JP5374666B1 - Liquid crystal dropping method sealing agent, vertical conduction material, and liquid crystal display element - Google Patents

Abstract

An object of this invention is to provide the sealing agent for liquid crystal dropping methods excellent in drawing property, adhesiveness, and moisture resistance of hardened | cured material. Moreover, an object of this invention is to provide the vertical conduction material and liquid crystal display element which are manufactured using this sealing compound for liquid crystal dropping methods.
The present invention is a sealing agent for a liquid crystal dropping method containing a curable resin, talc, and a radical polymerization initiator or a thermosetting agent, or both a radical polymerization initiator and a thermosetting agent, This is a liquid crystal dropping method sealing agent in which the total content of CaMg (CO ₃ ) ₂ and MgCO ₃ is 0.1% by weight or less.

Description

The present invention relates to a sealant for a liquid crystal dropping method that is excellent in drawing properties, adhesiveness, and moisture resistance of a cured product. Moreover, this invention relates to the vertical conduction material and liquid crystal display element which are manufactured using this sealing compound for liquid crystal dropping methods.

In recent years, a method for manufacturing a liquid crystal display element such as a liquid crystal display cell has been disclosed in, for example, Patent Document 1 and Patent Document 2 from the conventional vacuum injection method from the viewpoint of shortening tact time and optimizing the amount of liquid crystal used. Such a photocurable resin, a photopolymerization initiator, a thermosetting resin, and a liquid crystal dropping method called a dropping method using a light and heat combined curing type sealant containing a thermosetting agent are being replaced.

In the dropping method, first, a rectangular seal pattern is formed on one of two transparent substrates with electrodes by dispensing. Next, a liquid crystal micro-droplet is dropped on the entire surface of the transparent substrate frame with the sealant being uncured, and the other transparent substrate is immediately overlaid, and the seal portion is irradiated with light such as ultraviolet rays to perform temporary curing. . Thereafter, heating is performed at the time of liquid crystal annealing to perform main curing, and a liquid crystal display element is manufactured. If the substrates are bonded together under reduced pressure, a liquid crystal display element can be manufactured with extremely high efficiency, and this dripping method is currently the mainstream method for manufacturing liquid crystal display elements.

In a liquid crystal display element, a sealing agent is required to have excellent drawing performance, and at the time of manufacturing, it is required to increase the dispensing speed in order to improve the efficiency of the process. However, when the conventional sealant is drawn at high speed, the sealant cannot be drawn stably, and there is a problem that a disconnection failure occurs or the sealant line after drawing is wavy. It was. Normally, an inorganic filler is blended in the sealing agent, and in order to improve the drawability, it is conceivable to reduce the amount of the inorganic filler to be blended in the sealing agent, but if the amount of the inorganic filler is reduced, In addition, there is a problem that the adhesion of the sealing agent to the substrate or the alignment film is lowered, or the moisture resistance of the sealing agent is lowered.
Patent Document 3 discloses a method of blending talc as an inorganic filler in a sealant for the purpose of improving the adhesiveness of the sealant, and in particular, talc is used as an inorganic filler in this way. When blended, it was difficult to stably draw the sealant.

JP 2001-133794 A International Publication No. 02/092718 Pamphlet JP 2008-40015 A

An object of this invention is to provide the sealing agent for liquid crystal dropping methods excellent in drawing property, adhesiveness, and moisture resistance of hardened | cured material. Moreover, an object of this invention is to provide the vertical conduction material and liquid crystal display element which are manufactured using this sealing compound for liquid crystal dropping methods.

The present invention is a sealing agent for a liquid crystal dropping method containing a curable resin, talc, and a radical polymerization initiator or a thermosetting agent, or both a radical polymerization initiator and a thermosetting agent. This is a liquid crystal dropping method sealing agent in which the total content of CaMg (CO ₃ ) ₂ and MgCO ₃ is 0.1% by weight or less.
The present invention is described in detail below.

Generally, talc is mixed with impurities such as dolomite (CaMg (CO ₃ ) ₂ ) and magnesite (MgCO ₃ ). As a result of intensive studies, the present inventors have surprisingly found that CaMg (CO ₃ ) ₂ and MgCO ₃ have a great influence on the deterioration of the drawability of the sealant.
Therefore, the inventors of the present invention blended talc with a content of CaMg (CO ₃ ) ₂ and MgCO ₃ below a specific amount into a sealing agent for liquid crystal dropping method, thereby reducing drawability, adhesiveness, and cured product. It has been found that a sealing agent for liquid crystal dropping method having excellent moisture resistance can be obtained, and the present invention has been completed.

The sealing agent 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 agent for liquid crystal dropping method is inferior in drawability. The total content of CaMg (CO ₃ ) ₂ and MgCO _{3 in} the talc is preferably as small as possible, and is 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 talc is 0.0001% by weight.
The content of CaMg (CO ₃ ) _{2 in} the talc can be determined from the area ratio of the peak at a diffraction angle of 30.9 ° derived from CaMg (CO ₃ ) ₂ in X-ray diffraction measurement (± 0.2 An error of about ° is allowed).
The content of MgCO _{3 in} the talc can be determined from the area ratio of the peak at a diffraction angle of 32.6 ° derived from MgCO ₃ in the X-ray diffraction measurement (an error of about ± 0.2 ° is allowed). To do).
In addition, the measurement conditions of the X-ray diffraction measurement in this invention are as follows.
Measuring instrument: X'Pert-PRO-MPD (Spectris)
Target: Cu
Scan angle: 5 ° -60 °
Scanning speed: 2 ° / distributor voltage: 40 kV
Tube current: 30 mA
Incident side slit: 0.04 ° solar slit, automatic variable divergence slit, AS1 °
Receiving side slit: 0.04 °
The detection limit under this condition is 0.1%.
In this specification, “the total content of CaMg (CO ₃ ) ₂ and MgCO ₃ in talc” means the total content of CaMg (CO ₃ ) ₂ and MgCO ₃ derived from talc with respect to the entire talc including impurities. Means quantity.

Examples of commercially available talc having a total content of CaMg (CO ₃ ) ₂ and MgCO ₃ of 0.1% by weight or less include FG-15F and D-800F (both manufactured by Nippon Talc Co., Ltd.). ) And the like.

Examples of the method for reducing the total content of CaMg (CO ₃ ) ₂ and MgCO _{3 in} the talc to 0.1% by weight or less include separation and purification by classification.
Examples of separation and purification methods for reducing the total content of CaMg (CO ₃ ) ₂ and MgCO ₃ to 0.1% by weight or less include classifiers such as a forced vortex classifier and a semi-free vortex classifier And the like. Examples of commercially available classifiers include turbo classifiers and eddy classifiers (both manufactured by Nisshin Engineering Co., Ltd.).

The talc is preferably surface-treated with a surface treatment agent.
Examples of the surface treatment agent include silane coupling agents, fatty acids, titanate coupling agents, and the like. Especially, since it is excellent in the effect which improves the adhesiveness of the sealing agent obtained, a silane coupling agent is preferable, and also the silane coupling agent which has an epoxy group among these is more preferable.

Examples of the silane coupling agent used as the talc surface treatment agent include vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and 3-glycidoxypropylmethyldimethoxy. Silane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3 -Methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl)- -Aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1 , 3-dimethylbutylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane Dimethyl diethoxy silane, phenyl triethoxy silane, hexyl trimethoxy silane, hexyl triethoxysilane, decyl trimethoxysilane, trifluoropropyl trimethoxysilane, and the like.

Examples of commercially available silane coupling agents include KBM-303, KBM-403, KBM-502, KBM-602, and KBM-603 (all manufactured by Shin-Etsu Silicone).

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

Examples of titanate coupling agents used as the surface treatment agent for talc include titanium acylates such as tributoxy titanium stearate, isopropoxy titanium triisostearate, mono-i-propoxy titanium tri-i-stearate, Titanium alkoxides such as titanium tetraethoxide, titanium tetrapropoxide, titanium tetrabutoxide, tetracyclohexyl titanate, tetrabenzyl titanate, di-n-butoxy bis (triethanolaminato) titanium, titanium diisopropoxy bis (acetylacetate) Acid), titanium tetraacetylacetonate, titanium di-2-ethylhexoxybis (2-ethyl-3-hydroxyhexoxide), titanium diisopropoxybis (ethylacetoacetate), etc. Over doors and the like.

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

The preferable lower limit of the average particle diameter of the talc is 0.2 μm, and the preferable upper limit is 5 μm. When the average particle diameter of the talc is less than 0.2 μm, viscosity and thixotropy increase, which may result in poor workability. When the average particle diameter of the talc exceeds 5 μm, display unevenness may occur in the liquid crystal display element due to a gap defect. The more preferable lower limit of the average particle diameter of the talc is 0.6 μm, and the more preferable upper limit is 3 μm.
In the present specification, the average particle diameter means an average value of particle diameters (major diameters) of 10 particles observed at a magnification of 5000 using a scanning electron microscope. Moreover, as the scanning electron microscope, S-4300 (manufactured by Hitachi High-Technologies Corporation) or the like can be used.

The content of the talc is preferably 0.1 parts by weight and preferably 50 parts by weight with respect to 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 agent for liquid crystal dropping method is inferior in adhesiveness and peels off, or the cured product is inferior in moisture resistance. There is. If the content of the talc exceeds 50 parts by weight, the viscosity and thixotropy of the obtained sealing agent for liquid crystal dropping method may increase, resulting in poor workability. The minimum with more preferable content of the said talc is 1 weight part, and a more preferable upper limit is 40 weight part.

The sealing agent for liquid crystal dropping method of the present invention may contain other inorganic fillers other than the talc as long as the object of the present invention is not impaired.
The said other inorganic filler is not specifically limited, For example, a silica, an alumina, a titanium oxide, a calcium carbonate etc. are mentioned. Of these, silica is preferred.
Hereinafter, talc and other inorganic fillers are also simply referred to as inorganic fillers.

The minimum with the preferable average particle diameter of the said inorganic filler is 0.01 micrometer, and a preferable upper limit is 5.0 micrometers. When the average particle diameter of the inorganic filler is less than 0.01 μm, viscosity and thixotropy increase, which may result in poor workability. 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 a gap defect. The minimum with a more preferable average particle diameter of the said inorganic filler is 0.1 micrometer, and a more preferable upper limit is 3.0 micrometers.

When it contains the said other inorganic filler, the minimum with preferable content of the said whole inorganic filler is 1 weight%, and a preferable upper limit is 60 weight%. When the content of the whole inorganic filler is less than 1% by weight, the cured product of the obtained liquid crystal dropping method sealing agent may be inferior in moisture resistance. If the total content of the inorganic filler exceeds 60% by weight, the viscosity and thixotropy of the resulting liquid crystal dropping method sealing agent may increase, resulting in poor workability. A more preferable lower limit of the content of the whole inorganic filler is 10% by weight, and a more preferable upper limit is 50% by weight.

The sealing agent for liquid crystal dropping method of the present invention contains a curable resin.
Examples of the curable resin include (meth) acrylic resins and epoxy resins.
Especially, it is preferable that the said curable resin contains the (meth) acrylate which has an isocyanur skeleton, and / or the (meth) acrylate which has a dicyclopentadiene skeleton. By containing the (meth) acrylate having the isocyanuric skeleton and / or the (meth) acrylate having the dicyclopentadiene skeleton, the sealing agent for liquid crystal dropping method of the present invention is particularly excellent in moisture resistance of the cured product. Become.
In the present specification, the “(meth) acrylic” means acryl or methacryl, and the “(meth) acrylic resin” means a resin having a (meth) acryloyl group. The term “(meth) acryloyl group” means an acryloyl group or a methacryloyl group. Moreover, in this specification, (meth) acrylate means an acrylate or a methacrylate.

Examples of the (meth) acrylate having an isocyanuric skeleton include ethoxylated isocyanuric triacrylate, ethoxylated isocyanuric trimethacrylate, caprolactone-modified ethoxylated isocyanuric triacrylate, caprolactone-modified ethoxylated isocyanuric trimethacrylate, and the like. Of these, ethoxylated isocyanuric triacrylate having good adhesiveness is preferable.

Examples of the (meth) acrylate having a dicyclopentadiene skeleton include tricyclodecane dimethanol diacrylate and tricyclodecane dimethanol dimethacrylate. Of these, tricyclodecane dimethanol diacrylate having good adhesiveness is preferable.

The content of the (meth) acrylate having the isocyanuric skeleton and the (meth) acrylate having the dicyclopentadiene skeleton is preferably 0.1 parts by weight and preferably has a preferable upper limit with respect to 100 parts by weight of the entire curable resin. 30 parts by weight. When the content of the (meth) acrylate having the isocyanuric skeleton and the (meth) acrylate having the dicyclopentadiene skeleton is less than 0.1 parts by weight, the moisture resistance of the cured product of the liquid crystal dropping method sealing agent is improved. The effect may not be fully exhibited. When the content of the (meth) acrylate having the isocyanuric skeleton and the (meth) acrylate having the dicyclopentadiene skeleton exceeds 30 parts by weight, liquid crystal contamination may be increased. The more preferable lower limit of the content of the (meth) acrylate having the isocyanuric skeleton and the (meth) acrylate having the dicyclopentadiene skeleton is 1 part by weight, and the more preferable upper limit is 20 parts by weight.

The curable resin preferably contains an epoxy (meth) acrylate.
In addition, in this specification, the said "epoxy (meth) acrylate" represents the compound which made all the epoxy groups in an epoxy resin react with (meth) acrylic acid.
The epoxy (meth) acrylate is not particularly limited, and examples thereof include those obtained by reacting (meth) acrylic acid and an epoxy resin in the presence of a basic catalyst according to a conventional method. Among these, an epoxy methacrylate resin is preferable because the cured product has excellent moisture resistance.

The epoxy resin used as a raw material for synthesizing the epoxy (meth) acrylate is not particularly limited. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, 2,2′-diallylbisphenol A Type epoxy resin, hydrogenated bisphenol type epoxy resin, propylene oxide added bisphenol A type epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy resin, sulfide type epoxy resin, diphenyl ether type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy Resin, phenol novolac epoxy resin, orthocresol novolac epoxy resin, dicyclopentadiene novolac epoxy resin, biphenyl novolac epoxy resin Naphthalene phenol novolac-type epoxy resin, glycidyl amine type epoxy resin, alkyl polyol type epoxy resin, rubber modified epoxy resin, glycidyl ester compounds, bisphenol A type episulfide resins.

As what is marketed among the said bisphenol A type epoxy resin, Epicoat 828EL, Epicoat 1004 (all are the Mitsubishi Chemical company make), Epiklon 850 (made by DIC company), etc. are mentioned, for example.
As what is marketed among the said bisphenol F type epoxy resins, Epicoat 806, Epicoat 4004 (all are Mitsubishi Chemical Corporation make) etc. are mentioned, for example.
As what is marketed among the said bisphenol S-type epoxy resins, Epicron EXA1514 (made by DIC Corporation) etc. are mentioned, for example.
As what is marketed among the said 2,2'- diallyl bisphenol A type epoxy resins, RE-810NM (made by Nippon Kayaku Co., Ltd.) etc. are mentioned, for example.
As what is marketed among the said hydrogenated bisphenol type | mold epoxy resins, Epicron EXA7015 (made by DIC Corporation) etc. are mentioned, for example.
As what is marketed among the said propylene oxide addition bisphenol A type epoxy resins, EP-4000S (made by ADEKA) etc. are mentioned, for example.
As what is marketed among the said resorcinol type epoxy resins, EX-201 (made by Nagase ChemteX Corporation) etc. are mentioned, for example.
As what is marketed among the said biphenyl type epoxy resins, Epicoat YX-4000H (made by Mitsubishi Chemical Corporation) etc. are mentioned, for example.
As what is marketed among the said sulfide type epoxy resins, YSLV-50TE (made by Tohto Kasei Co., Ltd.) etc. are mentioned, for example.
As what is marketed among the said diphenyl ether type epoxy resins, YSLV-80DE (made by Tohto Kasei Co., Ltd.) etc. are mentioned, for example.
As what is marketed among the said dicyclopentadiene type epoxy resins, EP-4088S (made by ADEKA) etc. are mentioned, for example.
As what is marketed among the said naphthalene type | mold epoxy resins, Epicron HP4032, Epicron EXA-4700 (all are the products made from DIC) etc. are mentioned, for example.
As what is marketed among the said phenol novolak-type epoxy resins, Epicron N-770 (made by DIC Corporation) etc. are mentioned, for example.
As what is marketed among the said ortho cresol novolak-type epoxy resins, Epicron N-670-EXP-S (made by DIC) etc. are mentioned, for example.
As what is marketed among the said dicyclopentadiene novolak-type epoxy resins, epiclone HP7200 (made by DIC) etc. are mentioned, for example.
As what is marketed among the said biphenyl novolak-type epoxy resins, NC-3000P (made by Nippon Kayaku Co., Ltd.) etc. are mentioned, for example.
As what is marketed among the said naphthalene phenol novolak-type epoxy resins, ESN-165S (made by Tohto Kasei Co., Ltd.) etc. are mentioned, for example.
As what is marketed among the said glycidylamine type epoxy resins, Epicoat 630 (made by Mitsubishi Chemical Corporation), Epicron 430 (made by DIC Corporation), TETRAD-X (made by Mitsubishi Gas Chemical Co., Inc.) etc. are mentioned, for example.
Examples of commercially available alkyl polyol type epoxy resins include ZX-1542 (manufactured by Toto Kasei), Epicron 726 (manufactured by DIC), Epolite 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.), Denacol EX-611 ( Nagase ChemteX Corporation).
Examples of commercially available rubber-modified epoxy resins include YR-450, YR-207 (both manufactured by Tohto Kasei Co., Ltd.), Epolide PB (manufactured by Daicel Chemical Industries, Ltd.), and the like.
As what is marketed among the said glycidyl ester compounds, Denacol EX-147 (made by Nagase ChemteX Corporation) etc. is mentioned, for example.
As what is marketed among the said bisphenol A type | mold episulfide resin, Epicoat YL-7000 (made by Mitsubishi Chemical Corporation) etc. are mentioned, for example.
Other commercially available epoxy resins include, for example, 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 ( These include Mitsubishi Chemical Corporation), EXA-7120 (DIC Corporation), TEPIC (Nissan Chemical Corporation), and the like.

Examples of commercially available epoxy (meth) acrylates include, for example, Evecryl 860, Evekril 3200, Evekril 3201, Evekryl 3412, Evekril 3600, Evekril 3700, Evekrill 3703, Evekril 3703, Evekril 3800, Evekril 6040. , Evacryl RDX63182 (all manufactured by Daicel Cytec), EA-1010, EA-1020, EA-5323, EA-5520, 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 ester 30 2A, 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 (Both manufactured by Nagase ChemteX Corporation).

The sealing agent for liquid crystal dropping method of the present invention may contain an epoxy resin as a curable resin.
As said epoxy resin, if it is resin to which the epoxy group was provided, it can be used without a limitation, The epoxy resin used as a raw material for synthesize | combining the said epoxy (meth) acrylate etc. can be used.

Moreover, you may contain a partial (meth) acryl modified epoxy resin as said epoxy resin.
In the present specification, the “partially (meth) acryl-modified epoxy resin” means a resin having one or more epoxy groups and (meth) acryloyloxy groups in one molecule. In the present specification, the above (meth) acryloyloxy group means an acryloyloxy group or a methacryloyloxy group.
The partial (meth) acryl-modified epoxy resin can be obtained, for example, by reacting an epoxy group of a part of an epoxy resin having two or more epoxy groups with (meth) acrylic acid.

The upper limit with the preferable ratio of the epoxy group with respect to the total amount of the (meth) acryloyloxy group and an epoxy group in the said whole curable resin is 50 mol%. When the ratio of the epoxy group exceeds 50 mol%, the resulting liquid crystal dropping method sealing agent is highly soluble in liquid crystals, causing liquid crystal contamination, and the resulting liquid crystal display element may be inferior in display performance. is there. A more preferable upper limit of the ratio of the epoxy group is 20 mol%.

The sealing agent for liquid crystal dropping method of the present invention contains a radical polymerization initiator or a thermosetting agent, or both a radical polymerization initiator and a thermosetting agent.
In the present specification, the above-mentioned “containing a radical polymerization initiator or a thermosetting agent, or both a radical polymerization initiator and a thermosetting agent” means at least one of a radical polymerization initiator and a thermosetting agent. Is contained.
Examples of the radical polymerization initiator include a photo radical polymerization initiator and a thermal radical polymerization initiator.

Among the radical polymerization initiators, examples of the photo radical polymerization initiator that generates radicals when irradiated with light include benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, and oxime esters. A compound, a benzoin ether compound, thioxanthone, or the like can be preferably used.
Examples of commercially available photo radical polymerization initiators include Irgacure 184, Irgacure 369, Irgacure 379, Irgacure 651, Irgacure 819, Irgacure 907, Irgacure 2959, Irgacure OXE01, and Lucyrin TPO (all of which are BASF). Japan), benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether (all manufactured by Tokyo Chemical Industry Co., Ltd.) and the like. Among these, Irgacure 651, Irgacure 907, benzoin isopropyl ether, and Lucillin TPO are preferable because of their wide absorption wavelength range. These radical photopolymerization initiators may be used alone or in combination of two or more.

Among the above radical polymerization initiators, thermal radical polymerization initiators that generate radicals by heat are not particularly limited, and examples thereof include peroxides and azo compounds. Examples of commercially available ones include perbutyl O and perhexyl O. Perbutyl PV (all manufactured by NOF Corporation), V-30, V-501, V-601, VPE-0201 (all manufactured by Wako Pure Chemical Industries, Ltd.) and the like.

Although content of the said radical polymerization initiator is not specifically limited, A preferable minimum is 0.1 weight part and a preferable upper limit is 30 weight part with respect to 100 weight part of said curable resins. When the content of the radical polymerization initiator is less than 0.1 parts by weight, the polymerization of the obtained liquid crystal dropping method sealing agent may not sufficiently proceed. When the content of the radical polymerization initiator exceeds 30 parts by weight, a large amount of unreacted radical polymerization initiator remains, and the weather resistance of the obtained liquid crystal dropping method sealing agent may deteriorate. The minimum with more preferable content of the said radical polymerization initiator is 1 weight part, and a more preferable upper limit is 10 weight part.

The said thermosetting agent is not specifically limited, For example, organic acid hydrazide, an imidazole derivative, an amine compound, a polyhydric phenol type compound, an acid anhydride etc. are mentioned. Among these, solid organic acid hydrazide is preferably used.

The solid organic acid hydrazide is not particularly limited, and examples thereof include 1,3-bis [hydrazinocarboethyl-5-isopropylhydantoin], sebacic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide, and malonic acid dihydrazide. Examples of commercially available products include Amicure VDH, Amicure UDH (all manufactured by Ajinomoto Fine Techno Co.), SDH, IDH, ADH (all manufactured by Otsuka Chemical Co., Ltd.), and the like.

Although content of the said thermosetting agent is not specifically limited, A preferable minimum is 2 weight part with respect to 100 weight part of curable resin, and a preferable upper limit is 50 weight part. When the content of the thermosetting agent is less than 2 parts by weight, the obtained sealing agent for liquid crystal dropping method may be inferior in curability. When content of the said thermosetting agent exceeds 50 weight part, the viscosity of the sealing compound for liquid crystal dropping methods obtained will become high, and applicability | paintability may worsen. The minimum with more preferable content of the said thermosetting agent is 5 weight part, A more preferable upper limit is 20 weight part, Furthermore, a preferable upper limit is 15 weight part.

The sealing agent for liquid crystal dropping method of the present invention may 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 aromatic diazonium salts, aromatic iodonium salts, and aromatic sulfonium salts.
Examples of commercially available photocationic polymerization initiators include optomer SP-150, optomer SP-151, optomer SP-170, optomer SP-171 (all manufactured by ADEKA), UVE-1014 (general). Electronics Co., Ltd.), Irgacure 261 (BASF Japan), Sun-Aid SI-60L, Sun-Aid SI-80L, UVI-6990 (all from Union Carbide), BBI-103, MPI-103, TPS-103, MDS- 103, DTS-103, NAT-103, NDS-103 (all manufactured by Midori Chemical Co., Ltd.), Sun-Aid SI-100L (manufactured by Sanshin Chemical Industry Co., Ltd.), CI-2064, CI-2639, CI-2624, CI-2481 (Both made by Nippon Soda Co., Ltd.), RHODO RSIL PHOTOINITIATOR 2074 (manufactured by Rhone-Poulenc), CD-1012 (manufactured by Sartomer) and the like. These cationic photopolymerization initiators may be used alone or in combination of two or more. Moreover, you may use together sensitizers, such as anthracene type and a thioxanthone type, as needed.

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 sulfonium salt.

Examples of the quaternary ammonium salt include tetrabutylammonium tetrafluoroborate, tetrabutylammonium hexafluorophosphate, tetrabutylammonium hydrogen sulfate, tetraethylammonium tetrafluoroborate, tetraethylammonium p-toluenesulfonate, N, N-dimethyl. -N-benzylanilinium hexafluoroantimonate, N, N-dimethyl-N-benzylanilinium tetrafluoroborate, N, N-dimethyl-N-benzylpyridinium hexafluoroantimonate, N, N-diethyl-N-benzyl Trifluoromethanesulfonate, N, N-dimethyl-N- (4-methoxybenzyl) pyridinium hexafluoroantimonate, N, N-die -N- (4- methoxybenzyl) preparative Luigi hexafluoroantimonate and the like.

Examples of the phosphonium salt include ethyltriphenylphosphonium hexafluoroantimonate and tetrabutylphosphonium hexafluoroantimonate.
Examples of the sulfonium salt include triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluoroarsenate, tris (4-methoxyphenyl) sulfonium hexafluoroarsinate, and diphenyl (4-phenylthiophenyl). ) Sulfonium hexafluoroarsinate and the like.

Examples of commercially available thermal cationic polymerization initiators include Adeka Opton CP-66, Adeka Opton CP-77 (all manufactured by ADEKA), Sun-Aid SI-60L, Sun-Aid SI-80L, and Sun-Aid SI-100L ( All of them are manufactured by Sanshin Chemical Industry Co., Ltd.) and CI series (manufactured by Nippon Soda Co., Ltd.).

Although content of the said cationic polymerization initiator is not specifically limited, A preferable minimum is 0.1 weight part with respect to 100 weight part of whole curable resin, and a preferable upper limit is 10 weight part. If the content of the cationic polymerization initiator is less than 0.1 parts by weight, the sealing agent for liquid crystal display elements of the present invention may not be sufficiently cured. If the content of the cationic polymerization initiator exceeds 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 silane coupling agent. The silane coupling agent mainly has a role as an adhesion assistant for favorably bonding the sealing agent and the substrate.

Although the silane coupling agent is not particularly limited, it is excellent in the effect of improving adhesiveness with a substrate and the like, and it can suppress the outflow of the curable resin into the liquid crystal by chemically bonding with the curable resin. For example, γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-isocyanatopropyltrimethoxysilane and the like are preferably used. These silane coupling agents may be used alone or in combination of two or more.

The content of the silane coupling agent is such that the preferred lower limit is 0.1 parts by weight and the preferred upper limit is 20 parts by weight with respect to 100 parts by weight of the liquid crystal dropping method sealing agent of the present invention. When the content of the silane coupling agent is less than 0.1 parts by weight, the effect of blending the silane coupling agent may not be sufficiently exhibited. When content of the said silane coupling agent exceeds 20 weight part, the sealing compound for liquid crystal dropping methods obtained may cause liquid-crystal contamination. The minimum with more preferable content of the said silane coupling agent is 0.5 weight part, and a more preferable upper limit is 10 weight part.

The sealing agent for liquid crystal dropping method of the present invention may contain a light shielding agent. By containing the said light shielding agent, the sealing compound for liquid crystal dropping methods of this invention can be used suitably as a light shielding sealing agent.

Examples of the light-shielding agent include iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, and resin-coated carbon black. Of these, titanium black is preferable.

The titanium black is a substance having a higher transmittance in the vicinity of the ultraviolet region, particularly for light with a wavelength of 370 to 450 nm, compared to the average transmittance for light with a wavelength of 300 to 800 nm. That is, the above-described titanium black sufficiently shields light having a wavelength in the visible light region, thereby providing light shielding properties to the sealing agent for liquid crystal dropping method of the present invention, while transmitting light having a wavelength in the vicinity of the ultraviolet region. A shading agent. Therefore, the liquid crystal of the present invention can be used by using the photo radical polymerization initiator or the photo cationic polymerization initiator that can start the reaction with light having a wavelength (370 to 450 nm) at which the transmittance of the titanium black is high. The photocurability of the sealing agent for the dripping method can be further increased. On the other hand, the light shielding agent contained in the liquid crystal dropping method sealing agent of the present invention is preferably a highly insulating material, and titanium black is also suitable as the highly insulating light shielding agent.
The titanium black has an optical density (OD value) per μm of preferably 0.1 or more, and more preferably 0.2 or more. The higher the light-shielding property of titanium black, the better. There is no particular upper limit for the OD value of titanium black, but it is usually 3.0 or less.

The above-mentioned titanium black exhibits a sufficient effect even if it is not surface-treated, but the surface is treated with an organic component such as a coupling agent, silicon oxide, titanium oxide, germanium oxide, aluminum oxide, oxidized Surface-treated titanium black such as those coated with an inorganic component such as zirconium or magnesium oxide can also be used. Especially, what is processed with the organic component is preferable at the point which can improve insulation more.
In addition, the liquid crystal display device manufactured using the sealing agent for liquid crystal dropping method of the present invention containing the above-described titanium black as a light-shielding agent has a sufficient light-shielding property, and thus has a high contrast without light leakage. A liquid crystal display element having excellent image display quality can be realized.

Examples of commercially available titanium black include 12S, 13M, 13M-C, 13R-N (all manufactured by Mitsubishi Materials Corporation), Tilak D (manufactured by Ako Kasei Co., Ltd.), and the like.

The preferable lower limit of the specific surface area of the titanium black is 13 m ² / g, the preferable upper limit is 30 m ² / g, the more preferable lower limit is 15 m ² / g, and the more preferable upper limit is 25 m ² / g.
Further, the preferred lower limit of the volume resistance of the titanium black is 0.5 Ω · cm, the preferred upper limit is 3 Ω · cm, the more preferred lower limit is 1 Ω · cm, and the more preferred upper limit is 2.5 Ω · cm.

The primary particle diameter of the light-shielding agent is not particularly limited as long as it is not more than the distance between the substrates of the liquid crystal display element, but the preferred lower limit is 1 nm and the preferred upper limit is 5 μm. When the primary particle size of the light-shielding agent is less than 1 nm, the viscosity and thixotropy of the obtained liquid crystal dropping method sealing agent are greatly increased, and workability may be deteriorated. When the primary particle diameter of the light-shielding agent exceeds 5 μm, the coating property of the obtained liquid crystal dropping method sealing agent on the substrate may be deteriorated. The more preferable lower limit of the primary particle diameter of the light shielding agent is 5 nm, the more preferable upper limit is 200 nm, the still more preferable lower limit is 10 nm, and the still more preferable upper limit is 100 nm.

The preferable lower limit of the content of the light-shielding agent is 5% by weight and the preferable upper limit is 80% by weight with respect to the entire sealing agent for liquid crystal dropping method of the present invention. If the content of the light shielding agent is less than 5% by weight, sufficient light shielding properties may not be obtained. When the content of the light-shielding agent is more than 80% by weight, the adhesion of the obtained sealing agent for liquid crystal dropping method to the substrate and the strength after curing may be lowered, or the drawing property may be lowered. The more preferable lower limit of the content of the light-shielding agent is 10% by weight, the more preferable upper limit is 70% by weight, the still more preferable lower limit is 30% by weight, and the still more preferable upper limit is 60% by weight.

The liquid crystal dropping method sealing agent of the present invention further includes a reactive diluent for adjusting the viscosity, a spacer such as polymer beads for adjusting the panel gap, and 3-P-chlorophenyl-1,1- You may contain additives, such as hardening accelerators, such as a dimethyl urea, an antifoamer, a leveling agent, and a polymerization inhibitor.

The method for producing the sealing agent for liquid crystal dropping method of the present invention is not particularly limited. For example, using a mixer such as a homodisper, a homomixer, a universal mixer, a planetarium mixer, a kneader, or a three roll, a curable resin, Examples include a method of mixing talc and a radical polymerization initiator or a thermosetting agent, or both a radical polymerization initiator and a thermosetting agent, and an additive such as a silane coupling agent to be added as necessary. It is done.

A vertical conduction material can be manufactured by mix | blending electroconductive fine particles with the sealing compound for liquid crystal dropping methods of this invention. 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 liquid crystal display element which uses the sealing compound for liquid crystal dropping methods of this invention or the vertical conduction material of this invention is also one of this invention.

ADVANTAGE OF THE INVENTION According to this invention, the sealing compound for liquid crystal dropping methods which is excellent in drawing property, adhesiveness, and moisture resistance of hardened | cured material can be provided. Moreover, according to this invention, the vertical conduction material and liquid crystal display element which are manufactured using this sealing compound for liquid crystal dropping methods can be provided.

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

(Examples 1-17, Comparative Examples 1-3)
According to the blending ratio described in Tables 1 to 3, each material was mixed using a planetary stirrer (“Shinky Co., Ltd.“ Awatori Netaro ”), and then further mixed using three rolls. The sealing agent for liquid crystal dropping methods of Examples 1-17 and Comparative Examples 1-3 was prepared.
In Tables 1 to 3, “SG-2000” refers to talc in which the total content of CaMg (CO ₃ ) ₂ and MgCO ₃ measured using an X-ray diffractometer under the conditions described above is greater than 0.2% by weight. “FG-15F” is talc having a total content of CaMg (CO ₃ ) ₂ and MgCO ₃ measured by using an X-ray diffractometer under the above-described conditions of 0.1% by weight or less.
In Tables 1 to 3, “stearic acid-treated FG-15F” is a surface-treated talc obtained by dry-treating 100 parts by weight of “FG-15F” and 10 parts by weight of stearic acid. , “KBM-403-treated FG-15F” is obtained by dry-processing 100 parts by weight of “FG-15F” and 10 parts by weight of γ-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Silicone, “KBM-403”). This is a surface-treated talc obtained by surface treatment. “KBM-603-treated FG-15F” is composed of 100 parts by weight of “FG-15F” and N-2- (aminoethyl) -3-aminopropyltrimethoxy. This is a surface-treated talc obtained by dry-treating 10 parts by weight of silane (manufactured by Shin-Etsu Silicone Co., Ltd., “KBM-603”).

<Evaluation>
The following evaluation was performed about the sealing agent obtained by the Example and the comparative example. The results are shown in Tables 1-3.

(Drawability)
1% by weight of a silica spacer (“SI-H055” manufactured by Sekisui Chemical Co., Ltd.) is added to the sealing agent for liquid crystal dropping method obtained in Examples and Comparative Examples, and the foam in the sealing agent is removed by defoaming treatment. Then, a syringe for dispensing (“PSY-10E” manufactured by Musashi Engineering Co., Ltd.) was filled and defoamed again. Next, using a dispenser (“SHOTMASTER300” manufactured by Musashi Engineering Co., Ltd.), a sealing agent is applied to the transparent electrode substrate with the ITO thin film so as to draw a rectangular frame, and the other transparent substrate is coated with 5 Pa with a vacuum bonding apparatus. Bonding was performed under reduced pressure. The cells after pasting were irradiated with 3000 mJ / cm ² ultraviolet rays with a metal halide lamp, and then heated at 120 ° C. for 60 minutes to thermally cure the sealing agent, and five liquid crystal cells were prepared for each sealing agent. Observe the sealing agent in this liquid crystal cell, and if the sealing agent had a clean line with no disconnection and no waviness at the end, “◎”, no disconnection but a slight waviness at the end of the sealing agent. Evaluated as “○” if it occurred, “△” if there was a clear swell at the end of the sealant, but “×” if it was broken did.

(Adhesiveness)
1% by weight of a silica spacer (“SI-H055” manufactured by Sekisui Chemical Co., Ltd.) was added to the sealants obtained in the examples and comparative examples, and two alkali glass test pieces with ITO film (30 × 40 mm) Adhering a fine glass drop on one of them and pasting the other glass test piece in a cross shape onto the metal halide lamp by irradiating 3000 mJ / cm ² with ultraviolet rays and heating at 120 ° C. for 60 minutes. A specimen was obtained. This was subjected to a tensile test (5 mm / sec) with a chuck arranged vertically. The value obtained by dividing the measured value (kgf) by the cross-sectional area (cm ² ) applied to the seal is 30 kgf / cm ² or more, “◎”, if it is 20 kgf / cm ² or more and less than 30 kgf / cm ² Was evaluated as “◯” when “O” was 10 kgf / cm ² or more and less than 20 kgf / cm ² , and “X” when it was less than 10 kgf / cm ² .

(Humidity resistance of cured product)
After the sealing agents obtained in Examples and Comparative Examples were coated in a smooth release film shape with a coater to a thickness of 200 to 300 μm, irradiated with 3000 mJ / cm ² ultraviolet rays with a metal halide lamp, then 120 ° C. For 60 minutes to obtain a cured film for measuring moisture permeability. A moisture permeability test cup was prepared by a method according to JIS Z 0208 for moisture proof packaging materials (cup method), and the obtained cured film for moisture permeability measurement was attached, and the temperature was 80 ° C. and the humidity was 90% RH. The moisture permeability was measured by putting it in a high-temperature and high-humidity oven. The case where the obtained moisture permeability value is less than 40 g / m ² · 24 hr is “◎”, and the case where it is 40 g / m ² · 24 hr or more and less than 60 g / m ² · 24 hr is “◯”, 60 g / m ^The case where it was ² · 24 hr or more and less than 80 g / m ² · 24 hr was evaluated as “Δ”, and the case where it was 80 g / m ² · 24 hr or more was evaluated as “x”.

ADVANTAGE OF THE INVENTION According to this invention, the sealing compound for liquid crystal dropping methods which is excellent in drawing property, adhesiveness, and moisture resistance of hardened | cured material can be provided. Moreover, according to this invention, the vertical conduction material and liquid crystal display element which are manufactured using this sealing compound for liquid crystal dropping methods can be provided.

Claims (12)

A curable resin, talc, and a radical polymerization initiator or a thermosetting agent, or a liquid crystal dropping method sealing agent containing both a radical polymerization initiator and a thermosetting agent,
A total amount of CaMg (CO ₃ ) ₂ and MgCO _{3 in} the talc is 0.1% by weight or less. The sealing agent for liquid crystal dropping method according to claim 1, wherein the talc is surface-treated with a surface treating agent. The sealing agent for liquid crystal dropping method according to claim 2, wherein the surface treatment agent is a silane coupling agent. 4. The sealing agent for liquid crystal dropping method according to claim 3, wherein the silane coupling agent is a silane coupling agent having an epoxy group. 5. The liquid crystal dropping method sealing agent according to claim 1, wherein the talc content is 0.1 to 50 parts by weight with respect to 100 parts by weight of the curable resin. 6. The liquid crystal dropping method according to claim 1, wherein the curable resin contains (meth) acrylate having an isocyanuric skeleton and / or (meth) acrylate having a dicyclopentadiene skeleton. Sealing agent. The curable resin contains a (meth) acrylate having an isocyanuric skeleton,
The sealing agent for liquid crystal dropping method according to claim 6, wherein the (meth) acrylate having an isocyanuric skeleton is ethoxylated isocyanuric triacrylate. The curable resin contains a (meth) acrylate having a dicyclopentadiene skeleton,
The sealing agent for liquid crystal dropping method according to claim 6 or 7, wherein the (meth) acrylate having a dicyclopentadiene skeleton is tricyclodecane dimethanol diacrylate. The content of (meth) acrylate having an isocyanuric skeleton and (meth) acrylate having a dicyclopentadiene skeleton is 0.1 to 30 parts by weight with respect to 100 parts by weight of the entire curable resin. Item 9. A sealing agent for liquid crystal dropping method according to item 6, 7 or 8. The light-shielding agent is contained, The sealing agent for liquid crystal dropping methods of Claim 1, 2, 3, 4, 5, 6, 7, 8 or 9 characterized by the above-mentioned. A vertical conducting material comprising the sealing agent for a liquid crystal dropping method according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, and conductive fine particles. It is manufactured using the sealing agent for liquid crystal dropping methods according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, or the vertical conduction material according to claim 11. Liquid crystal display element.