactured by Asahi Denka Co.); Epicron HP4032 and Epicron EXA-4700 (any Naphthalene-type epoxy resin such as Dainippon Ink Co .; phenol novolac epoxy resin such as Epicron N-770 (Dainippon Ink Co.); Epicron N-670-EXP-S (Dainippon Ink Co.) Orthocresol novolac epoxy resin; Dicyclopentadiene novolac type epoxy resin such as Piclon HP7200 (manufactured by Dainippon Ink &Co.); Biphenyl novolac type epoxy resin such as NC-3000P (manufactured by Nippon Kayaku Co., Ltd.); Naphthalene phenol such as ESN-165S (manufactured by Tohto Kasei Co., Ltd.) Novolac type epoxy resin; Glycidylamine type epoxy resin such as Epicote 630 (manufactured by Japan Epoxy Resin Co., Ltd.), Epiklon 430 (manufactured by Dainippon Ink and Co., Ltd.), TETRAD-X (manufactured by Mitsubishi Gas Chemical Company); ZX-1542 (Tohto Kasei Co., Ltd.) ), Epiklon 726 (Dainippon Ink Co., Ltd.), Epolite 80MFA (Kyoeisha Chemical Co., Ltd.), Denacol EX-611, (Nagase ChemteX Co., Ltd.) and other alkyl polyol type epoxy resins; YR-450, YR-207 ( All are manufactured by Toto Kasei Co., Ltd.) Rubber-modified epoxy resins such as Daicel Chemical Industries; glycidyl ester compounds such as Denacol EX-147 (manufactured by Nagase ChemteX); Bisphenol A type episulfide resins such as Epicoat YL-7000 (manufactured by Japan Epoxy Resin); Others YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Toto Kasei Co., Ltd.), XAC4151 (manufactured by Asahi Kasei Co., Ltd.), Epicoat 1031, Epicoat 1032 (all manufactured by Japan Epoxy Resin Co., Ltd.), EXA-7120 (Dainippon Ink) ), TEPIC (Nissan Chemical Co., Ltd.) and the like.

Specific examples of the epoxy (meth) acrylate obtained by reacting the (meth) acrylic acid with the epoxy compound include, for example, resorcinol type epoxy resin (EX-201, manufactured by Nagase ChemteX Corporation) 360 parts by weight. In addition, 2 parts by weight of p-methoxyphenol as a polymerization inhibitor, 2 parts by weight of triethylamine as a reaction catalyst, and 210 parts by weight of acrylic acid can be obtained by reacting at 90 ° C. for 5 hours while stirring under reflux.

Moreover, as a commercial item of the said epoxy (meth) acrylate, for example, Evecri 3700, Evekril 3600, Evekril 3701, Evekrill 3703, Evekrill 3200, Evekrill 3201, Evekrill 3600, Evekrill 3702, Evekrill 3412, Evekril 860, Evekril RDX63182, 6040, Evekril 3800 (all manufactured by Daicel UCB), EA-1020, EA-1010, EA-5520, EA-5323, EA-CHD, EMA-1020 (all manufactured by Shin-Nakamura Chemical Co., Ltd.), epoxy ester M-600A, epoxy ester 40EM, epoxy ester 70PA, epoxy ester 200PA, epoxy ester 80MFA, epoxy ester 3002M, epoxy Steal 3002A, Epoxy ester 1600A, Epoxy ester 3000M, Epoxy ester 3000A, Epoxy ester 200EA, Epoxy ester 400EA (all manufactured by Kyoeisha Chemical Co., Ltd.), Denacol acrylate DA-141, Denacol acrylate DA-314, Denacol acrylate DA- 911 (all manufactured by Nagase ChemteX Corporation).

Examples of the urethane (meth) acrylate obtained by reacting the above isocyanate with a (meth) acrylic acid derivative having a hydroxyl group include, for example, a (meth) acrylic acid derivative having a hydroxyl group with respect to 1 equivalent of a compound having two isocyanate groups. Two equivalents can be obtained by reacting in the presence of a catalytic amount of a tin-based compound.

It does not specifically limit as isocyanate used as the raw material of the urethane (meth) acrylate obtained by making the said isocyanate react with the (meth) acrylic acid derivative which has a hydroxyl group, For example, 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) Ofosufeto, tetramethyl xylene diisocyanate, 1,6,10- undecene country isocyanate.

Moreover, it does not specifically limit as isocyanate used as the raw material of the urethane (meth) acrylate obtained by making the said isocyanate react with the (meth) acrylic acid derivative which has a hydroxyl group, For example, ethylene glycol, glycerol, sorbitol, a trimethylol propane It is also possible to use chain-extended isocyanate compounds obtained by reaction of polyols such as (poly) propylene glycol, carbonate diol, polyether diol, polyester diol, polycaprolactone diol and excess isocyanate.

The (meth) acrylic acid derivative having a hydroxyl group, which is a raw material for the urethane (meth) acrylate obtained by reacting the isocyanate with a hydroxyl group-containing (meth) acrylic acid derivative, is not particularly limited. For example, 2-hydroxy Commercial products such as ethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, ethylene glycol, propylene glycol, 1,3-propanediol, Mono (meth) acrylates of trivalent alcohols such as mono (meth) acrylates of divalent alcohols such as 1,3-butanediol, 1,4-butanediol and polyethylene glycol, trimethylolethane, trimethylolpropane and glycerin Or di (meth) acrylate, epoxy acrylates such as bisphenol A-modified epoxy acrylate.

Specific examples of urethane (meth) acrylate obtained by reacting the isocyanate with a hydroxyl group-containing (meth) acrylic acid derivative include, for example, 134 parts by weight of trimethylolpropane, and 0.2 part by weight of BHT as a polymerization inhibitor. Then, 0.01 parts by weight of dibutyltin dilaurate and 666 parts by weight of isophorone diisocyanate were added as reaction catalysts, and the mixture was reacted at 60 ° C. with stirring under reflux for 2 hours. Then, 51 parts by weight of 2-hydroxyethyl acrylate was added, and air was fed. The mixture can be obtained by reacting at 90 ° C. with stirring under reflux for 2 hours.

Examples of commercially available urethane (meth) acrylates include M-1100, M-1200, M-1210, and M-1600 (all manufactured by Toagosei Co., Ltd.), Evecryl 230, Evekril 270, Evekril 4858, Evecryl 8402, Evecril 8804, Evecril 8803, Evecril 8807, Evecril 9260, Evecril 1290, Evecril 5842, Evecril 210, Evecril 4827, Evecril 6700, Evecril 220, Evecryl 2220 UN-9000H, Art Resin UN-9000A, Art Resin UN-7100, Art Resin UN-1255, Art Resin UN-330, Art Resin UN-3320 B, Art Resin UN-1200TPK, Art Resin SH-500B (all manufactured by Negami Kogyo Co., Ltd.), U-122P, U-108A, U-340P, U-4HA, U-6HA, U-324A, U-15HA, UA-5201P, UA-W2A, U-1084A, U-6LPA, U-2HA, U-2PHA, UA-4100, UA-7100, UA-4200, UA-4400, UA-340P, U-3HA, UA- 7200, U-2061BA, U-10H, U-122A, U-340A, U-108, U-6H, UA-4000 (all manufactured by Shin-Nakamura Chemical Co., Ltd.), AH-600, AT-600, UA- 306H, AI-600, UA-101T, UA-101I, UA-306T, UA-306I, and the like.

In the sealing agent of the present invention, the curable resin may be, for example, a compound having at least one epoxy group and (meth) acryloyl group in one molecule.

Examples of the compound having at least one epoxy group and (meth) acryloyl group in one molecule include, for example, reacting a part of the epoxy group having two or more epoxy groups with (meth) acrylic acid. And a compound obtained by reacting a bifunctional or higher isocyanate with a (meth) acrylic acid derivative having a hydroxyl group and glycidol.

Examples of the compound obtained by reacting a part of the epoxy group having two or more epoxy groups with (meth) acrylic acid include, for example, an epoxy resin and (meth) acrylic acid in a basic manner according to a conventional method. It is obtained by reacting in the presence of a catalyst.

Examples of the epoxy compound used as a raw material of the compound obtained by reacting a part of the epoxy group having two or more epoxy groups with (meth) acrylic acid include, for example, Epicoat 828EL and Epicoat 1004 (both Japan Epoxy Bisphenol A type epoxy resin such as Epicote 806 and Epicoat 4004 (both made by Japan Epoxy Resin Co.); Bisphenol S type epoxy resin such as Epicron EXA1514 (manufactured by Dainippon Ink and Co.) ; 2,2′-diallyl bisphenol A type epoxy resin such as RE-810NM (manufactured by Nippon Kayaku Co., Ltd.), hydrogenated bisphenol type epoxy resin such as Epicron EXA7015 (manufactured by Dainippon Ink &Co.); EP-4000S (Asahi Denka Co., Ltd.) Etc.) Lopylene oxide-added bisphenol A type epoxy resin; Resorcinol type epoxy resin such as EX-201 (manufactured by Nagase ChemteX); Biphenyl type epoxy resin such as Epicoat YX-4000H (manufactured by Japan Epoxy Resin); YSLV-50TE (Tohto Kasei) Such as YSLV-80DE (manufactured by Tohto Kasei Co., Ltd.); dicyclopentadiene type epoxy resin such as EP-4088S (manufactured by Asahi Denka Co.); Epicron HP4032, Epicron EXA- Naphthalene type epoxy resin such as 4700 (all manufactured by Dainippon Ink Co.); Phenol novolac type epoxy resin such as Epicron N-770 (manufactured by Dainippon Ink Co.); Epicron N-670-EXP-S (manufactured by Dainippon Ink Co., Ltd.) ) Etc. Novolac type epoxy resin; dicyclopentadiene novolac type epoxy resin such as Epiklon HP7200 (manufactured by Dainippon Ink &Co.); biphenyl novolac type epoxy resin such as NC-3000P (manufactured by Nippon Kayaku Co., Ltd.); ESN-165S (manufactured by Toto Kasei Co., Ltd.) Naphthalenephenol novolak type epoxy resins such as Epicote 630 (manufactured by Japan Epoxy Resin Co., Ltd.), Epiklon 430 (manufactured by Dainippon Ink Co., Ltd.), TETRAD-X (manufactured by Mitsubishi Gas Chemical Company), etc .; ZX- 1542 (manufactured by Tohto Kasei Co., Ltd.), Epicron 726 (manufactured by Dainippon Ink & Co., Ltd.), Epolite 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.), Denacol EX-611, (manufactured by Nagase ChemteX Corporation), etc .; YR-207 (East Rubber-modified epoxy resins such as Tokasei Co., Ltd., Epolide PB (manufactured by Daicel Chemical Industries), etc .; Glycidyl ester compounds such as Denacol EX-147 (manufactured by Nagase ChemteX Corporation); Epicoat YL-7000 (manufactured by Japan Epoxy Resin Co., Ltd.) Bisphenol A type episulfide resin such as YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Tohto Kasei Co., Ltd.), XAC4151 (manufactured by Asahi Kasei Co., Ltd.), Epicoat 1031 and Epicoat 1032 (all manufactured by Japan Epoxy Resin Co., Ltd.) EXA-7120 (Dainippon Ink Co., Ltd.), TEPIC (Nissan Chemical Co., Ltd.) and the like.

Specific examples of the compound obtained by reacting a part of the epoxy group having two or more epoxy groups with (meth) acrylic acid include, for example, a phenol novolac type epoxy resin (manufactured by Dow Chemical Company): DEN 431) 1000 parts by weight, 2 parts by weight of p-methoxyphenol as a polymerization inhibitor, 2 parts by weight of triethylamine as a reaction catalyst, and 200 parts by weight of acrylic acid while stirring at 90 ° C. while refluxing. It can be obtained by reacting for 5 hours (in this case 50% partially acrylated).

Among the compounds obtained by reacting a part of the epoxy groups having two or more epoxy groups with (meth) acrylic acid, a commercially available product is, for example, Evecryl 1561 (manufactured by Daicel UC Corporation). It is done.

The compound obtained by reacting the (meth) acrylic acid derivative having a hydroxyl group with the bifunctional or higher isocyanate and glycidol is, for example, (meth) acrylic acid having a hydroxyl group with respect to 1 equivalent of the compound having two isocyanate groups. One equivalent each of the derivative and glycidol can be obtained by reacting in the presence of a catalytic amount of a tin-based compound.

The bifunctional or higher isocyanate used as a raw material for the compound obtained by reacting the bifunctional or higher isocyanate with a (meth) acrylic acid derivative having a hydroxyl group and glycidol is not particularly limited. For example, 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 dii Sosinate, tolidine diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris (isocyanate) Sulfonate phenyl) thiophosphate, tetramethylxylene diisocyanate, 1,6,10- undecene country isocyanate.

Examples of the isocyanate include, for example, a reaction between a polyol such as ethylene glycol, glycerin, sorbitol, trimethylolpropane, (poly) propylene glycol, carbonate diol, polyether diol, polyester diol, polycaprolactone diol and excess isocyanate. The resulting chain-extended isocyanate compound can also be used.

The (meth) acrylic acid derivative having a hydroxyl group, which is a raw material for the compound obtained by reacting a hydroxyl group-containing (meth) acrylic acid derivative and glycidol with the bifunctional or higher isocyanate, is not particularly limited. -Commercial products such as hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, ethylene glycol, propylene glycol, 1,3- Mono (meth) acrylates of dihydric alcohols such as propanediol, 1,3-butanediol, 1,4-butanediol, polyethylene glycol, etc., monovalents of trivalent alcohols such as trimethylolethane, trimethylolpropane, glycerin ( Meta) Relate or di (meth) acrylate, epoxy acrylates such as bisphenol A-modified epoxy acrylate.

Specific examples of the compound obtained by reacting a (meth) acrylic acid derivative having a hydroxyl group with a bifunctional or higher isocyanate and glycidol include, for example, 134 parts by weight of trimethylolpropane, and BHT0.2 as a polymerization initiator. Parts by weight, 0.01 parts by weight of dibutyltin dilaurate and 666 parts by weight of isophorone diisocyanate as reaction catalysts were added and reacted at 60 ° C. with stirring under reflux for 2 hours, followed by 25.5 parts by weight of 2-hydroxyethyl acrylate and glycidol It can be obtained by adding 111 parts by weight and reacting at 90 ° C. while refluxing for 2 hours while feeding air.

The sealing agent of the present invention may contain a curable resin other than the curable resin having a (meth) acryloyl group in the molecule, specifically, for example, epoxy resin, oxetane resin, ethylene Derivatives, styrene derivatives and the like.

The epoxy resin is not particularly limited, and examples thereof include epichlorohydrin derivatives, cycloaliphatic epoxy resins, compounds obtained from the reaction of isocyanate and glycidol, and the like.

Examples of the epichlorohydrin derivative include bisphenol A type epoxy resins such as Epicoat 828EL and Epicoat 1004 (both manufactured by Japan Epoxy Resin Co.); bisphenols such as Epicoat 806 and Epicoat 4004 (both manufactured by Japan Epoxy Resin Co., Ltd.). F type epoxy resin; Bisphenol S type epoxy resin such as Epicron EXA1514 (manufactured by Dainippon Ink &Co.); 2,2′-diallylbisphenol A type epoxy resin such as RE-810NM (manufactured by Nippon Kayaku Co., Ltd.); Epicron EXA7015 (large Hydrogenated bisphenol type epoxy resins such as Nippon Ink Co., Ltd .; Propylene oxide-added bisphenol A type epoxy resins such as EP-4000S (Asahi Denka Co.); Resorcinol type epoxy such as EX-201 (manufactured by Nagase ChemteX) Xylon resin; Biphenyl type epoxy resin such as Epicoat YX-4000H (manufactured by Japan Epoxy Resin Co., Ltd.); Sulfide type epoxy resin such as YSLV-50TE (manufactured by Toto Kasei Co., Ltd.); Ether type such as YSLV-80DE (manufactured by Toto Kasei Co., Ltd.) Epoxy resin; Dicyclopentadiene type epoxy resin such as EP-4088S (Asahi Denka); Naphthalene type epoxy resin such as Epicron HP4032, Epicron EXA-4700 (both manufactured by Dainippon Ink and Co.); Epicron N-770 (Large) Phenol novolac type epoxy resins such as Nippon Ink Co .; orthocresol novolac type epoxy resins such as Epicron N-670-EXP-S (Dainippon Ink Co.); dicyclo such as Epicron HP7200 (Dainippon Ink Co., Ltd.) Pentadiene novolac epoxy Fat; Biphenyl novolac type epoxy resin such as NC-3000P (manufactured by Nippon Kayaku Co., Ltd.); Naphthalene phenol novolac type epoxy resin such as ESN-165S (manufactured by Tohto Kasei Co., Ltd.); Epicoat 630 (manufactured by Japan Epoxy Resin Co., Ltd.) (Manufactured by Dainippon Ink, Inc.), glycidylamine type epoxy resins such as TETRAD-X (manufactured by Mitsubishi Gas Chemical Co., Inc.); Chemical), Denacol EX-611 (manufactured by Nagase ChemteX), etc., alkyl polyol type epoxy resins, YR-450, YR-207 (all manufactured by Tohto Kasei Co., Ltd.), Epolide PB (manufactured by Daicel Chemical) Rubber-modified epoxy resin, Denacol EX-147 (Nagase Chemtech) Glycidyl ester compounds such as Epicote YL-7000 (manufactured by Japan Epoxy Resin Co., Ltd.), etc .; other YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Toto Kasei Co., Ltd.), XAC4151 (made by Asahi Kasei Co., Ltd.), Epicoat 1031, Epicoat 1032 (all made by Japan Epoxy Resin Co., Ltd.), EXA-7120 (Dainippon Ink Co., Ltd.), TEPIC (Nissan Chemical Co., Ltd.), etc. are mentioned.

Examples of the cycloaliphatic epoxy resin include Celoxide 2021, Celoxide 2080, Celoxide 3000, Epolide GT300, EHPE (all manufactured by Daicel Chemical Industries), and the like.

The compound obtained from the reaction between the isocyanate and glycidol can be obtained, for example, by reacting a compound having two isocyanate groups with 2 equivalents of glycidol in the presence of a catalytic amount of a tin compound. .

Examples of the isocyanate include isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4,4′-diisocyanate (MDI), hydrogenated MDI, and polymeric. MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris (isocyanatophenyl) thiophosphate, tetramethylxylene diisocyanate 1,6,10-undecane triisocyanate and the like.

Examples of the isocyanate include, for example, a reaction between a polyol such as ethylene glycol, glycerin, sorbitol, trimethylolpropane, (poly) propylene glycol, carbonate diol, polyether diol, polyester diol, polycaprolactone diol and excess isocyanate. The resulting chain-extended isocyanate compound can also be used.

As a specific synthesis method of the compound obtained from the reaction of the isocyanate and glycidol, specifically, for example, 134 parts by weight of trimethylolpropane, 0.01 part by weight of dibutyltin dilaurate as a reaction catalyst, 666 parts by weight of isophorone diisocyanate The reaction mixture can be obtained by adding 2 parts and reacting at 60 ° C. with reflux stirring for 2 hours, and then adding 222 parts by weight of glycidol and reacting at 90 ° C. with reflux stirring for 2 hours while feeding air.

The sealing agent of the present invention further contains a solid organic acid hydrazide. By containing the solid organic acid hydrazide, the curability of the sealing agent of the present invention by irradiation with ultraviolet rays is improved. The reason for this is not clear, but is thought to be as follows.
That is, the solid organic acid hydrazide contained in the sealing agent of the present invention scatters the irradiated ultraviolet light in the sealing agent of the present invention, so that, for example, the portion irradiated with ultraviolet light irradiated with BM or the like is shielded. It is considered that the ultraviolet rays circulate, and as a result, the curability of the sealing agent of the present invention is improved.

The solid organic acid hydrazide is not particularly limited. For example, sebacic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide, other Amicure VDH, Amicure UDH (all manufactured by Ajinomoto Fine Techno Co., Ltd.), 2MZA-PW (Shikoku Chemicals) And ADH (manufactured by Otsuka Chemical Co., Ltd.).

Although it does not specifically limit as a compounding quantity of the said solid organic acid hydrazide, A preferable minimum is 1 weight part and a preferable upper limit is 50 weight part with respect to 100 weight part of said curable resins. If it is less than 1 part by weight, the effect of improving the curability of the sealant of the present invention is hardly obtained by blending solid organic acid hydrazide, and if it exceeds 50 parts by weight, the viscosity of the sealant of the present invention is not obtained. May become high and handling property may be impaired. A more preferred upper limit is 30 parts by weight.

In addition, since the solid organic acid hydrazide is usually used as a thermosetting agent for a sealing agent, when the solid organic acid dihydrazide is contained, heat for curing the sealing agent of the present invention by heat as it is. It can act as a curing agent.

The sealing agent of the present invention may contain a thermosetting agent other than the solid organic acid hydrazide. For example, as the thermosetting agent, an amine compound, a polyhydric phenol compound, an acid anhydride, or the like is contained. It may be.

The sealing agent of the present invention preferably further contains a silane coupling agent. The silane coupling agent mainly has a role as an adhesion assistant for favorably bonding the sealing agent and the liquid crystal display element substrate.

In addition to the (meth) acryloyl group, the curable resin may further have a thermally reactive functional group such as an epoxy group or a cyclic ether group such as an oxetane group in one molecule. In the case of having such a functional group, the sealing agent of the present invention is a combination type of a photo-curing type and a thermo-curing type, and is temporarily fixed by photo-curing in advance when a liquid crystal display element is produced by a dropping method. In addition to being completely cured by heat curing, more accurate and easy work can be performed, and contamination of the liquid crystal can also be prevented.

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

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.

Examples of commercially available phenol novolac epoxy resins include Epicron N-740, N-770, N-775 (all manufactured by Dainippon Ink and Chemicals), Epicoat 152, and Epicoat 154 (all Japan Epoxy Resin Co., Ltd.). Manufactured) 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 and Chemicals). 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) ), Tolidine diisocyanate (TPDI), hexamethylene diisocyanate (HDI), dicyclohexylmethane diisocyanate (HMDI), trimethylhexamethylene diisocyanate (TMHDI) and the like.

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 sealing agent 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 sealing agent 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 100 ° C. or lower 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 And 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 sealing agent 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 sealing agent 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, for example, talc, asbestos, silica, diatomaceous earth, smectite, bentonite, calcium carbonate, magnesium carbonate, alumina, montmorillonite, diatomaceous earth, zinc oxide, iron oxide, magnesium oxide, tin oxide, titanium oxide, Magnesium hydroxide, aluminum hydroxide, glass beads, silicon nitride, barium sulfate, gypsum, calcium silicate, talc, glass beads, sericite activated clay, bentonite, aluminum nitride and other inorganic fillers, polyester fine particles, polyurethane fine particles, vinyl heavy Organic fillers such as coalesced fine particles and acrylic polymer fine particles can be mentioned.

The sealing agent of the present invention further includes a reactive diluent for adjusting the viscosity, a thixotropic agent for adjusting thixotropy, a spacer such as polymer beads for adjusting the panel gap, and 3-P-chlorophenyl, if necessary. A curing accelerator such as -1,1-dimethylurea, an antifoaming agent, a leveling agent, a polymerization inhibitor, and other additives may be contained.

In the sealing agent 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 sealing agent of the present invention decreases, and the radical polymerization initiator is dissociated to sufficiently dissipate the curable resin. It may be difficult to polymerize.

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. If it exceeds 50, the amount of components other than the radical polymerization initiator is excessively increased, and the amount of the radical polymerization initiator absorbed in the ultraviolet rays irradiated to the sealing agent of the present invention becomes too small, and radical polymerization is initiated. The agent may dissociate and it may be difficult to sufficiently polymerize the curable resin.

The sealing agent 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, for example from the tensile strength required to peel off two glass substrates, after adhering and hardening two glass substrates using the sealing compound of this invention.

In the sealing agent of the present invention, it is preferable that the volume resistance value of the cured product is 1 × 10 ¹³ Ω · cm or more and the dielectric constant at 100 kHz is 3 or more. When the volume resistance value is less than 1 × 10 ¹³ Ω · cm, it means that the sealant of the present invention contains ionic impurities, and the liquid crystal display element manufactured using the sealant of the present invention When energized, ionic impurities are eluted into the liquid crystal, which affects the liquid crystal driving voltage and may cause display unevenness. The dielectric constant of the liquid crystal is usually about 10 for ε // (parallel) and about 3.5 for ε⊥ (vertical). Therefore, if the dielectric constant is less than 3, the curable resin is eluted in the liquid crystal. However, this may affect the liquid crystal driving voltage and cause display unevenness.

The method for producing the sealing agent of the present invention is not particularly limited, and examples thereof include a method of mixing the curable resin, the radical polymerization initiator, an additive blended as necessary, and the like by a conventionally known method. Can be mentioned. 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.

The sealant of the present invention comprises a radical polymerization initiator having a lower limit of a molar extinction coefficient at 350 nm measured in acetonitrile of 100 M ⁻¹ · cm ⁻¹ and an upper limit of 100,000 M ⁻¹ · cm ⁻¹ , 60% by mole or more of the reactive functional groups contained in the curable resin contains a curable resin having a (meth) acryloyl group, and can be sufficiently cured by irradiation with ultraviolet rays having a wavelength of about 350 nm.
Such a long-wavelength ultraviolet light having a wavelength of about 350 nm has a large property of going around (diffracting) to the back side of the shielding object even when there is a shielding object that prevents transmission on the irradiated object. That is, the sealant of the present invention is formed so that a part of the sealant pattern formed on the transparent substrate overlaps with the black matrix (BM), wiring, etc. in the thickness direction of the liquid crystal cell and is not directly irradiated with light. Even if there is a case, by irradiating with an ultraviolet ray of about 350 nm, the ultraviolet ray wraps around the back side of BM or the like and can be sufficiently cured. Therefore, the sealing agent of the present invention can be particularly suitably used when a liquid crystal display panel is manufactured with a narrow frame design.

In addition, the sealing agent of the present invention can reduce the wavelength of ultraviolet rays irradiated when it is cured to 350 nm or less, and the liquid crystal is not deteriorated when a liquid crystal display element is produced by a dropping method. .
Therefore, the liquid crystal display element obtained by using the sealant of the present invention has high reliability and can be suitably used as a display panel for characters and symbols of office equipment, home appliances, automobile meters and the like. it can.

A vertical conduction material can be manufactured by mix | blending electroconductive fine particles with such a sealing agent of this invention. If such a vertical conduction material is used, even if there is a portion that is not directly irradiated with light such as ultraviolet rays, the electrodes can be sufficiently conductively connected.
The vertical conduction material containing the sealing agent for liquid crystal dropping method of the present invention and conductive fine particles is also one aspect of the present invention.

The conductive fine particles are not particularly limited, and metal balls, those obtained by forming a conductive metal layer on the surface of resin fine particles, and the like 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 the conductive connection is possible without damaging the transparent substrate due to the excellent elasticity of the resin fine particles.

The method for producing a liquid crystal display element using the sealing agent of the present invention and / or the vertical conducting material of the present invention is not particularly limited, and for example, it can be produced by the following method.
First, a rectangular seal pattern is formed on one of two transparent substrates with electrodes such as an ITO thin film by screen printing, dispenser application or the like using the sealing agent of the present invention and / or the vertical conduction material of the present invention. 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 cured by irradiating the seal portion with ultraviolet rays. When the sealant or the like of the present invention has thermosetting properties, it is further cured by heating in an oven at 100 to 200 ° C. for 1 hour to complete the curing, thereby producing a liquid crystal display element.
A liquid crystal display element using the sealing agent of the present invention and / or the vertical conduction material of the present invention is also one aspect of the present invention.
Furthermore, the manufacturing method of the liquid crystal display element of the present invention, that is, at least one of the two transparent substrates with electrodes is coated with the sealing agent of the present invention and / or the vertical conduction material of the present invention to form a seal pattern. In the process, the liquid crystal micro-droplet is dropped on the entire surface of the transparent substrate with the sealant and / or the vertical conducting material of the present invention in an uncured state, and the other transparent substrate is immediately overlapped to form a seal portion. A method for producing a liquid crystal display element having a step of curing by irradiating with ultraviolet rays is also one aspect of the present invention.

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 may be hindered to cause 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 may be hindered to cause 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.

According to the present invention, in the production of a liquid crystal display element by the dropping method, the sealing agent for the liquid crystal dropping method can be sufficiently cured even if there is a portion where the light is not directly irradiated, and the ultraviolet ray irradiated when curing is performed. Provides a liquid crystal dropping method sealing agent capable of realizing high display quality and high reliability of the liquid crystal display element without deterioration of the liquid crystal, a vertical conduction material, and a liquid crystal display element using the same. be able to.
That is, the sealing agent of the present invention has a property of being cured by ultraviolet light having a long wavelength of about 350 nm, and such a long wavelength ultraviolet light having a wavelength of about 350 nm is a shield that prevents transmission on the irradiated object. Even in the presence of, there is a great property of wrapping around (diffracting) the back side of the shield. Therefore, a part of the sealant pattern formed on the transparent substrate using the sealant of the present invention is formed at a position where it overlaps the black matrix (BM), wiring, etc. in the thickness direction of the liquid crystal cell, and light is directly irradiated. Even if it is not done, it can be sufficiently cured by irradiating ultraviolet rays of about 350 nm so that the ultraviolet rays wrap around the back side of BM or the like. Such a sealant of the present invention can be particularly suitably used when a liquid crystal display panel is manufactured with a narrow frame design.

In addition, since the sealing agent of the present invention can make the wavelength of ultraviolet rays irradiated when it is cured have a low energy of 350 nm or more, the liquid crystal is not deteriorated even when the liquid crystal is directly irradiated with ultraviolet rays.
Therefore, the liquid crystal display element obtained using the sealing agent of the present invention can be designed with a narrow frame without causing liquid crystal contamination, and has a high quality, office equipment, and home appliances. Further, it can be suitably used as a display panel for characters and symbols of automobile meters and the like.

It is explanatory drawing explaining the measuring method of the acryloyl group conversion rate under pattern after UV irradiation of the sealing agent obtained by the Example and the comparative example.

Hereinafter, embodiments of 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 epoxy acrylate)
120 g of EX-201 (resorcinol type epoxy resin) was dissolved in 500 mL of toluene, and 0.1 g of triphenylphosphine was added thereto to obtain a uniform solution. To this solution, 70 g of acrylic acid was added dropwise over 2 hours with stirring under reflux, followed by further stirring under reflux for 8 hours.
Next, by removing toluene, an epoxy (meth) acrylate (EX-201 modified product: viscosity 60 Pa) in which all epoxy groups were converted to acryloyl groups was synthesized.

Example 1
60 parts by weight of EX-201 modified product, 40 parts by weight of Epicoat 828 (manufactured by Japan Epoxy Resin), 2 parts by weight of Irgacure 651 (manufactured by Ciba Specialty Chemicals), 10 parts by weight of Amicure VDH-J (manufactured by Ajinomoto Fine Techno) 3 parts by weight of KBM403 (manufactured by Shin-Etsu Chemical Co., Ltd.) and 30 parts by weight of SO-C1 (manufactured by Admatechs Co., Ltd.) using a planetary stirrer (Awatori Kentaro: manufactured by Shinky Corporation) A sealant was prepared by mixing using this roll.

The prepared sealing agent was applied to a black matrix (BM) and a substrate with a transparent electrode with a dispenser so as to draw a rectangular frame. Subsequently, a fine drop of liquid crystal (manufactured by Chisso Corporation; JC-5004LA) is dropped onto the entire surface of the transparent substrate frame, and another substrate with a transparent electrode (without BM) is immediately overlaid and sealed from the substrate side with BM. The part was irradiated with ultraviolet rays at 50 mW / cm ² for 20 seconds using a high-pressure mercury lamp. At this time, the line width of the squeezed sealant was about 1.2 mm, and 0.3 mm was drawn so as to overlap with BM. Thereafter, liquid crystal annealing was performed at 120 ° C. for 1 hour, and at the same time, the sealant was thermally cured to produce a liquid crystal display panel.
In addition, the (meth) acryloyl group which occupies for the reactive functional group which exists in curable resin of the sealing agent prepared in Example 1 was 60 mol%.

(Example 2)
EX-201 modified product 80 parts by weight, Epicoat 828 (manufactured by Japan Epoxy Resin Co., Ltd.) 20 parts by weight, Irgacure 651 (manufactured by Ciba Specialty Chemicals) 2 parts by weight, Amicure VDH-J (manufactured by Ajinomoto Fine Techno Co., Ltd.) 10 weights 3 parts by weight of KBM403 (manufactured by Shin-Etsu Chemical Co., Ltd.) and 30 parts by weight of SO-C1 (manufactured by Admatechs Co., Ltd.) using a planetary stirrer (Awatori Kentaro: manufactured by Shinky Corporation) A sealant was prepared by mixing using this roll.
A liquid crystal display panel was produced in the same manner as in Example 1, except that the prepared sealing agent according to Example 2 was used.
In addition, the (meth) acryloyl group which occupies for the reactive functional group which exists in curable resin of the sealing compound prepared in Example 2 was 80 mol%.

( Comparative Example 3 )
EX-201 modified product 100 parts by weight, Irgacure 651 (Ciba Specialty Chemicals) 2 parts, Amicure VDH-J (Ajinomoto Fine Techno Co.) 10 parts, KBM403 (Shin-Etsu Chemical Co.) 3 parts by weight, And after mixing 30 parts by weight of SO-C1 (manufactured by Admatechs) using a planetary stirrer (manufactured by Awatori Kentaro: manufactured by Sinky), a sealant is prepared by further mixing using three rolls. did.
Thereafter, a liquid crystal display panel was produced in the same manner as in Example 1 except that the prepared sealing agent according to Comparative Example 3 was used.
In addition, the (meth) acryloyl group which occupies for the reactive functional group which exists in curable resin of the sealing compound prepared in the comparative example 3 was 100 mol%.

(Example 4)
80 parts by weight of EX-201 modified product, 20 parts by weight of Epicoat 828 (manufactured by Japan Epoxy Resin Co., Ltd.), 2 parts by weight of Irgacure 651 (manufactured by Ciba Specialty Chemicals), 5 parts by weight of 2MZA-PW (manufactured by Shikoku Chemicals), 3 parts by weight of KBM403 (manufactured by Shin-Etsu Chemical Co., Ltd.) and 30 parts by weight of SO-C1 (manufactured by Admatechs) are mixed using a planetary stirrer (Awatori Kentaro: manufactured by Shinky Corporation), and further three rolls The sealant was prepared by mixing using
Thereafter, a liquid crystal display panel was produced in the same manner as in Example 1 except that the sealant according to Example 4 prepared was used.
In addition, the (meth) acryloyl group which occupies for the reactive functional group which exists in curable resin of the sealing compound prepared in Example 4 was 80 mol%.

(Example 5)
EX-201 modified 80 parts by weight, Epicoat 828 (Japan Epoxy Resin Co., Ltd.) 20 parts by weight, Irgacure 819 (Ciba Specialty Chemicals Co., Ltd.) 2 parts by weight, Amicure VDH-J (Ajinomoto Fine Techno Co., Ltd.) 10 parts by weight 3 parts by weight of KBM403 (manufactured by Shin-Etsu Chemical Co., Ltd.) and 30 parts by weight of SO-C1 (manufactured by Admatechs Co., Ltd.) using a planetary stirrer (Awatori Kentaro: manufactured by Shinky Corporation) A sealant was prepared by mixing using this roll.
A liquid crystal display panel was produced in the same manner as in Example 1 except that the prepared sealant according to Example 5 was used.
In addition, the (meth) acryloyl group which occupies for the reactive functional group which exists in curable resin of the sealing compound prepared in Example 5 was 80 mol%.

(Example 6)
80 parts by weight of EX-201 modified product, 20 parts by weight of Epicoat 828 (manufactured by Japan Epoxy Resin Co., Ltd.), 2 parts by weight of Irgacure 651 (manufactured by Ciba Specialty Chemicals), 10 parts by weight of pulverized ADH (manufactured by Otsuka Chemical Co., Ltd.) 3 parts by weight of KBM403 (manufactured by Shin-Etsu Chemical Co., Ltd.) and 30 parts by weight of SO-C1 (manufactured by Admatechs) are mixed using a planetary stirrer (Awatori Kentaro: manufactured by Shinky Corporation), and further three rolls The sealant was prepared by mixing using
A liquid crystal display panel was produced in the same manner as in Example 1 except that the prepared sealing agent according to Example 6 was used.
In addition, the (meth) acryloyl group which occupies for the reactive functional group which exists in curable resin of the sealing compound prepared in Example 6 was 80 mol%.

(Comparative Example 1)
EX-201 modified product 80 parts by weight, Epicoat 828 (manufactured by Japan Epoxy Resin Co., Ltd.) 20 parts by weight, Irgacure 2959 (manufactured by Ciba Specialty Chemicals) 2 parts by weight, Amicure VDH-J (manufactured by Ajinomoto Fine Techno Co., Ltd.) 10 weights 3 parts by weight of KBM403 (manufactured by Shin-Etsu Chemical Co., Ltd.) and 30 parts by weight of SO-C1 (manufactured by Admatechs Co., Ltd.) using a planetary stirrer (Awatori Kentaro: manufactured by Shinky Corporation) A sealant was prepared by mixing using this roll.
A liquid crystal display panel was produced in the same manner as in Example 1 except that the prepared sealant according to Comparative Example 1 was used.
In addition, the (meth) acryloyl group which occupies for the reactive functional group which exists in curable resin of the sealing compound prepared in the comparative example 1 was 80 mol%.

(Comparative Example 2)
EX-201 modified product 40 parts by weight, Epicoat 828 (Japan Epoxy Resin Co., Ltd.) 60 parts by weight, Irgacure 651 (Ciba Specialty Chemicals Co., Ltd.) 2 parts by weight, Amicure VDH-J (Ajinomoto Fine Techno Co., Ltd.) 10 parts by weight 3 parts by weight of KBM403 (manufactured by Shin-Etsu Chemical Co., Ltd.) and 30 parts by weight of SO-C1 (manufactured by Admatechs Co., Ltd.) using a planetary stirrer (Awatori Kentaro: manufactured by Shinky Corporation) A sealant was prepared by mixing using this roll.
A liquid crystal display panel was produced in the same manner as in Example 1 except that the prepared sealant according to Comparative Example 2 was used.
In addition, the (meth) acryloyl group which occupies for the reactive functional group which exists in curable resin of the sealing compound prepared in the comparative example 2 was 40 mol%.

(Evaluation)
The following evaluation was performed about the produced sealing agent concerning Examples 1, 2 , 4-6, and Comparative Examples 1-3 , and a liquid crystal display element.

(1) Stability under fluorescent lamp Each of the obtained sealing agents was allowed to stand under a fluorescent lamp for 12 hours, and the change in viscosity was examined.
The results are shown in Table 1. In Table 2, those having a viscosity change of 2 times or less were shown as ◯, and those having a viscosity change of 2 times or more were shown as x.

(2) Adhesive strength 3 parts by weight of polymer beads having an average particle diameter of 5 μm (manufactured by Sekisui Chemical Co., Ltd .; Micropearl SP) are dispersed with a planetary stirrer with respect to 100 parts by weight of each obtained sealant. A very small amount is placed in the center of Corning glass 1737 (20 mm x 50 mm x 1.1 mmt), and the same type of glass is placed on top of it to spread the sealant. Ultraviolet rays are applied at 50 mW / cm ² for 60 seconds. Irradiated. 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 (comparative unit: N / cm ² ).
The results are shown in Table 1.

(3) Measurement of acryloyl group conversion under pattern after UV irradiation (see FIG. 1)
First, a substrate 1 on which a half surface of Corning glass 0.7 mmt was vapor-deposited with chromium and a substrate 2 on which the front surface was vapor-deposited with chromium were separately prepared (FIG. 1A). A sealant containing polymer beads is applied to the central portion A of the substrate 1 and the substrate 2 is bonded together and then sufficiently crushed (FIG. 1B).
Next, after irradiating the combined substrate with ultraviolet rays from the surface of the substrate 1 at 50 mW / cm ² for 60 seconds, the substrates 1 and 2 were torn using a cutter, and the UV direct irradiation part (place 1) by the microscopic IR method. Measure the spectrum of the sealant at a point 100 μm away from the direct irradiation part (place 2), 200 μm away (place 3), and 300 μm away (place 4). The conversion rate of the acrylic functional group was determined (FIG. 1 (c)).
In addition, the quantification of the acrylic functional group used a peak area of 810 m ⁻¹ .
The results are shown in Table 1.

(4) Panel display unevenness evaluation
For the liquid crystal display panels obtained in Examples 1, 2 , 4 to 6 and Comparative Examples 1 to 3 , color unevenness generated in the liquid crystal around the seal portion was visually observed according to the following criteria.
◎ (No color irregularity)
○ (There is almost no uneven color)
△ (Slight color irregularity)
× (There is considerable color unevenness)
The results are shown in Table 1.

According to the present invention, in the production of a liquid crystal display element by the dropping method, the sealing agent for the liquid crystal dropping method can be sufficiently cured even if there is a portion where the light is not directly irradiated, and the ultraviolet ray irradiated when curing is performed. Provides a liquid crystal dropping method sealing agent capable of realizing high display quality and high reliability of the liquid crystal display element without deterioration of the liquid crystal, a vertical conduction material, and a liquid crystal display element using the same. be able to.

Claims (5)

A radical polymerization initiator that generates an active radical by irradiating light, a curable resin, and a sealing agent for liquid crystal dropping method containing a solid organic acid hydrazide,
The radical polymerization initiator has a molar extinction coefficient at 350 nm measured in acetonitrile of 100 to 100,000 M ⁻¹ · cm ⁻¹ , and 60 mol% or more of the reactive functional group contained in the curable resin (meta ) An acryloyl group,
The curable resin is obtained by reacting (meth) acrylic acid with a resorcinol type epoxy resin, and contains an epoxy (meth) acrylate in which all the epoxy groups of the resorcinol type epoxy resin are converted into acryloyl groups,
The curable resin, the liquid crystal dropping process sealant you wherein <br/> that contain bisphenol A type epoxy resin as an epoxy resin. The sealing agent for liquid crystal dropping method according to claim 1 , wherein the curable resin has a hydrogen bonding functional group in one molecule. 3. The sealing agent for liquid crystal dropping method according to claim 2 , wherein the hydrogen bonding functional group is a urethane group and / or a hydroxyl group. A vertical conduction material comprising the sealing agent for liquid crystal dropping method according to claim 1, 2 or 3 , and conductive fine particles. A liquid crystal display element comprising the sealing agent for a liquid crystal dropping method according to claim 1, 2 or 3 , and / or the vertical conduction material according to claim 4 .

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