TW201346016A - Sealing agent for liquid crystal dropping method, vertical conduction material, and liquid crystal display element - Google Patents

Abstract

The purpose of the present invention is to provide a sealing agent for a liquid crystal dropping method with excellent rendering, adhesion, and moisture resistance of the cured product. The further purpose of the present invention is to provide a vertical conduction material and a liquid crystal display element produced using said sealing agent for the liquid crystal dropping method. This sealing agent for a liquid crystal dropping method contains a curable resin, talc, and a radical polymerization initiator or a heat curing agent, or both a radical polymerization initiator and a heat curing agent, wherein the content of the total of CaMg(CO3)2 and MgCO3 in the talc is less than or equal to 0.1 wt%.

Description

Sealant for liquid crystal dropping method, upper and lower conductive materials and liquid crystal display elements

The present invention relates to a sealing compound for a liquid crystal dropping method which is excellent in drawability, adhesion, and moisture resistance of a cured product. Further, the present invention relates to an upper conductive material and a liquid crystal display element which are produced by using the sealing compound for a liquid crystal dropping method.

In recent years, from the viewpoint of shortening the tact time and optimizing the amount of liquid crystal, a method of manufacturing a liquid crystal display element such as a liquid crystal display unit is being used by a conventional vacuum injection method, for example, Patent Document 1 and Patent. The photocurable resin, the photopolymerization initiator, the thermosetting resin, and the thermosetting agent disclosed in Document 2 are converted into a liquid crystal dropping method called a dropping method.

In the dropping method, first, a rectangular sealing pattern is formed by dispensing on one of the two transparent substrates with electrodes. Then, the liquid crystal droplets are dropped onto the entire surface of the transparent substrate in a state where the sealant is not cured, and the other transparent substrate is immediately superposed, and the sealing portion is temporarily hardened by irradiating light such as ultraviolet rays. Thereafter, it is heated and solidified during the liquid crystal annealing to form a liquid crystal display element. When the substrate is bonded under reduced pressure, the liquid crystal display element can be manufactured with extremely high efficiency, and the dropping method is currently the mainstream of the method for producing a liquid crystal display element.

In the liquid crystal display device, the sealant is required to have excellent drawability, and in order to achieve efficiency in the production process, it is required to increase the speed of distribution. However, in order to make the previous sealant In the case of high-speed drawing, there is a problem that the sealant cannot be stably drawn, and the wire breakage is poor or the line of the sealant after drawing is bent. An inorganic filler is usually formulated in the sealant. In order to improve the drawability, it is conceivable to reduce the amount of the inorganic filler formulated in the sealant. However, if the amount of the inorganic filler is reduced, the sealant is applied to the substrate or the alignment film. The problem of lowering the durability or the moisture resistance of the sealant is lowered.

Patent Document 3 discloses a method of blending talc as an inorganic filler with a sealant for the purpose of improving the adhesion of a sealant, etc., but particularly when the talc is blended as an inorganic filler in this manner, it is difficult to seal. The agent is stable in drawing.

Patent Document 1: Japanese Laid-Open Patent Publication No. 2001-133794

Patent Document 2: International Publication No. 02/092718

Patent Document 3: Japanese Laid-Open Patent Publication No. 2008-40015

An object of the present invention is to provide a sealing compound for a liquid crystal dropping method which is excellent in drawability, adhesion, and moisture resistance of a cured product. Further, an object of the present invention is to provide an upper and lower conductive material and a liquid crystal display element which are produced by using the sealing compound for a liquid crystal dropping method.

The sealing compound for liquid crystal dropping method of the present invention contains a curable resin, talc, and a radical polymerization initiator or a heat hardener, or both a radical polymerization initiator and a heat hardener, and CaMg in the above talc ( The total content of CO ₃ ) ₂ and MgCO ₃ is 0.1% by weight or less.

Hereinafter, the present invention will be described in detail.

Usually, impurities such as dolomite (CaMg(CO ₃ ) ₂ ) and magnesite (MgCO ₃ ) are mixed in the talc. The inventors of the present invention conducted intensive studies, and as a result, it was surprisingly found that the CaMg(CO ₃ ) ₂ and MgCO ₃ have a large influence on the deterioration of the drawability of the sealant.

Therefore, the present inventors have found that talc having a content of CaMg(CO ₃ ) ₂ and MgCO ₃ of a specific amount or less can be blended in a sealing compound for a liquid crystal dropping method to obtain portability, adhesion, and hardening. The sealing agent for a liquid crystal dropping method excellent in moisture resistance of the object is used to complete the present invention.

The sealant for liquid crystal dropping method of the present invention contains talc.

The total content of CaMg(CO ₃ ) ₂ and MgCO _{3 in} the talc is 0.1% by weight or less. When the total content of CaMg(CO ₃ ) ₂ and MgCO _{3 in} the talc exceeds 0.1% by weight, the obtained sealing compound for liquid crystal dropping method may be inferior in drawability. The content of the total of CaMg(CO ₃ ) ₂ and MgCO _{3 in} the talc is preferably as small as possible, and preferably less than 0.1% by weight. The substantial lower limit of the total content of CaMg(CO ₃ ) ₂ and MgCO _{3 in} the above talc is 0.0001% by weight.

Further, the content of CaMg(CO ₃ ) _{2 in} the talc can be determined from the peak area ratio of the diffraction angle of 30.9° from CaMg(CO ₃ ) ₂ in the X-ray diffraction measurement (allowable ± 0.2° or so) error).

The content of MgCO _{3 in} the talc can be determined from the peak area ratio of the diffraction angle of 32.6° from MgCO ₃ in the X-ray diffraction measurement (allowing an error of about ±0.2°).

Further, the measurement conditions of the X-ray diffraction measurement in the present invention are as follows.

Measuring machine: X'Pert-PRO-MPD (manufactured by Spectris)

Target: Cu

Scanning angle: 5°-60°

Scanning speed: 2°/min

Tube voltage: 40kV

Tube current: 30mA

Incident side slit: 0.04° Soller-slit, automatic variable divergence slit, AS1°

Light receiving side slit: 0.04°

Furthermore, the detection limit in this condition is 0.1%.

Further, in this specification, the term "talc CaMg (CO _{3) 2,} and the sum of the contents of MgCO _3" means the overall talc containing CaMg respect of impurities from talc (CO _{3) 2} and MgCO ₃ of Total content.

As the total content of CaMg (CO _{3) 2} MgCO ₃ and 0.1 wt% of the talc of any commercially available, for example, include: FG-15F, D-800F ( both Nippon Talc Co., Ltd.).

The method of setting the total content of CaMg(CO ₃ ) ₂ and MgCO _{3 in} the talc to 0.1% by weight or less is, for example, separation and purification by classification.

The separation and purification method for setting the total content of CaMg(CO ₃ ) ₂ and MgCO ₃ to 0.1% by weight or less is, for example, classification using a classification device such as a forced scroll classifier or a semi-free vortex classifier. Method and so on. As a commercial item of such a classification apparatus, Turbo Classifier and Eddy Classifier (both manufactured by Nisshin Engineering Co., Ltd.), etc. are mentioned, for example.

The talc is preferably formed by surface treatment with a surface treatment agent.

Examples of the surface treatment agent include a decane coupling agent, a fatty acid, and a titanate coupling agent. Among them, a decane coupling agent is preferred in terms of improving the adhesion of the obtained sealant, and more preferably a decane coupling agent having an epoxy group.

As a decane coupling agent used as a surface treatment agent for the above talc, for example, it can be listed For example: vinyl trimethoxy decane, vinyl triethoxy decane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxy decane, 3-glycidoxypropylmethyldimethoxy 3-Glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxydecane, 3-glycidoxypropyltriethyl, 3-glycidoxypropyltrimethoxysilane Oxydecane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methylpropenyloxypropyl Trimethoxy decane, 3-methyl propylene methoxy propyl methyl diethoxy decane, 3-methyl propylene methoxy propyl triethoxy decane, 3- propylene methoxy propyl trimethoxy Baseline, N-2-(aminoethyl)-3-aminopropylmethyldimethoxydecane, N-2-(aminoethyl)-3-aminopropyltrimethoxydecane, 3-Aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-triethoxydecyl-N-(1,3-dimethylbutylidene)propylamine (3 -triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine) , N-phenyl-3-aminopropyltrimethoxydecane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxydecane, 3-ureidopropyl Triethoxy decane, 3-mercaptopropylmethyldimethoxydecane, 3-mercaptopropyltrimethoxydecane, 3-isocyanatepropyltriethoxydecane, methyltrimethoxydecane, dimethyl Dimethoxy decane, phenyl trimethoxy decane, methyl triethoxy decane, dimethyl diethoxy decane, phenyl triethoxy decane, hexyl trimethoxy decane, hexyl triethoxy Decane, decyltrimethoxydecane, trifluoropropyltrimethoxydecane, and the like.

For example, KBM-303, KBM-403, KBM-502, KBM-602, and KBM-603 (all manufactured by Shin-Etsu Silicones Co., Ltd.), etc. are mentioned as a commercial item of the said decane coupling agent.

Examples of the fatty acid used as the surface treatment agent for the talc include stearic acid, palmitic acid, lauric acid, oleic acid, and linoleic acid.

Examples of the titanate coupling agent used as the surface treatment agent for the talc include tributoxytitanium stearate, isopropoxytitanium triisostearate, and monoisopropoxytitanium trioxide. Titanium oxide such as stearate; or titanium tetraethoxide, tetrapropoxy titanium, tetrabutoxy titanium, tetracyclohexyl titanate, tetrabenzyl titanate or the like; or -di-n-butoxy bis(triethanolaminato)titanium, diisopropoxy bis(acetylacetonate)titanium, titanium tetraacetate pyruvate, di- A titanium chelate compound such as 2-ethylhexyloxybis(2-ethyl-3-hydroxyhexanol)titanium or diisopropoxy bis(ethylethanoacetic acid)titanium or the like.

The commercially available ones of the titanate coupling agents include, for example, TAA, TOG, A-1, TOT, and B-1 (all manufactured by Nippon Soda Co., Ltd.).

A preferred lower limit of the average particle diameter of the talc is 0.2 μm, and a preferred upper limit is 5 μm. When the average particle diameter of the talc is less than 0.2 μm, the viscosity and the thixotropy may increase and the workability may be poor. When the average particle diameter of the talc exceeds 5 μm, display unevenness may occur in the liquid crystal display element due to poor gap. A more preferred lower limit of the average particle diameter of the talc is 0.6 μm, and a more preferred upper limit is 3 μm.

In the present specification, the average particle diameter refers to an average value of particle diameters (long diameters) of 10 particles observed at a magnification of 5000 times using a scanning electron microscope. Further, as the scanning electron microscope, S-4300 (manufactured by Hitachi High-Technologies Co., Ltd.) or the like can be used.

The content of the talc is preferably 0.1 part by weight, and preferably 50 parts by weight, based on 100 parts by weight of the curable resin. When the content of the talc is less than 0.1 part by weight, the obtained sealing compound for a liquid crystal dropping method may be peeled off poorly or the cured product may be inferior in moisture resistance. When the content of the talc is more than 50 parts by weight, the viscosity and the shakeability of the sealant for a liquid crystal dropping method obtained may be increased, and the workability may be poor. condition. A more preferred lower limit of the content of the talc is 1 part by weight, and a more preferred upper limit is 40 parts by weight.

The sealing compound for a liquid crystal dropping method of the present invention may contain other inorganic fillers other than the above-described talc, within a range not inhibiting the object of the present invention.

The other inorganic filler is not particularly limited, and examples thereof include cerium oxide, aluminum oxide, titanium oxide, and calcium carbonate. Among them, cerium oxide is preferred.

Hereinafter, talc and other inorganic fillers are combined and are also simply referred to as inorganic fillers.

A preferred lower limit of the average particle diameter of the inorganic filler is 0.01 μm, and a preferred upper limit is 5.0 μm. When the average particle diameter of the inorganic filler is less than 0.01 μm, viscosity and shakeability may increase and workability may be poor. When the average particle diameter of the inorganic filler exceeds 5.0 μm, display unevenness may occur in the liquid crystal display element due to poor gap. A more preferred lower limit of the average particle diameter of the inorganic filler is 0.1 μm, and a more preferred upper limit is 3.0 μm.

In the case where the other inorganic filler is contained, a preferred lower limit of the total content of the inorganic filler is 1% by weight, and preferably the upper limit is 60% by weight. When the content of the entire inorganic filler is less than 1% by weight, the cured product of the sealing compound for liquid crystal dropping method obtained may have poor moisture resistance. When the content of the inorganic filler as a whole exceeds 60% by weight, the viscosity or the shakeability of the sealant for a liquid crystal dropping method obtained may be increased, and the workability may be deteriorated. A more preferred lower limit of the content of the inorganic filler as a whole is 10% by weight, and a more preferred upper limit is 50% by weight.

The sealing compound for a liquid crystal dropping method of the present invention contains a curable resin.

Examples of the curable resin include a (meth)acrylic resin and an epoxy resin.

Wherein, the curable resin preferably contains a (meth) acrylate having a hetero-cyanuric acid skeleton. And/or a (meth) acrylate having a dicyclopentadiene skeleton. The liquid crystal dropping method sealing agent of the present invention is hardened by containing the above (meth) acrylate having an isomeric cyanuric acid skeleton and/or the above (meth) acrylate having a dicyclopentadiene skeleton. The moisture resistance of the material is particularly excellent.

In the present specification, the term "(meth)acrylic" means acrylic or methacrylic, and the above-mentioned "(meth)acrylic resin" means having (meth)acrylic acid. The term "(meth)acryl fluorenyl" as used herein means acryl fluorenyl or methacryl fluorenyl. Further, in the present specification, the term "(meth)acrylate" means acrylate or methacrylate.

Examples of the (meth) acrylate having an isomeric cyanuric acid skeleton include ethoxylated isocyanuric acid triacrylate, ethoxylated isocyanuric acid trimethacrylate, and caprolactone modified. Ethoxylated isocyanuric acid triacrylate, caprolactone modified ethoxylated isocyanuric acid trimethacrylate, and the like. Among them, ethoxylated isocyanuric acid triacrylate having good adhesion is preferred.

Examples of the (meth) acrylate having a dicyclopentadiene skeleton include tricyclodecane dimethanol diacrylate and tricyclodecane dimethanol dimethacrylate. Among them, tricyclodecane dimethanol diacrylate having good adhesion is preferred.

The content of the (meth) acrylate having a different isocyanuric acid skeleton and the (meth) acrylate having the dicyclopentadiene skeleton is preferably 0.1 or less based on 100 parts by weight of the entire curable resin. The weight is preferably 30 parts by weight. When the content of the (meth) acrylate having an isomeric cyanuric acid skeleton and the (meth) acrylate having the dicyclopentadiene skeleton is less than 0.1 part by weight, the liquid crystal dropping method may not be sufficiently exhibited. The effect of improving the moisture resistance of the cured product of the sealant. If the content of the (meth) acrylate having an isomeric cyanuric acid skeleton and the above (meth) acrylate having a dicyclopentadiene skeleton exceeds 30 parts by weight, There is a case where the liquid crystal pollution is increased. A more preferred lower limit of the content of the (meth) acrylate having a different isocyanuric acid skeleton and the above (meth) acrylate having a dicyclopentadiene skeleton is 1 part by weight, and more preferably 20 parts by weight.

The curable resin preferably contains an epoxy (meth) acrylate.

In the present specification, the term "epoxy (meth) acrylate" means a compound obtained by reacting all of the epoxy groups in the epoxy resin with (meth)acrylic acid.

The epoxy (meth) acrylate is not particularly limited, and examples thereof include those obtained by reacting (meth)acrylic acid with an epoxy resin in the presence of a basic catalyst according to a usual method. Among them, an epoxy methacrylate resin is preferred in terms of excellent moisture resistance of the cured product.

The epoxy resin to be used as a raw material for synthesizing the above epoxy (meth) acrylate is not particularly limited, and examples thereof include bisphenol A type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type epoxy resin. Resin, 2,2'-diallyl bisphenol A type epoxy resin, hydrogenated bisphenol type epoxy resin, propylene oxide addition bisphenol A type epoxy resin, resorcinol type epoxy resin, joint Benzene type epoxy resin, thioether type epoxy resin, diphenyl ether type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, phenol novolak type epoxy resin, o-cresol novolac Epoxy resin, dicyclopentadiene novolac type epoxy resin, biphenyl novolac type epoxy resin, naphthol novolac type epoxy resin, epoxy propyl amine type epoxy resin, alkyl polyol type Epoxy resin, rubber modified epoxy resin, epoxy propyl ester compound, bisphenol A type episulfide resin, and the like.

For example, Epikote 828EL, Epikote 1004 (all manufactured by Mitsubishi Chemical Corporation), Epiclon 850 (made by DIC Corporation), etc. are mentioned as a commercial item of the said bisphenol A type epoxy resin.

As a commercial item among the said bisphenol F type epoxy resin, the Epikote 806 is mentioned, for example. Epikote 4004 (all manufactured by Mitsubishi Chemical Corporation) and the like.

As a commercial item of the said bisphenol S type epoxy resin, Epiclon EXA1514 (made by the DIC company) etc. are mentioned, for example.

The commercially available one of the 2,2'-diallyl bisphenol A type epoxy resins is, for example, RE-810NM (manufactured by Nippon Kayaku Co., Ltd.).

As a commercial item of the said hydrogenated bisphenol type epoxy resin, Epiclon EXA7015 (made by the DIC company) etc. are mentioned, for example.

The commercially available one of the above-mentioned propylene oxide-added bisphenol A-type epoxy resins is, for example, EP-4000S (manufactured by Adeka Co., Ltd.).

The commercially available one of the resorcinol-type epoxy resins is, for example, EX-201 (manufactured by Nagase ChemteX Co., Ltd.).

As a commercial item of the above-mentioned biphenyl type epoxy resin, Epikote YX-4000H (made by Mitsubishi Chemical Corporation), etc. are mentioned, for example.

For example, YSLV-50TE (manufactured by Tohto Kasei Co., Ltd.) and the like are mentioned as a commercial product of the above-mentioned sulfide-type epoxy resin.

The commercially available one of the above-mentioned diphenyl ether type epoxy resins is YSLV-80DE (manufactured by Tohto Kasei Co., Ltd.).

The commercially available one of the above-mentioned dicyclopentadiene type epoxy resins is, for example, EP-4088S (manufactured by Adeka Co., Ltd.).

As a commercial item of the above-mentioned naphthalene type epoxy resin, Epiclon HP4032, Epiclon EXA-4700 (all manufactured by DIC Corporation), etc. are mentioned, for example.

As a commercial item of the said phenol type novolak type epoxy resin, Epiclon is mentioned, for example. N-770 (manufactured by DIC Corporation) and the like.

As a commercial item of the above-mentioned o-cresol novolak type epoxy resin, Epiclon N-670-EXP-S (made by DIC Corporation) etc. are mentioned, for example.

The commercially available one of the above-mentioned dicyclopentadiene novolac type epoxy resins is Epiclon HP7200 (manufactured by DIC Corporation).

The commercially available one of the above-mentioned biphenol novolak type epoxy resins is, for example, NC-3000P (manufactured by Nippon Kayaku Co., Ltd.).

As a commercial item of the above-mentioned naphthol type novolak type epoxy resin, ESN-165S (made by Todo Kasei Co., Ltd.), etc. are mentioned, for example.

For example, Epikote 630 (manufactured by Mitsubishi Chemical Corporation), Epiclon 430 (manufactured by DIC Corporation), TETRAD-X (manufactured by Mitsubishi Gas Chemical Co., Ltd.), and the like are exemplified as the commercially available ones of the above-mentioned epoxy propylamine type epoxy resins.

For example, ZX-1542 (manufactured by Tohto Kasei Co., Ltd.), Epiclon 726 (manufactured by DIC Corporation), Epolight 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.), and Denacol EX- are mentioned as a commercial product of the above-mentioned alkyl polyol type epoxy resin. 611 (manufactured by Nagase ChemteX Co., Ltd.).

For example, YR-450, YR-207 (all manufactured by Tohto Kasei Co., Ltd.), Epolead PB (manufactured by Daicel Chemical Industry Co., Ltd.), and the like are exemplified as the commercially available ones of the rubber-modified epoxy resins.

The commercially available one of the above-mentioned glycidyl ester compounds may, for example, be Denacol EX-147 (manufactured by Nagase ChemteX Co., Ltd.).

The commercially available one of the above-mentioned bisphenol A-type episulfide resins is, for example, Epikote YL-7000 (manufactured by Mitsubishi Chemical Corporation).

Other examples of the above-mentioned epoxy resin include YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Tohto Kasei Co., Ltd.), XAC4151 (made by Asahi Kasei Corporation), Epikote 1031, and Epikote 1032 (both of them). It is manufactured by Mitsubishi Chemical Corporation, EXA-7120 (manufactured by DIC Corporation), TEPIC (manufactured by Nissan Chemical Co., Ltd.), and the like.

As a commercially available one of the above epoxy (meth) acrylates, for example, Ebecryl 860, Ebecryl 3200, Ebecryl 3201, Ebecryl 3412, Ebecryl 3600, Ebecryl 3700, Ebecryl 3701, Ebecryl 3702, Ebecryl 3703, Ebecryl 3800, Ebecryl 6040, Ebecryl RDX63182 (all manufactured by Daicel-Cytec), EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, EMA-1020 (all manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), Epoxy Ester M-600A, Epoxy Ester 40EM, Epoxy Ester 70PA, Epoxy Ester 200PA, Epoxy Ester 80MFA, Epoxy Ester 3002M, Epoxy Ester 3002A, Epoxy Ester 1600A, Epoxy Ester 3000M, Epoxy Ester 3000A, Epoxy Ester 200EA, Epoxy Ester 400EA (both It is manufactured by Kyoeisha Chemical Co., Ltd., Denacol Acrylate DA-141, Denacol Acrylate DA-314, Denacol Acrylate DA-911 (all manufactured by Nagase Chemtech X), and the like.

The sealing compound for a liquid crystal dropping method of the present invention may further contain an epoxy resin as a curable resin.

The epoxy resin is not particularly limited as long as it is an epoxy group-containing resin, and an epoxy resin or the like which is a raw material for synthesizing the above epoxy (meth) acrylate can be used.

Further, the epoxy resin may contain a partial (meth)acrylic modified epoxy resin.

In addition, in the present specification, the above-mentioned "partial (meth)acrylic modified epoxy resin" It means a resin having one or more epoxy groups and (meth) acryloxy group in one molecule. Further, in the present specification, the above (meth)acryloxy group means an acryloxy group or a methacryloxy group.

The partial (meth)acrylic modified epoxy resin can be obtained, for example, by reacting an epoxy group which is a part of an epoxy resin having two or more epoxy groups with (meth)acrylic acid.

The epoxy group in the whole curable resin as a whole is relative to the (meth) acryloxy group The ratio of the total amount to the epoxy group is preferably 50 mol%. When the ratio of the epoxy group exceeds 50 mol%, the solubility of the liquid crystal dropping method for the liquid crystal dropping method becomes high, which causes liquid crystal contamination, and the obtained liquid crystal display element becomes poor in display performance. Happening. The upper limit of the above ratio of the epoxy group is preferably 20 mol%.

The sealant for liquid crystal dropping method of the present invention contains a radical polymerization initiator or a heat hardener, or both a radical polymerization initiator and a heat hardener.

In the present specification, the phrase "containing a radical polymerization initiator or a thermal curing agent, or both a radical polymerization initiator and a heat curing agent" means a radical polymerization initiator and heat. At least one of the hardeners.

Examples of the radical polymerization initiator include a photoradical polymerization initiator and a thermal radical polymerization initiator.

As the photoradical polymerization initiator which generates a radical by irradiation with light in the radical polymerization initiator, for example, a diphenylketone compound, an acetophenone compound, or a mercaptophosphine oxide can be preferably used. Acylphosphine oxide compound, titanocene compound, oxime ester compound, benzoin ether compound, 9-oxosulfur Wait.

Further, as a commercially available one of the photoradical polymerization initiators, for example, Irgacure 184, Irgacure 369, Irgacure 379, Irgacure 651, Irgacure 819, Irgacure 907, Irgacure 2959, Irgacure OXE01, Lucirin TPO (all manufactured by BASF Japan), benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether (all are Tokyo Chemicals) Manufactured by an industrial company). Among them, in terms of a wide absorption wavelength range, Irgacure 651, Irgacure 907, benzoin isopropyl ether, and Lucirin TPO are preferred. These photoradical polymerization initiators may be used singly or in combination of two or more.

The thermal radical polymerization initiator which generates a radical by heat in the radical polymerization initiator is not particularly limited, and examples thereof include a peroxide and an azo compound. Commercially available, for example, Perbutyl O , Perhexyl O, Perbutyl PV (all manufactured by Nippon Oil Co., Ltd.), V-30, V-501, V-601, VPE-0201 (all manufactured by Wako Pure Chemical Industries, Ltd.).

The content of the radical polymerization initiator is not particularly limited, and a lower limit is preferably 0.1 part by weight, and preferably an upper limit of 30 parts by weight, based on 100 parts by weight of the curable resin. When the content of the above-mentioned radical polymerization initiator is less than 0.1 part by weight, the polymerization of the sealing compound for liquid crystal dropping method obtained may not be sufficiently performed. When the content of the radical polymerization initiator is more than 30 parts by weight, a large amount of unreacted radical polymerization initiator remains, and the weather resistance of the obtained liquid crystal dropping method sealant may be deteriorated. The lower limit of the content of the above radical polymerization initiator is preferably 1 part by weight, more preferably 10 parts by weight.

The above-mentioned thermosetting agent is not particularly limited, and examples thereof include an organic acid hydrazide, an imidazole derivative, an amine compound, a polyphenol compound, and an acid anhydride. Among them, a solid organic acid hydrazine is preferably used.

The solid organic acid hydrazine is not particularly limited, and examples thereof include 1,3-bis[mercaptocarbonylethyl-5-isopropylhydantoin], sebacic acid hydrazide, and Phthalic As a commercially available product, for example, Amicure VDH, Amicure UDH (all manufactured by Ajinomoto Fine-Techno Co., Ltd.), SDH, IDH, and ADH (both are bismuth phthalate, bismuth succinate, bismuth malonate, and the like). Manufactured for Otsuka Chemical Co., Ltd.).

The content of the above-mentioned thermosetting agent is not particularly limited, and a lower limit is preferably 2 parts by weight, and preferably an upper limit of 50 parts by weight, based on 100 parts by weight of the curable resin. When the content of the above-mentioned thermosetting agent is less than 2 parts by weight, the obtained sealing compound for liquid crystal dropping method may be inferior in hardenability. When the content of the above-mentioned heat-hardening agent exceeds 50 parts by weight, the viscosity of the sealing compound for liquid crystal dropping methods obtained may become high, and coatability may deteriorate. A more preferred lower limit of the content of the above-mentioned thermosetting agent is 5 parts by weight, more preferably 20 parts by weight, and still more preferably 15 parts by weight.

The sealing agent for a liquid crystal dropping method of the present invention may further contain a cationic polymerization initiator.

Examples of the cationic polymerization initiator include a photocationic polymerization initiator and a thermal cationic polymerization initiator.

The photocationic polymerization initiator is not particularly limited, and examples thereof include an aromatic diazonium salt, an aromatic onium salt, and an aromatic onium salt.

As a commercial one of the above-mentioned photocationic polymerization initiators, for example, Optomer SP-150, Optomer SP-151, Optomer SP-170, Optomer SP-171 (all manufactured by ADEKA), UVE-1014 (General) Manufactured by Electronics, Irgacure 261 (manufactured by BASF Japan), San-Aid SI-60L, San-Aid SI-80L, UVI-6990 (both manufactured by Union Carbide), BBI-103, MPI-103, TPS- 103, MDS-103, DTS-103, NAT-103, NDS-103 (all manufactured by Midori Kagaku Co., Ltd.), San-Aid SI-100L (manufactured by Sanshin Chemical Industry Co., Ltd.), CI-2064, CI-2639, CI -2624, CI-2481 (all manufactured by Japan Soda Co., Ltd.), RHODORSIL PHOTOINITIATOR 2074 (manufactured by Rhone-Poulenc Co., Ltd.), CD-1012 (manufactured by Sartomer Co., Ltd.), and the like. These photocationic polymerization initiators may be used singly or in combination of two or more. Also, if necessary, it can also be combined with lanthanide, 9-oxosulfur A sensitizer such as a system.

The thermal cationic polymerization initiator is not particularly limited, and examples thereof include various onium salts such as a quaternary ammonium salt, a phosphonium salt, and a phosphonium salt.

Examples of the above quaternary ammonium salt include tetrabutylammonium tetrafluoroborate, tetrabutylammonium hexafluorophosphate, tetrabutylammonium hydrogensulfate, tetraethylammonium tetrafluoroborate, and tetraethylammonium. p-Toluenesulfonate, N,N-dimethyl-N-benzylanilinium hexafluoroantimonate, N,N-dimethyl-N-benzylanilinium tetrafluoroborate, N,N-di Methyl-N-benzylpyridinium hexafluoroantimonate, N,N-diethyl-N-benzyl trifluoromethanesulfonate, N,N-dimethyl-N-(4-methoxy Benzyl)pyridinium hexafluoroantimonate, N,N-diethyl-N-(4-methoxybenzyl)toluene hexafluoroantimonate, and the like.

Examples of the onium salt include ethyltriphenylphosphonium hexafluoroantimonate and tetrabutylphosphonium hexafluoroantimonate.

Examples of the above phosphonium salt include triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluoroaluminate, and tris(4-methoxyphenyl)phosphonium hexafluoroaluminate. An acid salt, diphenyl (4-phenylthienyl) ruthenium hexafluoroaluminate or the like.

As a commercial one of the above-mentioned thermal cationic polymerization initiators, for example, Adekaopton CP-66, Adekaopton CP-77 (all manufactured by ADEKA), San-Aid SI-60L, San-Aid SI-80L, San -Aid SI-100L (all manufactured by Sanshin Chemical Industry Co., Ltd.), CI Series (manufactured by Nippon Soda Co., Ltd.), etc.

The content of the above cationic polymerization initiator is not particularly limited, and is relative to curability. The total weight of the resin is 100 parts by weight, preferably 0.1 part by weight, and preferably 10 parts by weight. When the content of the cationic polymerization initiator is less than 0.1 part by weight, the sealing agent for a liquid crystal display element of the present invention may not be sufficiently cured. When the content of the cationic polymerization initiator is more than 10 parts by weight, the storage stability may be lowered.

The sealing agent for liquid crystal dropping method of the present invention preferably contains a decane coupling agent. The above decane coupling agent mainly functions as a bonding aid for adhering a sealing agent to a substrate or the like well.

The decane coupling agent is not particularly limited, but is excellent in the effect of improving the adhesion to a substrate or the like, and is chemically bonded to the curable resin to suppress the flow of the curable resin into the liquid crystal. For example, Preferably, γ-aminopropyltrimethoxydecane, γ-mercaptopropyltrimethoxydecane, γ-glycidoxypropyltrimethoxydecane, γ-isocyanatepropyltrimethoxydecane, etc. are used. . These decane coupling agents may be used singly or in combination of two or more.

The content of the above-mentioned decane coupling agent is preferably 0.1 part by weight, and preferably 20 parts by weight, based on 100 parts by weight of the sealing compound for liquid crystal dropping method of the present invention. When the content of the above decane coupling agent is less than 0.1 part by weight, the effect produced by the preparation of the decane coupling agent may not be sufficiently exhibited. When the content of the above decane coupling agent exceeds 20 parts by weight, liquid crystal contamination may occur due to the obtained sealing compound for liquid crystal dropping method. A more preferred lower limit of the content of the above decane coupling agent is 0.5 part by weight, and a more preferred upper limit is 10 parts by weight.

The sealing agent for a liquid crystal dropping method of the present invention may further contain an opacifier. The sealing compound for liquid crystal dropping method of the present invention can be preferably used as a light-shielding sealant by containing the above-mentioned sunscreen agent.

Examples of the sunscreen agent include cerium oxide, titanium black, aniline black, and flowers. Cyan, fullerene, carbon black, resin-coated carbon black, and the like. Among them, titanium black is preferred.

The titanium black is a substance having a higher transmittance in the vicinity of an ultraviolet region, particularly a wavelength of 370 to 450 nm, in comparison with an average transmittance of light having a wavelength of 300 to 800 nm. In other words, the titanium black has a light-shielding agent which imparts light-shielding property to the sealing compound for liquid crystal dropping method of the present invention by sufficiently shielding the wavelength light in the visible light region, and transmits light of a wavelength near the ultraviolet region. Therefore, the present invention can be started by using light having a wavelength (370 to 450 nm) in which the transmittance of the titanium black becomes high, and the reaction can be started as the photoradical polymerization initiator or the photocationic polymerization initiator described above. The photocurability of the sealant for liquid crystal dropping method is further increased. On the other hand, the light-shielding agent contained in the sealing compound for liquid crystal dropping methods of the present invention is preferably a material having high insulating properties, and is preferably a titanium black as a light-shielding agent having high insulating properties.

The optical density (OD (optical density) value) per 1 μm of the titanium black is preferably 0.1 or more, and more preferably 0.2 or more. The higher the light-shielding property of the titanium black, the better, and there is no particularly preferable upper limit of the OD value of the titanium black, but it is usually 3.0 or less.

The titanium black may exhibit sufficient effects without surface treatment, but may be treated with an organic component such as a surface coupler or an inorganic component such as cerium oxide, titanium oxide, cerium oxide, aluminum oxide, zirconium oxide or magnesium oxide. Surface treated titanium black. Among them, it is preferable that the organic component is treated in terms of further improving the insulating property.

Moreover, the liquid crystal display element manufactured using the sealing compound for liquid crystal dropping methods of the present invention containing the above-mentioned titanium black as a light-shielding agent has sufficient light-shielding property, so that light leakage can be achieved, and a high contrast ratio can be obtained and excellent. The image displays a quality liquid crystal display element.

As a commercial one of the above-mentioned titanium black, for example, 12S, 13M, 13M-C, 13R-N (all manufactured by Mitsubishi Materials Co., Ltd.), Tilack D (manufactured by Ako Chemical Co., Ltd.), and the like.

The preferred lower limit of the specific surface area of the titanium black is 13m ² / g, the upper limit is preferably 30m ² / g, more preferably of a lower limit of 15m ² / g, more preferably the upper limit is 25m ² / g.

Moreover, the preferred lower limit of the volume resistance of the titanium black is 0.5 Ω. Cm, the preferred upper limit is 3Ω. Cm, the lower limit is 1Ω. The upper limit of cm, better is 2.5Ω. Cm.

The primary particle diameter of the light-shielding agent is not particularly limited as long as it is equal to or less than the distance between the substrates of the liquid crystal display device, and a preferred lower limit is 1 nm, and a preferred upper limit is 5 μm. When the primary particle diameter of the above-mentioned sunscreen agent is less than 1 nm, the viscosity or the shakeability of the sealant for liquid crystal dropping method obtained may be greatly increased, and the workability may be deteriorated. When the primary particle diameter of the above-mentioned sunscreen agent exceeds 5 μm, the coating property of the liquid crystal dropping method for the substrate may be deteriorated. A lower limit of the primary particle diameter of the above-mentioned opacifier is 5 nm, more preferably 200 nm, and still more preferably 10 nm, and further preferably 100 nm.

The content of the above-mentioned sunscreen agent is preferably 5% by weight, and preferably 80% by weight, based on the entire sealing agent for liquid crystal dropping method of the present invention. If the content of the above-mentioned sunscreen agent is less than 5% by weight, sufficient light-shielding properties may not be obtained. When the content of the above-mentioned light-shielding agent exceeds 80% by weight, the adhesion of the liquid crystal dropping method sealant to the substrate may be lowered or the strength after curing may be lowered or the drawability may be lowered. A more preferred lower limit of the content of the above-mentioned sunscreen agent is 10% by weight, more preferably 70% by weight, and still more preferably 30% by weight, and still more preferably 60% by weight.

Further, if necessary, the sealing agent for liquid crystal dropping method of the present invention may further contain a reactive diluent for adjusting the viscosity, a spacer such as a polymer bead for adjusting the gap of the panel, and An additive such as a hardening accelerator such as p-chlorophenyl-1,1-dimethylurea, an antifoaming agent, a leveling agent, or a polymerization inhibitor.

The method for producing the sealing compound for a liquid crystal dropping method of the present invention is not particularly limited, and examples thereof include a method using a homodisperser, a homomixer, a universal agitator, a planetary mixer, a kneader, and a three-roll mill. An additive such as a curable resin, talc, and a radical polymerization initiator, or a thermosetting agent, or a radical polymerization initiator, and a thermosetting agent, and optionally a decane coupling agent are added.

By disposing the conductive fine particles in the sealing compound for liquid crystal dropping method of the present invention, the upper and lower conductive materials can be produced. Further, such a sealing agent for a liquid crystal dropping method of the present invention and a conductive material for the upper and lower conductive particles are also one of the inventions.

The conductive fine particles are not particularly limited, and a metal ball or a conductive metal layer formed on the surface of the resin fine particles can be used. Among them, those having a conductive metal layer formed on the surface of the resin fine particles are preferred because they are excellent in elasticity by the resin fine particles so as not to damage the transparent substrate or the like.

Further, a liquid crystal display element obtained by using the sealing compound for a liquid crystal dropping method of the present invention or the conductive material for the upper and lower sides of the present invention is also one of the inventions.

According to the present invention, it is possible to provide a sealing compound for a liquid crystal dropping method which is excellent in drawability, adhesion, and moisture resistance of a cured product. Moreover, according to the present invention, it is possible to provide an upper and lower conductive material and a liquid crystal display element which are produced by using the sealing compound for a liquid crystal dropping method.

The invention is further illustrated in the following examples, but the invention is not limited to the examples.

(Examples 1 to 17 and Comparative Examples 1 to 3)

According to the blending ratios shown in Tables 1 to 3, each material was mixed using a planetary mixer ("Defoaming Stirling" manufactured by Thinky Co., Ltd.), and then mixed using a three-roll mill, thereby preparing Example 1~ 17. The sealing agent for the liquid crystal dropping method of Comparative Examples 1 to 3.

In addition, "SG-2000" in Tables 1-3 is a talc having a total content of CaMg(CO ₃ ) ₂ and MgCO ₃ of more than 0.2% by weight measured by an X-ray diffraction apparatus under the above conditions, "FG-15F" The talc having a total content of CaMg(CO ₃ ) ₂ and MgCO ₃ measured by an X-ray diffraction apparatus under the above conditions was 0.1% by weight or less.

Further, in Tables 1 to 3, "stearic acid-treated FG-15F" is a surface-treated talc obtained by dry-surface-treating 100 parts by weight of "FG-15F" and 10 parts by weight of stearic acid. "KBM-403 Process FG-15F" is manufactured by Shin-Etsu Silicones Co., Ltd. by 100 parts by weight of "FG-15F" and 10 parts by weight of γ-glycidoxypropyltrimethoxydecane. "KBM-403") Surface-treated talc obtained by dry surface treatment, "KBM-603 treated FG-15F" by using 100 parts by weight of "FG-15F" and 10 parts by weight of N-2-( Aminoethyl)-3-aminopropyltrimethoxydecane (manufactured by Shin-Etsu Silicones Co., Ltd., "KBM-603") is a surface-treated talc obtained by dry surface treatment.

<evaluation>

The following evaluations were performed on the sealants obtained in the examples and the comparative examples. The results are shown in Tables 1 to 3.

(drawability)

1% by weight of a ceria spacer ("SI-H055" manufactured by Sekisui Chemical Co., Ltd.) was added to the sealing compound for liquid crystal dropping method obtained in the examples and the comparative examples, and the defoaming treatment was carried out to remove the sealant. After the foaming, it was filled in a syringe for dispensing ("PSY-10E" manufactured by Musashi Engineering Co., Ltd.), and defoaming treatment was performed again. Then, a sealant was applied to a transparent electrode substrate with an ITO film by using a dispenser (manufactured by Musashi Engineering Co., Ltd., "SHOTMASTER 300"), and the sealing agent was applied by a vacuum bonding apparatus under a reduced pressure of 5 Pa. Another transparent substrate. After irradiating the unit after bonding with a metal halide lamp to ultraviolet rays of 3,000 mJ/cm ² and then heating at 120 ° C for 60 minutes, the sealing agent was thermally cured, and each of the five sealing liquid crystal cells was produced. The sealant in the liquid crystal cell was observed, and the case where the sealant was not broken or bent at the end and the beautiful line was drawn was evaluated as "◎", and the sealant was not broken. In the case where the end portion is slightly bent or the like, it is evaluated as "○", and the case where the end portion of the sealant is clearly bent or the like is not changed, and the case where the end portion of the sealant is clearly bent is evaluated as "Δ", and the disconnection is caused. The situation is set to "X" for evaluation.

(adhesive)

1% by weight of a ceria spacer ("SI-H055" manufactured by Sekisui Chemical Co., Ltd.) was added to the sealant obtained in the examples and the comparative examples, and the droplets were dropped to 2 sheets of an alkali glass with an ITO film. One of the sheets (30 × 40 mm), and another glass test piece was attached thereto in a cross shape, and after irradiating ultraviolet rays of 3000 mJ/cm ² with a metal halide lamp, heating at 120 ° C for 60 minutes, borrowed Thus, a test piece was obtained. The tensile test (5 mm/sec) was carried out using a collet disposed on the upper and lower sides. The value obtained by dividing the obtained measurement value (kgf) by the seal coating cross-sectional area (cm ² ) is 30 kgf/cm ² or more, and it is evaluated as "◎", and is 20 kgf/cm ² or more and less than 30 kgf. In the case of /cm ^{2 ,} it is evaluated as "○", and when 10 kgf/cm ² or more and less than 20 kgf/cm ^{2 are} set to "△", the evaluation is made, and when it is less than 10 kgf/cm ^{2 ,} it is set to "X". Conduct an evaluation.

(moisture resistance of hardened material)

The sealant obtained in the examples and the comparative examples was applied to a smooth release film having a thickness of 200 to 300 μm by a coater, and then irradiated with ultraviolet rays of 3000 mJ/cm ² with a metal halide lamp, and thereafter, at 120 After heating at ° C for 60 minutes, a cured film for moisture permeability measurement was obtained. A cylindrical plate for moisture permeability test is produced by a method for measuring the moisture permeability of a moisture-proof packaging material according to JIS Z 0208 (cylinder plate method), and the obtained cured film for moisture permeability measurement is attached and put into a humidity of 80 ° C. The moisture permeability was measured in a 90% RH high temperature and high humidity oven. The value of the obtained moisture permeability is less than 40 g/m ² . The case of 24 hr was set to "◎" for evaluation, and 40 g/m ^{2 was used} . More than 24hr and less than 60g/m ² . The case of 24 hr was set to "○" for evaluation, and 60 g/m ^{2 was used} . More than 24hr and less than 80g/m ² . The case of 24 hr was set to "△" for evaluation, and 80 g/m ^{2 was used} . The case of 24 hr or more is set to "x" for evaluation.

[Industrial availability]

According to the present invention, it is possible to provide a sealing compound for a liquid crystal dropping method which is excellent in drawability, adhesion, and moisture resistance of a cured product. Moreover, according to the present invention, it is possible to provide an upper and lower conductive material and a liquid crystal display element which are produced by using the sealing compound for a liquid crystal dropping method.

Claims (12)

A sealant for a liquid crystal dropping method, comprising a curable resin, talc, a radical polymerization initiator or a heat hardener, or a radical polymerization initiator and a heat hardener, characterized in that the talc is The total content of CaMg(CO ₃ ) ₂ and MgCO ₃ is 0.1% by weight or less. The sealing agent for a liquid crystal dropping method according to the first aspect of the patent application, wherein the talc is surface-treated by a surface treatment agent. The sealant for liquid crystal dropping method of claim 2, wherein the surface treatment agent is a decane coupling agent. The sealant for liquid crystal dropping method according to claim 3, wherein the decane coupling agent is a decane coupling agent having an epoxy group. The sealant for a liquid crystal dropping method according to the first, second, third or fourth aspect of the invention, wherein the content of the talc is 0.1 to 50 parts by weight based on 100 parts by weight of the curable resin. The sealant for liquid crystal dropping method according to claim 1, 2, 3, 4 or 5, wherein the curable resin contains a (meth) acrylate having a hetero-cyanuric acid skeleton and/or has a dicyclopentane A (meth) acrylate of a diene skeleton. The sealant for a liquid crystal dropping method according to the sixth aspect of the invention, wherein the curable resin contains a (meth) acrylate having a hetero-cyanuric acid skeleton, and the above-mentioned (meth) acrylate having a hetero-cyanuric acid skeleton Acrylate is ethoxylated isomeric cyanuric acid triacrylate. The sealant for liquid crystal dropping method according to claim 6 or 7, wherein the curable resin contains a (meth) acrylate having a dicyclopentadiene skeleton, and The above (meth) acrylate tricyclodecane dimethanol diacrylate having a dicyclopentadiene skeleton. The sealant for liquid crystal dropping method according to claim 6, 7 or 8, wherein the (meth) acrylate having a hetero-cyanuric acid skeleton and the (meth) acrylate having a dicyclopentadiene skeleton The content is 0.1 to 30 parts by weight based on 100 parts by weight of the entire curable resin. A sealant for a liquid crystal dropping method according to the first, second, third, fourth, fifth, sixth, seventh, eighth or ninth aspect of the patent application, which contains an opacifier. The upper and lower conductive materials are the sealing agent for liquid crystal dropping method and the conductive fine particles according to the first, second, third, fourth, fifth, sixth, seventh, eighth, ninth or tenth patent application. A liquid crystal display element using the liquid crystal dropping method sealing agent of the first, second, third, fourth, fifth, sixth, seventh, eighth, ninth or tenth patent application, or the upper conductive material of the eleventh item of the patent application scope Made.