TWI723060B - Sealant for liquid crystal display element, vertical conduction material and liquid crystal display element - Google Patents

Abstract

The object of the present invention is to provide a sealant for liquid crystal display elements that can achieve both low-temperature curability and storage stability. In addition, an object of the present invention is to provide an upper and lower conduction material and a liquid crystal display element using this sealant for liquid crystal display elements.

The present invention relates to a sealant for liquid crystal display elements, which contains a curable resin and a thermosetting agent, wherein the curable resin contains a curable resin having an epoxy group, and the thermosetting agent contains an epoxy resin The structure and the amine addition compound derived from the structure of the amine compound, the amine compound that becomes the source of the above-mentioned amine addition compound is an alkylimidazole with a carbon number of 1-20.

Description

Sealant for liquid crystal display element, vertical conduction material and liquid crystal display element

The present invention relates to a sealant for liquid crystal display elements that can achieve both low-temperature curability and storage stability. In addition, the present invention relates to an upper and lower conduction material and a liquid crystal display element using this sealing compound for liquid crystal display elements.

In recent years, as a method of manufacturing liquid crystal display elements such as liquid crystal display units, from the viewpoints of shortening the tact time and optimizing the amount of liquid crystal used, the methods disclosed in Patent Document 1 and Patent Document 2 have been used. The method of using a hardening type sealant with light and heat containing a hardening resin, a photopolymerization initiator, and a heat hardening agent is called the drip method. In the instillation method, a rectangular seal pattern is first formed on one of the two substrates with electrodes by dispensing glue. Then, the liquid crystal droplets are dropped into the sealing frame of the substrate in a state where the sealant is not hardened, another substrate is superimposed under vacuum, and the sealing part is irradiated with light such as ultraviolet rays to temporarily harden. After that, heating is performed to perform main curing, and a liquid crystal display element is produced. At present, the drip method has become the mainstream of the manufacturing method of liquid crystal display elements.

From the viewpoint of energy saving and liquid crystal stability, the above-mentioned sealant is desirably thermally cured by heating at a low temperature for a short time. As a method for hardening the sealant by heating at a low temperature and a short time, previously, a thermal hardening agent or hardening accelerator with a lower melting point has been used. however, If a thermal hardening agent or hardening accelerator with a low melting point is used, there is a problem that the reaction is likely to occur near room temperature, so the storage stability of the sealant will be reduced.

Prior art literature

Patent literature

Patent Document 1: Japanese Patent Application Publication No. 2001-133794

Patent Document 2: International Publication No. 02/092718

The object of the present invention is to provide a sealant for liquid crystal display elements that can achieve both low-temperature curability and storage stability. In addition, an object of the present invention is to provide an upper and lower conduction material and a liquid crystal display element using this sealant for liquid crystal display elements.

The present invention is a sealant for liquid crystal display elements, which contains a curable resin and a thermosetting agent, wherein the curable resin contains a curable resin having an epoxy group, and the thermosetting agent contains an epoxy resin-derived sealant. The structure and the amine addition compound derived from the structure of the amine compound, the amine compound that becomes the source of the above-mentioned amine addition compound is an alkylimidazole having an alkyl group of 1 to 20 carbon atoms.

Hereinafter, the present invention will be described in detail.

The present inventors found that by using an addition object of an alkyl imidazole having a specific length of an alkyl chain and an epoxy resin as a thermosetting agent, a seal for liquid crystal display elements that can achieve both low-temperature curability and storage stability can be obtained Agent, thus completing the present invention.

The sealing compound for liquid crystal display elements of this invention contains a thermosetting agent.

The above-mentioned thermosetting agent has a structure derived from an epoxy resin and a structure derived from an amine compound, and the amine compound is an amine addition compound of the following alkylimidazole. By using such an amine addition compound as the above-mentioned thermosetting agent, it is possible to improve the curability at low temperatures while maintaining excellent storage stability.

As the epoxy resin which becomes the source of the said amine addition compound, the same thing as the curable resin which has an epoxy group demonstrated below can be used, for example. Among them, epoxy resins having aromatic rings are preferred. Since the epoxy resin which becomes the source of the said amine addition compound has an aromatic ring, the storage stability of the sealing compound for liquid crystal display elements obtained can be improved further. The epoxy resin that becomes the source of the above-mentioned amine addition compound is more preferably at least one selected from the group consisting of bisphenol A epoxy resin, bisphenol F epoxy resin, and bisphenol E epoxy resin .

The amine compound used as the source of the above-mentioned amine addition compound is an alkylimidazole having 1-20 carbon atoms in the alkyl group.

As the alkylimidazole having a carbon number of 1 to 20 in the above-mentioned alkyl group, one having a carbon number of 1 to 2 in the alkyl group is preferable, and 2-methylimidazole is more preferable.

As the above-mentioned amine addition compound, a compound represented by the following formula (1-1) and/or a compound represented by the following formula (1-2) can be preferably used.

In addition, the following sealing compound for liquid crystal display elements is also one of the present invention, which contains a curable resin and a thermosetting agent, and the curable resin contains a curable resin having an epoxy group, and the thermosetting agent contains the following The compound represented by the formula (1-1) and/or the compound represented by the following formula (1-2).

In formula (1-1) and formula (1-2), R ¹ is an alkyl group with 1 to 20 carbon atoms. In formula (1-1), R ² and R ³ are hydrogen or methyl, which may be the same Can be different.

In addition, the thermosetting agent preferably contains a compound selected from the group consisting of a compound represented by the following formula (2-1), a compound represented by the following formula (2-2), a compound represented by the following formula (2-3), and the following At least one of the group consisting of the compound represented by the above formula (2-4) is the compound represented by the above formula (1-1) and/or the compound represented by the above formula (1-2).

The preferred upper limit of the average particle diameter of the above-mentioned amine addition compound is 3 μm. By making the average particle diameter of the above-mentioned amine addition compound 3 μm or less, it is possible to suppress gap defects of the obtained liquid crystal display element. The average particle diameter of the above-mentioned amine addition compound does not have a particularly preferred lower limit, but the actual lower limit is 0.1 μm.

Furthermore, when a commercially available amine addition compound having an average particle diameter exceeding 3 μm is used, the average particle diameter can be made 3 μm or less by performing treatments such as pulverization or classification.

Furthermore, in this specification, the average particle size of the above-mentioned amine addition compound and the following maximum particle size mean the addition of the amine before being blended into the sealant by using a laser diffraction particle size distribution measuring device The compound is measured to obtain the value. As the above-mentioned laser diffraction type particle size distribution measuring device, Mastersizer 2000 (manufactured by Malvern Corporation) or the like can be used.

The preferred upper limit of the maximum particle size of the above-mentioned amine addition compound is 5.0 μm. By setting the maximum particle size of the amine addition compound to 5.0 μm or less, the obtained liquid crystal display element has more excellent gap retention properties. The upper limit of the maximum particle size of the above-mentioned amine addition compound is more preferably 4.5 μm. The maximum particle size of the above-mentioned amine addition compound does not have a particularly preferred lower limit, but the actual lower limit is 0.1 μm.

Regarding the above-mentioned amine addition compound, among the particle size distribution of the amine addition compound measured by the above-mentioned laser diffraction particle size distribution measuring device, the content ratio of particles with a particle diameter of 3.0 μm or less is preferably based on volume frequency Counted as 99% or more. By setting the content ratio of particles with a particle diameter of 3.0 μm or less to 99% or more in terms of volume frequency, the obtained liquid crystal display element has more excellent gap retention properties. The best content of particles with a particle size of 3.0μm or less is 100%.

Regarding the content of the amine addition compound, relative to 100 parts by weight of the curable resin, the lower limit is preferably 0.3 parts by weight, and the upper limit is preferably 15 parts by weight. When the content of the amine addition compound is within this range, the obtained sealing compound for liquid crystal display elements is more excellent in low-temperature curability and more excellent in the effect of suppressing liquid crystal contamination. The lower limit of the content of the amine addition compound is more preferably 0.4 parts by weight, the upper limit is more preferably 12 parts by weight, the lower limit is still more preferably 0.5 parts by weight, and the upper limit is still more preferably 10 parts by weight.

The said thermosetting agent may contain other thermosetting agents in addition to the said amine addition compound.

Examples of the above-mentioned other thermosetting agents include hydrazine-based curing agents, imidazole-based curing agents, polyphenol-based curing agents, and acid anhydride-based curing agents. Among them, hydrazine-based hardeners can be preferably used.

Examples of the above-mentioned hydrazine-based hardener include: 1,3-bis(hydrazinocarbonylethyl-5-isopropylhydantoin), dihydrazine sebacate, dihydrazide isophthalate, Commercially available products such as dihydrazine adipic acid and dihydrazine malonate include Amicure VDH, Amicure UDH (all manufactured by Ajinomoto Fine-Techno), SDH, IDH, and ADH (all are Otsuka Chemical Manufactured by the company), MDH (manufactured by Japan Finechem), etc.

When the other thermosetting agent is contained, the content of the entire thermosetting agent is preferably 1 part by weight and the upper limit is 50 parts by weight with respect to 100 parts by weight of the curable resin. When the content of the entire thermosetting agent is within this range, the obtained sealing compound for liquid crystal display elements is more excellent in thermosetting and coating properties. The more preferable upper limit of the total content of the thermal hardening agent is 30 parts by weight.

The sealing compound for liquid crystal display elements of this invention contains a curable resin.

The said curable resin contains the curable resin which has an epoxy group.

Examples of the curable resin having an epoxy group include: bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, 2,2 '-Diallyl bisphenol A epoxy resin, hydrogenated bisphenol epoxy resin, propylene oxide addition bisphenol A epoxy resin, resorcinol epoxy resin, biphenyl 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 novolak type epoxy resin, Dicyclopentadiene novolac type epoxy resin, biphenyl novolac type epoxy resin, naphthol novolac type epoxy resin, glycidamine type epoxy resin, alkyl polyol type epoxy resin, rubber modification Type epoxy resin, glycidyl ester compound, etc.

As commercially available products among the above-mentioned bisphenol A epoxy resins, for example, jER828, jER828EL, jER1004 (all manufactured by Mitsubishi Chemical Corporation), EPICLON 850 (DIC Company manufacturing) and so on.

As a commercial item among the said bisphenol F type epoxy resin, jER806, jER4004 (all are manufactured by Mitsubishi Chemical Corporation) etc. are mentioned, for example.

Examples of commercially available products among the above-mentioned bisphenol E epoxy resins include EPOX-MK R710, EPOX-MK R1710 (all manufactured by Printec), and the like.

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

As a commercial item among the said 2,2'-diallyl bisphenol A type epoxy resin, RE-810NM (manufactured by Nippon Kayaku Co., Ltd.) etc. are mentioned, for example.

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

As a commercial item among the said propylene oxide addition bisphenol A type epoxy resin, EP-4000S (made by ADEKA company) etc. are mentioned, for example.

As a commercial item among the said resorcinol-type epoxy resin, EX-201 (manufactured by Nagase chemteX company) etc. are mentioned, for example.

As a commercial item among the said biphenyl type epoxy resin, jER YX-4000H (manufactured by Mitsubishi Chemical Corporation) etc. are mentioned, for example.

Examples of commercially available products among the above-mentioned sulfide epoxy resins include YSLV-50TE (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) and the like.

Examples of commercially available products among the above-mentioned diphenyl ether type epoxy resins include YSLV-80DE (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) and the like.

As a commercially available product among the above-mentioned dicyclopentadiene type epoxy resins, for example, EP-4088S can be cited (Manufactured by ADEKA) and so on.

Examples of commercially available products among the naphthalene-type epoxy resins include EPICLON HP4032, EPICLON EXA-4700 (all manufactured by DIC Corporation), and the like.

As a commercial item among the said phenol novolak type epoxy resin, EPICLON N-770 (made by DIC Corporation) etc. are mentioned, for example.

As a commercial item among the said ortho-cresol novolak type epoxy resin, EPICLON N-670-EXP-S (made by DIC Corporation) etc. are mentioned, for example.

As a commercial item among the said dicyclopentadiene novolak-type epoxy resin, EPICLON HP7200 (made by DIC Corporation) etc. are mentioned, for example.

As a commercial item among the said biphenol novolak type epoxy resin, NC-3000P (manufactured by Nippon Kayaku Co., Ltd.) etc. are mentioned, for example.

As a commercially available product among the naphthol novolak type epoxy resins, for example, ESN-165S (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) and the like can be cited.

Examples of commercially available products among the glycidamine-type epoxy resins include jER630 (manufactured by Mitsubishi Chemical Corporation), EPICLON 430 (manufactured by DIC Corporation), TETRAD-X (manufactured by Mitsubishi Gas Chemical Corporation), and the like.

Examples of commercially available products among the aforementioned alkyl polyol type epoxy resins include: ZX-1542 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), EPICLON 726 (manufactured by DIC Corporation), and Epolight 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.) ), DENACOL EX-611 (manufactured by Nagase chemteX), etc.

Examples of commercially available products among the above-mentioned rubber-modified epoxy resins include YR-450, YR-207 (all manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), Epolead PB (manufactured by Daicel), and the like.

Examples of commercially available products among the above glycidyl ester compounds include: DENACOL EX-147 (Manufactured by Nagase chemteX) and so on.

As other commercially available products among the above-mentioned epoxy compounds, for example, YH-300, YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), XAC4151 (manufactured by Asahi Kasei Co., Ltd.), jER1031, jER1032 (all manufactured by Mitsubishi Chemical Corporation), EXA-7120 (manufactured by DIC Corporation), TEPIC (manufactured by Nissan Chemical Corporation), etc.

The above-mentioned curable resin having an epoxy group may be a partially (meth)acrylic modified epoxy resin. The above-mentioned partial (meth)acrylic modified epoxy resin means a compound having one or more epoxy groups and (meth)acrylic groups in one molecule. For example, it can be made by having two It is obtained by reacting a part of the epoxy group of the epoxy compound with more than one epoxy group and (meth)acrylic acid.

In addition, in this specification, the above-mentioned "(meth)acrylic acid" means acrylic acid or methacrylic acid, and the above-mentioned "(meth)acryloyl group" means acryloyl group or methacrylic acid group.

As a commercial item among the said partially (meth)acrylic modified epoxy resin, UVACURE1561 (made by Daicel-Allnex company) etc. are mentioned, for example.

The lower limit of the content of the epoxy group-containing curable resin in 100 parts by weight of the curable resin is preferably 1 part by weight, and the upper limit is preferably 100 parts by weight. When the content of the curable resin having an epoxy group is within this range, the obtained sealing compound for liquid crystal display elements is more excellent in adhesiveness. The lower limit of the content of the above-mentioned epoxy-containing curable resin is more preferably 2 parts by weight.

The said curable resin may contain other curable resin in addition to the said curable resin which has an epoxy group. As the above-mentioned other curable resin, a (meth)acrylic compound is preferable.

Examples of the (meth)acrylic compound include: a (meth)acrylate compound obtained by reacting a compound having a hydroxyl group with (meth)acrylic acid; and a (meth)acrylic acid compound obtained by reacting (meth)acrylic acid with an epoxy compound Epoxy (meth)acrylate obtained by the reaction, amine (meth)acrylate obtained by reacting a (meth)acrylic acid derivative having a hydroxyl group with an isocyanate compound, and the like. Among them, epoxy (meth)acrylate is more preferred. In addition, the above-mentioned (meth)acrylic compound is preferably one having two or more (meth)acrylic groups in the molecule in terms of high reactivity.

Examples of the monofunctional among the above-mentioned (meth)acrylate compounds include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and n-butyl (meth)acrylate. Ester, isobutyl (meth)acrylate, tertiary butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate , Isononyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, isomyristyl (meth)acrylate, stearyl (meth)acrylate, (meth) 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, cyclohexyl (meth)acrylate, ( Isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxy (meth)acrylate Ethyl, 2-butoxyethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, methoxyethylene glycol (meth)acrylate, methoxypolyethylene glycol ( Meth) acrylate, phenoxy diethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, ethyl carbitol ( (Meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, (meth)acrylate 1H, 1H, 5H -Otafluoropentyl ester, imine (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, 2-(meth)acrylic acid succinate Oxyethyl, 2-(meth)propenyloxyethyl hexahydrophthalate, 2-(meth)propenyloxyethyl 2-hydroxypropyl phthalate Ester, 2-(meth)acryloxyethyl phosphate, glycidyl (meth)acrylate, etc.

In addition, examples of the bifunctional one among the above-mentioned (meth)acrylate compounds include 1,3-butanediol di(meth)acrylate and 1,4-butanediol di(meth)acrylate , 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, ethylene glycol two (Meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 2-n-butyl-2 -Ethyl-1,3-propanediol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, neopentyl diacrylate Alcohol di(meth)acrylate, ethylene oxide addition bisphenol A di(meth)acrylate, propylene oxide addition bisphenol A di(meth)acrylate, ethylene oxide addition bisphenol F di(meth)acrylate, dimethylol dicyclopentadienyl di(meth)acrylate, ethylene oxide modified isocyanuric acid di(meth)acrylate, (meth) 2-hydroxy-3-(meth)acryloxypropyl acrylate, carbonate diol di(meth)acrylate, polyether diol di(meth)acrylate, polyester diol di(meth) ) Acrylate, polycaprolactonediol di(meth)acrylate, polybutadienediol di(meth)acrylate, etc.

In addition, examples of the above-mentioned (meth)acrylate compounds having three or more functions include trimethylolpropane tri(meth)acrylate, ethylene oxide addition trimethylolpropane tri(methyl) )Acrylate, propylene oxide addition trimethylolpropane tri(meth)acrylate, caprolactone modified trimethylolpropane tri(meth)acrylate, ethylene oxide addition isocyanuric acid Acid tri(meth)acrylate, glycerol tri(meth)acrylate, propylene oxide addition glycerol tri(meth)acrylate, neopentylerythritol tri(meth)acrylate, phosphoric acid tri(meth) Acrylic oxyethyl ester, di-trimethylolpropane tetra (meth) acrylate, neopentyl erythritol tetra (meth) acrylate, dineopentyl pentaerythritol penta (meth) acrylate, dineopentyl Tetraol hexa(meth)acrylate and the like.

As said epoxy (meth)acrylate, what is obtained by making an epoxy compound and (meth)acrylic acid react conventionally in the presence of a basic catalyst etc. are mentioned, for example.

As the epoxy compound used as a raw material for synthesizing the above-mentioned epoxy (meth)acrylate, the same epoxy compound as exemplified as the above-mentioned curable resin having an epoxy group can be used.

Examples of commercially available products among the aforementioned epoxy (meth)acrylates include: 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-Allnex), EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, EMA-1020 (all manufactured by Shinnakamura Chemical Industry Co.), 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 400 Kyoeisha Chemical Co., Ltd.), DENACOL Acrylate DA-141, DENACOL Acrylate DA-314, DENACOL Acrylate DA-911 (all manufactured by Nagase chemteX), etc.

The above-mentioned (meth)acrylic acid amine ester obtained by reacting a (meth)acrylic acid derivative having a hydroxyl group with an isocyanate compound can be made by, for example, a (methyl) ) Obtained by reacting 2 equivalents of an acrylic derivative with 1 equivalent of an isocyanate compound having 2 isocyanate groups.

Examples of the isocyanate compound used as the raw material of the (meth)acrylate amine ester include isophorone diisocyanate, 2,4-toluene diisocyanate, and 2,6-toluene diisocyanate. Isocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4,4'-diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norcampan Alkyl diisocyanate, toluidine diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris(isocyanatophenyl) phosphorothioate, tetramethyl Xylylene diisocyanate, 1,6,11-undecane triisocyanate, etc.

In addition, as the isocyanate compound used as the raw material of the above-mentioned (meth)acrylate amine ester, for example, ethylene glycol, propylene glycol, glycerin, sorbitol, trimethylolpropane, carbonate diol, polyether two A chain-extended isocyanate compound obtained by the reaction of polyols such as alcohols, polyester diols, polycaprolactone diols and excess isocyanate compounds.

Examples of (meth)acrylic acid derivatives having hydroxyl groups used as raw materials for the above (meth)acrylate amine esters include: 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, Hydroxyalkyl mono(meth)acrylates such as 2-hydroxybutyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate; or ethylene glycol, propylene glycol, 1,3-propanediol, 1,3- Mono(meth)acrylates of dihydric alcohols such as butanediol, 1,4-butanediol, polyethylene glycol; or trihydric alcohols such as trimethylolethane, trimethylolpropane, glycerin, etc. (Meth)acrylate or di(meth)acrylate; or epoxy (meth)acrylate such as bisphenol A type epoxy acrylate, etc.

Examples of commercially available products among the above (meth)acrylate amine esters include: M-1100, M-1200, M-1210, M-1600 (all manufactured by Toagosei Co., Ltd.), EBECRYL 210, EBECRYL 220, EBECRYL 230, EBECRYL 270, EBECRYL 1290, EBECRYL 2220, EBECRYL 4827, EBECRYL 4842, EBECRYL 4858, EBECRYL 5129, EBECRYL 6700, EBECRYL 8402, EBECRYL 8803, EBECRYL 8804, EBECRYL 8807, EBECRYL 9260 (all manufactured by EBECRYL 8807, EBECRYL 9260) Artresin UN-330, Artresin SH-500B, Artresin UN-1200TPK, Artresin UN-1255, Artresin UN-3320HB, Artresin UN-7100, Artresin UN-9000A, Artresin UN-9000H (all manufactured by Negami Industries), U-2HA, U-2PHA, U-3HA, U-4HA, U-6H, U-6HA, U-6LPA, U-10H, U-15HA, U-108, U-108A, U-122A, U-122P, U-324A, U- 340A, U-340P, U-1084A, U-2061BA, UA-340P, UA-4000, UA-4100, UA-4200, UA-4400, UA-5201P, UA-7100, UA-7200, UA-W2A( All manufactured by Shinnakamura Chemical Industry Co., Ltd.), AH-600, AI-600, AT-600, UA-101I, UA-101T, UA-306H, UA-306I, UA-306T (all manufactured by Kyoeisha Chemical Co., Ltd.) )Wait.

When the curable resin contains the partially (meth)acrylic modified epoxy resin or the (meth)acrylic compound, the epoxy group and the (meth)acrylic group in the curable resin are preferred The ratio becomes 30:70~95:5. By making the ratio of the epoxy group and the (meth)acryl group within the range, the adhesiveness of the obtained sealing compound for liquid crystal display elements can be further improved or the liquid crystal display using the obtained sealing compound for liquid crystal display elements can be further improved The display performance of the component.

The above-mentioned curable resin is preferably one having hydrogen bonding units such _{as -OH group, -NH- group, -NH 2 group, etc., from the viewpoint of suppressing liquid crystal contamination.}

The sealing compound for liquid crystal display elements of this invention may contain a radical polymerization initiator.

As the above-mentioned radical polymerization initiator, a thermal radical polymerization initiator or a photo radical polymerization initiator can be used.

Examples of the thermal radical polymerization initiator include those composed of an azo compound, an organic peroxide, or the like. Among them, from the viewpoint of suppressing liquid crystal contamination, a starter composed of an azo compound (hereinafter, also referred to as an "azo starter") is preferred, and a polymer is more preferred. An initiator composed of an azo compound (hereinafter, also referred to as a "polymer azo initiator").

Furthermore, in this specification, the above-mentioned "polymer azo compound" means a radical having an azo group, and the number average molecular weight of a radical that can harden the (meth)acryloyl group generated by heat is 300 or more Compound.

The preferred lower limit of the number average molecular weight of the polymer azo initiator is 1,000, and the preferred upper limit is 300,000. By making the number average molecular weight of the polymer azo starter 1000 or more, liquid crystal contamination can be suppressed. By making the number average molecular weight of the above-mentioned polymer azo initiator within this range, it is possible to prevent adverse effects on the liquid crystal and to be more easily mixed into the curable resin. The lower limit of the number average molecular weight of the polymer azo initiator is more preferably 5,000, the upper limit is more preferably 100,000, the lower limit is more preferably 10,000, and the upper limit is more preferably 90,000.

In addition, in this specification, the said number average molecular weight is the value calculated|required by the polystyrene conversion measured by gel permeation chromatography (GPC). As a column for measuring the number average molecular weight based on polystyrene conversion by GPC, for example, Shodex LF-804 (manufactured by Showa Denko Corporation) and the like can be cited.

Examples of the above-mentioned polymer azo initiator include those having a structure in which a plurality of units such as polyalkylene oxide or polydimethylsiloxane are bonded via an azo group.

The polymer azo initiator having a structure in which a plurality of units such as polyalkylene oxide or polydimethylsiloxane are bonded via an azo group is preferably one having a polyethylene oxide structure. As such a polymer azo initiator, for example, a condensation polymer of 4,4'-azobis(4-cyanovaleric acid) and polyalkylene glycol, or 4,4'-azo The polycondensate of bis(4-cyanovaleric acid) and polydimethylsiloxane having a terminal amine group, etc., specifically, for example: VPE-0201, VPE-0401, VPE-0601, VPS-0501 , VPS-1001 (all manufactured by Wako Pure Chemical Industries, Ltd.), etc.

In addition, examples of azo initiators other than the polymer azo initiator include V-65, V-501 (all manufactured by Wako Pure Chemical Industries, Ltd.) and the like.

Examples of the organic peroxide include ketone peroxide, peroxyketal, hydrogen peroxide, dialkyl peroxide, peroxyester, diacyl peroxide, and peroxydicarbonate.

Regarding the content of the thermal radical polymerization initiator, relative to 100 parts by weight of the curable resin, the lower limit is preferably 0.05 parts by weight, and the upper limit is preferably 10 parts by weight. When the content of the thermal radical polymerization initiator is 0.05 parts by weight or more, the obtained sealing compound for liquid crystal display elements is more excellent in thermosetting properties. When the content of the thermal radical polymerization initiator is 10 parts by weight or less, the obtained sealing compound for liquid crystal display elements is more excellent in the effect of suppressing liquid crystal contamination. The lower limit of the content of the thermal radical polymerization initiator is more preferably 0.1 parts by weight, and the upper limit is more preferably 5 parts by weight.

等。 Examples of the aforementioned photoradical polymerization initiator include benzophenone-based compounds, acetophenone-based compounds, phosphine oxide-based compounds, titanocene-based compounds, oxime ester-based compounds, benzoin ether-based compounds, Benzol, 9-oxysulfur

Wait.

Examples of commercially available products among the aforementioned photoradical polymerization initiators include: IRGACURE 184, IRGACURE 369, IRGACURE 379, IRGACURE 651, IRGACURE 819, IRGACURE 907, IRGACURE 2959, IRGACURE OXE01, IRGACURE OXE02, Lucirin TPO (all Made by BASF Corporation), benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether (all manufactured by Tokyo Chemical Industry Co., Ltd.), etc.

Regarding the content of the photo-radical polymerization initiator, relative to 100 parts by weight of the curable resin, the lower limit is preferably 0.1 parts by weight, and the upper limit is preferably 10 parts by weight. By making the content of the above-mentioned photoradical polymerization initiator 0.1 parts by weight or more, the obtained liquid crystal display element The sealant for parts is more excellent in photocurability. By setting the content of the photo radical polymerization initiator to 10 parts by weight or less, the obtained sealing compound for liquid crystal display elements is more excellent in weather resistance. The lower limit of the content of the photo radical polymerization initiator is more preferably 0.2 parts by weight, and the upper limit is more preferably 8 parts by weight.

The sealing compound for liquid crystal display elements of the present invention may contain a filler in order to increase the viscosity, improve the adhesiveness based on the stress dispersion effect, improve the linear expansion rate, and further improve the moisture resistance of the cured product.

Examples of the above-mentioned filler include: talc, asbestos, silica, diatomaceous earth, bentonite, bentonite, calcium carbonate, magnesium carbonate, alumina, montmorillonite, zinc oxide, iron oxide, and magnesium oxide , Tin oxide, titanium oxide, magnesium hydroxide, aluminum hydroxide, glass beads, silicon nitride, barium sulfate, gypsum, calcium silicate, sericite, activated clay, aluminum nitride and other inorganic fillers, or polyester particles, Organic fillers such as polyurethane microparticles, vinyl polymer microparticles, acrylic polymer microparticles, core-shell acrylate copolymer microparticles, etc. These fillers may be used alone or in combination of two or more kinds.

The lower limit of the content of the filler in 100 parts by weight of the sealing compound for liquid crystal display elements of the present invention is preferably 10 parts by weight, and the upper limit is preferably 70 parts by weight. By making the content of the above-mentioned filler to be 10 parts by weight or more, the effects such as improvement of adhesiveness can be further improved. By setting the content of the filler to 70 parts by weight or less, the obtained sealing compound for liquid crystal display elements is more excellent in coatability. The lower limit of the filler content is more preferably 20 parts by weight, and the upper limit is more preferably 60 parts by weight.

The sealing compound for liquid crystal display elements of this invention may contain a silane coupling agent. The above-mentioned silane coupling agent has an adhesive agent mainly used to bond the sealant and the substrate well. Features.

As the above-mentioned silane coupling agent, it is excellent in the effect of improving the adhesion with the substrate, etc., and can suppress the outflow of the curable resin into the liquid crystal by chemical bonding with the curable resin, for example, N can be preferably used. -Phenyl-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, etc. These silane coupling agents may be used alone or in combination of two or more kinds.

The lower limit of the content of the silane coupling agent in 100 parts by weight of the sealing compound for liquid crystal display elements of the present invention is preferably 0.1 parts by weight, and the upper limit is preferably 20 parts by weight. By making the content of the above-mentioned silane coupling agent 0.1 parts by weight or more, the adhesion to the substrate and the like can be further improved. When the content of the silane coupling agent is 20 parts by weight or less, the obtained sealing compound for liquid crystal display elements is more excellent in the effect of suppressing liquid crystal contamination. The lower limit of the content of the silane coupling agent is more preferably 0.5 parts by weight, and the upper limit is more preferably 10 parts by weight.

The sealing compound for liquid crystal display elements of the present invention may further contain a reactive diluent for adjusting the viscosity, spacers such as polymer beads for adjusting the gap between the panels, and 3-p-chlorophenyl-1,1- Additives such as hardening accelerators such as dimethylurea and isocyanuric acid, defoamers, leveling agents, polymerization inhibitors, and other coupling agents.

As a method of manufacturing the sealing compound for liquid crystal display elements of the present invention, for example, the curable resin is mixed with a mixer such as a homogeneous disperser, homomixer, universal mixer, planetary mixer, kneader, and three-roll mill. , Thermosetting agent, and if necessary, filler or silane coupling agent and other additives are mixed together.

By blending conductive fine particles in the sealing compound for liquid crystal display elements of the present invention Sub, can make up and down conductive materials. In addition, such a top and bottom conduction material containing the sealing compound for liquid crystal display elements of the present invention and conductive fine particles is also one of the present invention.

The conductive fine particles are not particularly limited, and metal balls, those having a conductive metal layer formed on the surface of the resin fine particles, and the like can be used. Among them, those with a conductive metal layer formed on the surface of the resin particles are preferable because of the excellent elasticity of the resin particles, which can be electrically connected without damaging the transparent substrate or the like.

Moreover, the liquid crystal display element which uses the sealing compound for liquid crystal display elements of this invention or the top and bottom conduction material of this invention is also one of this invention.

As a method of manufacturing the liquid crystal display element of the present invention, a liquid crystal dropping method can be preferably used. Specifically, for example, a method having the following steps: by screen printing, dispenser coating, etc., the sealant for liquid crystal display elements of the present invention is applied to two transparent substrates having electrodes such as an ITO film One piece, the step of forming a frame-shaped sealing pattern; the step of applying tiny droplets of liquid crystal on the entire surface of the frame of the sealing pattern, and overlapping another substrate under vacuum; and irradiating the part of the sealing pattern with ultraviolet rays, etc. The step of temporarily hardening the sealant with light; and the step of heating the temporarily hardened sealant to formally harden it.

According to the present invention, it is possible to provide a sealant for liquid crystal display elements that can achieve both low-temperature curability and storage stability. In addition, according to the present invention, it is possible to provide an upper and lower conduction material and a liquid crystal display element using the sealing compound for liquid crystal display elements.

Hereinafter, examples are given to explain the present invention in further detail, but the present invention is not limited to these examples.

(Manufacturing of Amine Addition Compound A)

Put 300 mL of the n-butanol/toluene mixed solution with a mixing ratio of 1:1 into a three-necked flask, and then put in 38.0 parts by weight of bisphenol A epoxy resin (manufactured by Mitsubishi Chemical Corporation, "jER828") and 2-methylimidazole (Manufactured by Tokyo Chemical Industry Co., Ltd.) 4.1 parts by weight. After heating and stirring at 65°C for 4 hours, solvent removal and vacuum drying are performed to obtain an amine addition compound A having a structure derived from bisphenol A epoxy resin and a structure derived from 2-methylimidazole.

^{The 1} H-NMR, ¹³ C-NMR, and IR measurement of the obtained amine addition compound A confirmed that it was a compound represented by the above formula (2-1).

(Manufacturing of Amine Addition Compound B)

Put 300 mL of the n-butanol/toluene mixed solution with a mixing ratio of 1:1 into a three-necked flask, and then put in 30.0 parts by weight of an aliphatic epoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., "YH-300") and 2- Methylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) 4.1 parts by weight. After heating and stirring at 65°C for 4 hours, solvent removal and vacuum drying were performed to obtain an amine addition compound B having a structure derived from an aliphatic epoxy resin and a structure derived from 2-methylimidazole.

^{By performing 1} H-NMR, ¹³ C-NMR, and IR measurements on the obtained amine addition compound B, it was confirmed that it was a compound represented by the above formula (2-2).

(Manufacturing of amine addition compound C)

Put 300mL of the mixed solution of n-butanol/toluene with a mixing ratio of 1:1 into a three-necked flask, and In addition, 38.0 parts by weight of bisphenol A epoxy resin (manufactured by Mitsubishi Chemical Corporation, "jER828") and 20.3 parts by weight of 2-heptadecylimidazole (manufactured by Shikoku Chemical Industry Co., Ltd., "C17Z") were added. After heating and stirring at 65°C for 4 hours, solvent removal and vacuum drying were performed to obtain an amine addition compound C having a structure derived from bisphenol A epoxy resin and a structure derived from 2-heptadecylimidazole .

^{By performing 1} H-NMR, ¹³ C-NMR, and IR measurements on the obtained amine addition compound C, it was confirmed that it was a compound represented by the above formula (2-3).

(Manufacturing of amine addition compound D)

Put 300 mL of the n-butanol/toluene mixed solution with a mixing ratio of 1:1 into a three-necked flask, and then put in 30.0 parts by weight of an aliphatic epoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., "YH-300") and 2- Heptadecyl imidazole (manufactured by Shikoku Chemical Industry Co., Ltd., "C17Z") 20.3 parts by weight. After heating and stirring at 65°C for 4 hours, solvent removal and vacuum drying are performed to obtain an amine addition compound D having a structure derived from an aliphatic epoxy resin and a structure derived from 2-heptadecylimidazole.

^{The 1} H-NMR, ¹³ C-NMR, and IR measurement of the obtained amine addition compound D confirmed that it is a compound represented by the above formula (2-4).

(Manufacturing of Amine Addition Compound E)

Put 300 mL of the n-butanol/toluene mixed solution with a mixing ratio of 1:1 into a three-necked flask, and then put in 38.0 parts by weight of bisphenol A epoxy resin (manufactured by Mitsubishi Chemical Corporation, "jER828") and 2-phenylimidazole (Manufactured by Wako Pure Chemical Industries, Ltd.) 7.2 parts by weight. After heating and stirring at 65°C for 4 hours, solvent removal and vacuum drying were performed to obtain an amine addition compound E having a structure derived from bisphenol A epoxy resin and a structure derived from 2-phenylimidazole.

^{The 1} H-NMR, ¹³ C-NMR, and IR measurement of the obtained amine addition compound E confirmed that it is a compound represented by the following formula (3).

(Examples 1 to 7, Comparative Examples 1 to 4)

According to the blending ratio described in Table 1, the materials were mixed using a planetary mixer (manufactured by Thinky, "Defoaming Stir Taro"), and then mixed using a three-roll mill to prepare Examples 1-7. Each of the sealing compounds for liquid crystal display elements of Comparative Examples 1 to 4.

<evaluation>

About each sealing compound for liquid crystal display elements obtained in an Example and a comparative example, the following evaluation was performed. The results are shown in Table 1.

(Storage stability)

For each liquid crystal display element sealing compound obtained in the Examples and Comparative Examples, the initial viscosity immediately after the manufacture and the viscosity when stored at 25°C for 3 days were measured, and the (viscosity after storage at 25°C for 3 days) /(Initial viscosity) is the rate of change of viscosity. If the rate of change of viscosity is less than 1.3, set to "◎", if the rate of change of viscosity is greater than 1.3 and less than 1.5, set to "○", and if the rate of change is greater than 1.5 and less than 2.0 Set it as "△", and set it as "×" for those of 2.0 or higher, and evaluate the storage stability.

Furthermore, the viscosity of the sealant was measured using an E-type viscometer (manufactured by BROOK Field, "DV-III") at 25°C and a rotation speed of 1.0 rpm.

(Low temperature hardening)

Each liquid crystal display element sealant obtained in the examples and comparative examples was filled in a dispensing syringe (manufactured by Musashi Engineering, "PSY-10E"), and subjected to defoaming treatment. Then, using a dispenser (manufactured by Musashi Engineering, "SHOTMASTER300"), the sealant was applied to one of the two transparent electrode substrates with ITO film by drawing a rectangular frame. Then, a liquid crystal dropping device is used to inject tiny droplets coated with TN liquid crystal (manufactured by Chisso, "JC-5001LA") into the frame of the formed sealant, and the vacuum laminating device is used to reduce the pressure of 5Pa. Press down and attach another transparent substrate. After irradiating the bonded cell with 3000 mJ/cm ² of ultraviolet rays with a metal halide lamp, it was heated at 100° C. for 60 minutes to thermally harden the sealant to produce a liquid crystal display element. The irradiation of ultraviolet rays is performed by cutting off light with a wavelength below 340nm by a filter. After storing the obtained liquid crystal display element at a temperature of 80°C for 100 hours, it was driven with a voltage of AC 3.5V and observed by visual observation. Set the case where there is no display unevenness (color unevenness) at the periphery of the liquid crystal display element as "◎", and set the case where a little lighter display unevenness is seen as "○", which will be clear and darker The display unevenness is set to "△", and the clear and deep display unevenness not only exists in the periphery, but also extends to the center, set to "×", and the display performance of the liquid crystal display element is evaluated .

(Visible light hardening)

The sealant for each liquid crystal display element obtained in Example 5 was coated on a glass substrate with a thickness of about 5 μm, and a glass substrate of the same size was overlapped on the substrate. Next, a metal halide lamp was used to irradiate 100 mW/cm ² of light 10 Seconds. The light irradiation is performed by cutting off light with a wavelength below 380nm by a filter. Using an infrared spectrometer (manufactured by BIORAD, "FTS3000"), the peaks derived from the acrylic acid group before and after the light irradiation were measured, and the reduction rate of the peaks derived from the acrylic acid group after the light irradiation was derived. If the reduction rate of the peak derived from the acrylic base after light irradiation is 93% or more, set it as "◎", and if it will be over 85% and less than 93%, set it as "○" and it will be 75% The cases above and less than 85% are set as "△", and the cases less than 75% are set as "×", and the visible light curability is evaluated.

[Industrial availability]

According to the present invention, it is possible to provide a sealant for liquid crystal display elements that can achieve both low-temperature curability and storage stability. In addition, it is possible to provide an upper and lower conduction material and a liquid crystal display element using this sealing compound for liquid crystal display elements.

Claims (7)

A sealant for liquid crystal display elements, which contains a curable resin and a thermosetting agent, characterized in that the curable resin contains a curable resin having an epoxy group, and the thermosetting agent contains an epoxy resin-derived sealant. The structure and the amine addition compound derived from the structure of the amine compound, the amine compound that becomes the source of the above-mentioned amine addition compound is an alkylimidazole having an alkyl group of 1 to 20 carbon atoms. For example, the sealing compound for liquid crystal display element of the first item of the scope of patent application, wherein the alkyl imidazole with the carbon number of the alkyl group of 1-20 is 2-methylimidazole. For example, the sealing compound for liquid crystal display elements of the first or second patent application, in which the epoxy resin that is the source of the amine addition compound has an aromatic ring. For example, the sealant for liquid crystal display elements of the first or second patent application, wherein the epoxy resin that becomes the source of the amine addition compound is selected from the group consisting of bisphenol A type epoxy resin, bisphenol F type epoxy resin, and At least one of the group consisting of bisphenol E epoxy resin. A sealant for liquid crystal display elements, which contains a curable resin and a thermosetting agent, characterized in that the curable resin contains a curable resin having an epoxy group, and the thermosetting agent contains the following formula (1-1 ) And/or the compound represented by the following formula (1-2),

In formula (1-1) and formula (1-2), R ¹ is an alkyl group with 1 to 20 carbon atoms. In formula (1-1), R ² and R ³ are hydrogen or methyl, which may be the same Can be different. An up-and-down conduction material, which contains the sealing compound for liquid crystal display elements and conductive fine particles of item 1, 2, 3, 4, or 5 in the scope of patent application. A liquid crystal display element, which is formed by using the sealant for liquid crystal display elements of item 1, 2, 3, 4, or 5 in the scope of patent application or the upper and lower conductive materials of item 6 in the scope of patent application.