TWI747862B - 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 storage stability and rapid curing properties at low temperatures. 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 sealing compound for a liquid crystal display element, which contains a curable resin and a thermosetting agent, and the thermosetting agent contains a compound having a structure represented by the following formula (1).

In formula (1), X is a structure having an aromatic ring, n is an integer of 1 or more, and * is a bonding position.

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 balance storage stability and rapid curing at low temperatures. In addition, the present invention relates to an upper and lower conduction material and a liquid crystal display element using this sealant for liquid crystal display elements.

In recent years, as a method for 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 liquid crystal dropping method called the dripping method using light and heat containing a curable resin, a photopolymerization initiator and a thermosetting agent and a hardening type sealant are used.

In the dropping method, a rectangular seal pattern is formed on one of the two substrates with electrodes by dispensing. Then, the small 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 dropping method has become the mainstream of the manufacturing method of liquid crystal display elements.

In addition, in the modernization of the popularization of various mobile devices with LCD panels such as mobile phones and portable game consoles, miniaturization of the devices is the most important issue. As a method of miniaturization of the machine, the narrow edge of the liquid crystal display part can be cited, for example, the position of the sealing part is arranged in the black Operations under the matrix (hereinafter, also referred to as narrow-edge design).

However, in the narrow-edge design, since the sealant is placed directly under the black matrix, if the drip method is implemented, the light irradiated when the sealant is hardened by light is shielded, and it is difficult for the light to reach the inside of the sealant. In the conventional sealant, hardening becomes insufficient. If the curing of the sealant becomes insufficient in this way, there is a problem that the uncured sealant component is eluted into the liquid crystal, and liquid crystal contamination becomes easy to occur.

Therefore, it has been examined to heat the sealant to harden it, and from the viewpoint of energy saving and liquid crystal stability, it is desirable to heat the sealant by heating at a low temperature and in a short time.

As a method for hardening the sealant by heating at a low temperature and for a short time, it is considered to use a thermal hardener with a lower melting point. However, when a thermal hardener with a lower melting point is used, a seal can be obtained. The storage stability of the agent deteriorates.

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 storage stability and rapid curing properties at low temperatures. 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 sealing compound for a liquid crystal display element, which contains a curable resin and a thermosetting agent, and the thermosetting agent contains a compound having a structure represented by the following formula (1).

In formula (1), X is a structure having an aromatic ring, n is an integer of 1 or more, and * is a bonding position.

The present invention will be described in detail below.

The inventors of the present invention have found that by using a compound having a specific structure as a thermosetting agent, a sealing compound for liquid crystal display elements that can achieve both storage stability and rapid curing at low temperatures can be obtained, thereby completing the present invention.

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

The above-mentioned thermosetting agent contains a compound having the structure represented by the above-mentioned formula (1). By containing a compound having a structure represented by the above formula (1) as the above-mentioned thermosetting agent, the sealing compound for liquid crystal display elements of the present invention can achieve both storage stability and rapid curing properties at low temperatures.

In the above formula (1), n is preferably an integer of 1-10, more preferably an integer of 1-5.

In addition, in the above formula (1), X is preferably a structure represented by the following formula (2-1), (2-2), (2-3), (2-4), or (2-5), It is more preferably a structure represented by the following formula (2-1), and still more preferably a structure in which R ¹ and R ² in the following formula (2-1) are methyl groups.

In the formula (2-1), R ¹ and R ² are each independently hydrogen or a methyl group, and in the formulas (2-1) to (2-5), * is a bonding position.

The compound having the structure represented by the above formula (1) preferably has a structure derived from a primary diamine compound having a divalent aliphatic hydrocarbon group, and more preferably has: a structure derived from a divalent alicyclic hydrocarbon group The structure of the primary diamine compound of is more preferably a structure derived from a primary diamine compound having a cyclohexylene group, particularly preferably a compound having the structure represented by the following formula (3) or having the following formula (4) The compound of the structure shown.

In formula (3), X is the same structure as X in formula (1), n is the same number as n in formula (1), and * is the bonding position.

In formula (4), X is the same structure as X in formula (1), n is the same number as n in formula (1), and * is the bonding position.

The compound having the structure represented by the above formula (1) preferably has an epoxy group or a primary amino group at the end of the main chain, more preferably has a primary amino group at the end of the main chain, and more preferably has a primary amino group at the end of the main chain. Both ends have a primary amine group.

The preferred lower limit of the melting point of the compound having the structure represented by the above formula (1) is 60°C, and the preferred upper limit is 100°C. When the melting point of the compound having the structure represented by the above formula (1) is in this range, the obtained sealing compound for liquid crystal display elements is more excellent in the effect of having both storage stability and rapid hardening at low temperature. The lower limit of the melting point of the compound having the structure represented by the above formula (1) is more preferably 65°C, and the more preferable upper limit is 95°C.

As a method for producing a compound having a structure represented by the above formula (1), specifically, for example, the following method can be cited, that is, making 1,4-bis(aminomethyl)cyclohexane and other aliphatic First-grade diamine, and bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol E diglycidyl ether, bisphenol S diglycidyl ether, bis(4-epoxypropoxy) Phenyl) ether, resorcinol diglycidyl ether, biphenyl-4,4'-diyl bis(glycidyl ether) and other reactions.

For the content of the compound having the structure represented by the above formula (1), relative to 100 parts by weight of the curable resin, the preferred lower limit is 5 parts by weight, and the preferred upper limit is 120 parts by weight. When the content of the compound having the structure represented by the above formula (1) is within this range, the obtained sealing compound for liquid crystal display elements is more excellent in the effect of having both storage stability and rapid hardening at low temperature. The lower limit of the content of the compound having the structure represented by the above formula (1) is more preferably 10 parts by weight, the upper limit is more preferably 100 parts by weight, the lower limit is more preferably 20 parts by weight, and the upper limit is more preferably 60 parts by weight.

In addition to the compound having the structure represented by the above formula (1), the above-mentioned thermosetting agent may also contain other thermosetting agents within a range that does not interfere with the purpose of the present invention.

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 Made by the company), MDH (made by Japan Finechem), etc.

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

The curable resin preferably contains an epoxy compound.

Examples of the epoxy compound include: bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, and 2,2'-diallyl Bisphenol A type Epoxy resin, hydrogenated bisphenol type epoxy resin, propylene oxide addition bisphenol A type epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy resin, thioether type epoxy resin, diphenyl Ether type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, phenol novolak type epoxy resin, o-cresol novolak type epoxy resin, dicyclopentadiene novolak type epoxy resin Resin, biphenol novolac type epoxy resin, naphthol novolac type epoxy resin, glycidamine type epoxy resin, alkyl polyol type epoxy resin, rubber modified type epoxy resin, glycidyl ester compound Wait.

Examples of commercially available products among the above-mentioned bisphenol A epoxy resins include jER828EL, jER1004 (all manufactured by Mitsubishi Chemical Corporation), EPICLON 850 (manufactured by DIC Corporation), and the like.

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.

As a commercial item among the said bisphenol E type epoxy resin, EPOMIK R710 (manufactured by Mitsui Chemicals Co., Ltd.) etc. are mentioned, for example.

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.

Examples of commercially available products among the above resorcinol type epoxy resins include: EX-201 (Manufactured by Nagase chemteX) and so on.

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

As a commercially available product among the above-mentioned sulfide-type epoxy resins, YSLV-50TE (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) etc. are mentioned, for example.

As a commercial item among the said diphenyl ether type epoxy resin, YSLV-80DE (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) etc. are mentioned, for example.

As a commercial item among the said dicyclopentadiene type epoxy resin, EP-4088S (made by ADEKA company) etc. are mentioned, for example.

Examples of commercially available products among the above-mentioned 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.

As a commercially available product among the above-mentioned glycidyl amine epoxy resins, for example, jER630 (Mitsubishi Chemical Corporation), EPICLON 430 (manufactured by DIC Corporation), TETRAD-X (manufactured by Mitsubishi Gas Chemical Corporation), etc.

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.

As a commercial item among the said glycidyl ester compound, DENACOL EX-147 (manufactured by Nagase chemteX company) etc. are mentioned, for example.

As other commercially available products among the above epoxy compounds, for example, 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 are manufactured by Mitsubishi Chemical Corporation), EXA-7120 (manufactured by DIC Corporation), TEPIC (manufactured by Nissan Chemical Corporation), etc.

As the above-mentioned epoxy compound, part of (meth)acrylic modified epoxy resin is also suitable.

Furthermore, in this specification, the above-mentioned partial (meth)acrylic modified epoxy resin means a compound having more than one epoxy group and (meth)acryloyl group in one molecule, for example, It is obtained by reacting a part of an epoxy group of an epoxy compound having two or more epoxy groups with (meth)acrylic acid.

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

Moreover, it is preferable that the said curable resin contains a (meth)acrylic compound.

As the above-mentioned (meth)acrylic compound, for example, a (meth)acrylate compound obtained by reacting a compound having a hydroxyl group with (meth)acrylic acid, and a (meth)acrylic acid compound 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, etc. Among them, epoxy (meth)acrylate is 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.

Furthermore, in this specification, the above-mentioned "(meth)acrylic acid" means acrylic acid or methacrylic acid, and the above-mentioned "(meth)acrylic acid compound" means having an acrylic group or a methacrylic acid group (hereinafter, also Also called "(meth)acryloyl") compounds. In addition, the above-mentioned "(meth)acrylate" means acrylate or methacrylate, and the above-mentioned "epoxy (meth)acrylate" means that all epoxy groups in the epoxy compound are combined with (meth)acrylic acid. The compound formed by the reaction.

Examples of monofunctional ones in 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, ( Isocamyl methacrylate, (A Base) dicyclopentenyl acrylate, benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-(meth)acrylate Butoxy ethyl, 2-phenoxy ethyl (meth) acrylate, methoxy glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, phenoxy two Ethylene glycol (meth)acrylate, phenoxy polyethylene glycol (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, ethyl carbitol (meth)acrylate, (meth) 2,2,2-trifluoroethyl acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, 1H,1H,5H-octafluoropentyl (meth)acrylate, imine ( Meth) acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, 2-(meth)acryloyloxyethyl succinate, hexahydrophthalic acid 2-(meth)acryloyloxy ethyl formate, 2-(meth)acryloyloxyethyl 2-hydroxypropyl phthalate, 2-(meth)acryloyloxyethyl phosphoric acid, (Meth) glycidyl acrylate and the like.

In addition, examples of the bifunctional one of the (meth)acrylate compounds described above 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) Acrylic acid 2-hydroxy-3 -(Meth)acryloxy propyl ester, carbonate diol di(meth)acrylate, polyether diol di(meth)acrylate, polyester diol di(meth)acrylate, polyhexane Lactonediol 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 modification 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, di-trimethylolpropane tetra(meth)acrylate, neopentylerythritol tetra(meth)acrylate, dineopentyl pentaerythritol penta(meth)acrylate, dineopentyl Tetraol hexa(meth)acrylate and the like.

As said epoxy (meth)acrylate, the thing obtained by conventionally making an epoxy compound and (meth)acrylic acid react in the presence of a basic catalyst etc. is 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 the above-mentioned epoxy compound as the curable resin contained in the sealing compound for liquid crystal display elements of the present invention 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., Ltd.); Epoxy Ester M-600A, Epoxy Ester 40EM, Epoxy Ester 70PA, Epoxy Ester 200PA, Epoxy Ester 80MFA, Epoxy Ester 3002M, Epoxy Ester 3002A, Epoxy Ester 1600A, Epoxy Ester 3000M , Epoxy Ester 3000A, Epoxy Ester 200EA, Epoxy Ester 400EA (all manufactured by Kyoeisha Chemical Co., Ltd.); DENACOL Acrylate DA-141, DENACOL Acrylate DA-314, DENACOL Acrylate DA-911 (all manufactured by Nagase chemteX), etc.

As the above-mentioned (meth)acrylate amine ester, for example, it can be obtained by the following method, that is, in the presence of a catalyst amount of a tin-based compound, 2 equivalents of a (meth)acrylic acid derivative having a hydroxyl group and 2 One isocyanate compound of one isocyanate group reacts with 1 equivalent.

As the isocyanate compound used as the raw material of the (meth) amine acrylate, for example, isophorone diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, hexamethylene diisocyanate, tri Methylhexamethylene diisocyanate, diphenylmethane-4,4'-diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, toluidine diisocyanate, Xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris(isocyanatophenyl) phosphorothioate, tetramethylxylylene diisocyanate, 1,6 , 11-Undecane triisocyanate and so on.

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, polyester diols, polycaprolactone diols, and other polyols with excess isocyanate compounds.

(A (Meth)acrylic acid derivatives, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxyethyl (meth)acrylate Hydroxyalkyl mono(meth)acrylates such as hydroxybutyl ester; or ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, polyethylene glycol, etc. Mono(meth)acrylate of trihydric alcohol; or mono(meth)acrylate or di(meth)acrylate of trihydric alcohol such as trimethylolethane, trimethylolpropane, glycerin, etc.; or bisphenol Epoxy (meth)acrylates such as type A epoxy acrylates, 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.); EBECRYL210, EBECRYL220, EBECRYL230, EBECRYL270 , EBECRYL1290, EBECRYL2220, EBECRYL4827, EBECRYL4842, EBECRYL4858, EBECRYL5129, EBECRYL6700, EBECRYL8402, EBECRYL8803, EBECRYL8804, EBECRYL8807, EBECRYL9260 (all manufactured by Dares, Artresin UN-330, Artresin UN-330, Artresin UN-500, Artresin Artresin); UN-1255, Artresin UN-3320HB, Artresin UN-7100, Artresin UN-9000A, Artresin UN-9000H (all manufactured by Nejo Kogyo); 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.), etc.

When the sealing compound for liquid crystal display elements of the present invention contains the epoxy compound and the (meth)acrylic compound, it is preferable that the ratio of the epoxy group to the (meth)acrylic group is 5:95 to 70 : The above-mentioned epoxy compound and the above-mentioned (meth)acrylic compound are blended in a mode of 30. By setting the ratio of the epoxy group to this range, the obtained sealing compound for liquid crystal display elements suppresses the occurrence of liquid crystal contamination and has more excellent adhesiveness.

From the viewpoint of suppressing liquid crystal contamination, the curable resin is preferably a unit having hydrogen bonding properties such _{as -OH group, -NH- group, and -NH 2 group.}

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

Examples of the radical polymerization initiator include photoradical polymerization initiators that generate radicals by light irradiation, or thermal radical polymerization initiators that generate radicals by heating.

等。 As the aforementioned photoradical polymerization initiator, for example, benzophenone-based compounds, acetophenone-based compounds, phosphine oxide-based compounds, titanocene-based compounds, oxime ester-based compounds, benzoin ether-based compounds, Benzyl, 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, Lucirin TPO (all of which are from BASF Manufacturing); Benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether (all manufactured by Tokyo Chemical Industry Co., Ltd.), etc.

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 "polymeric azo compound" means a radical having an azo group and generating a radical which can harden the (meth)acryloyl group by heat. The number average molecular weight of the radical 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 above-mentioned polymer azo starter 1000 or more, liquid crystal contamination can be suppressed, and it can be easily mixed with a 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.

Moreover, as an example of an azo initiator other than the polymer azo initiator, for example: V -65, V-501 (all manufactured by Wako Pure Chemical Industries, Ltd.), etc.

As said organic peroxide, for example, ketone peroxide, peroxyketal, hydrogen peroxide, dialkyl peroxide, peroxyester, diacyl peroxide, peroxydicarbonate, etc. are mentioned.

Regarding the content of the 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 setting the content of the radical polymerization initiator in this range, the obtained sealing compound for liquid crystal display elements suppresses liquid crystal contamination and is more excellent in storage stability or curability. The lower limit of the content of the 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 viscosity, improve adhesion based on the stress dispersion effect, improve linear expansion coefficient, and further improve the moisture resistance of the cured product.

Examples of the above-mentioned fillers include: silica, talc, glass beads, asbestos, gypsum, diatomaceous earth, bentonite, bentonite, montmorillonite, sericite, activated clay, alumina, zinc oxide, Inorganic fillers such as iron oxide, magnesium oxide, tin oxide, titanium oxide, calcium carbonate, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, aluminum nitride, silicon nitride, barium sulfate, calcium silicate, etc.; or polyester particles, Organic fillers such as polyurethane microparticles, vinyl polymer microparticles, and acrylic polymer microparticles.

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. When the content of the filler is within this range, the coating properties and the like are not deteriorated, and the effects such as improvement of adhesiveness are more excellent. 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.

It is preferable that the sealing compound for liquid crystal display elements of this invention contains a silane coupling agent. The above-mentioned silane coupling agent mainly functions as an adhesive auxiliary agent for bonding the sealant to the substrate and the like well.

As the above-mentioned silane coupling agent, it is excellent in the effect of improving the adhesion to the substrate, etc., by chemically bonding with the curable resin, it can suppress the curable resin from flowing out into the liquid crystal, for example: N-phenyl-3 -Aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanatopropyl Trimethoxysilane, etc.

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. With the content of the silane coupling agent in this range, the effect of suppressing the occurrence of liquid crystal contamination and improving adhesion is more excellent. 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 this invention may contain a light-shielding agent. By containing the said light-shielding agent, the sealing compound for liquid crystal display elements of this invention can be used suitably as a light-shielding sealing compound.

As said light-shielding agent, iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, resin-coated carbon black, etc. are mentioned, for example. Among them, titanium black is preferred.

The above-mentioned titanium black is a substance that has an improved transmittance in the vicinity of the ultraviolet region, especially light with a wavelength of 370 to 450 nm, compared with the average transmittance of light with a wavelength of 300 to 800 nm. That is, the above-mentioned titanium black is a light-shielding agent having the following properties: it imparts light-shielding properties to the sealant for liquid crystal display elements of the present invention by sufficiently shielding light of a wavelength in the visible light region, and on the other hand, makes light of a wavelength near the ultraviolet region penetrate. Therefore, by using the above-mentioned peptide black to wear The light of the wavelength (370-450nm) whose transmittance is increased and the reaction can start to be used as the above-mentioned radical photopolymerization initiator can further increase the photocurability of the sealing compound for liquid crystal display elements of the present invention. Furthermore, on the other hand, as the light-shielding agent contained in the sealing compound for liquid crystal display elements of the present invention, a substance with high insulation is preferable, and as a light-shielding agent with high insulation, titanium black is also preferable .

The optical density (OD value) per 1 μm of the titanium black is preferably 3 or more, more preferably 4 or more. The higher the light-shielding property of the titanium black, the better, and the OD value of the titanium black does not particularly have a preferred upper limit, and it is usually 5 or less.

The above-mentioned titanium black exhibits a sufficient effect even if it is not surface-treated, but it can also be treated with organic components such as coupling agents, or with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, zirconium oxide, etc. Titanium black that has been surface-treated with inorganic components such as magnesium oxide. Among them, from the viewpoint that the insulation can be further improved, those treated with organic components are preferred.

In addition, the liquid crystal display element manufactured using the sealant for liquid crystal display element of the present invention blended with the above-mentioned titanium black as a light-shielding agent has sufficient light-shielding properties, and therefore can achieve no light leakage, high contrast, and excellent graphics. Image display quality liquid crystal display element.

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

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

In addition, the lower limit of the volume resistance of the titanium black is preferably 0.5Ω‧cm, and the upper limit is preferably 3Ω‧cm, the better lower limit is 1Ω‧cm, and the better upper limit is 2.5Ω‧cm.

The primary particle size of the aforementioned light-shielding agent is not particularly limited as long as it is less than the distance between the substrates of the liquid crystal display element. The preferred lower limit is 1 nm, and the preferred upper limit is 5000 nm. When the primary particle size of the above-mentioned light-shielding agent is in this range, it is possible to obtain one that does not deteriorate the coating properties of the obtained sealing compound for liquid crystal display elements and has more excellent light-shielding properties. The lower limit of the primary particle size of the sunscreen is more preferably 5 nm, the upper limit is more preferably 200 nm, the lower limit is still more preferably 10 nm, and the upper limit is more preferably 100 nm.

In addition, the primary particle size of the sunscreen can be measured by dispersing the sunscreen in a solvent (water, organic solvent, etc.) using NICOMP 380ZLS (manufactured by PARTICLE SIZING SYSTEMS).

The lower limit of the content of the light-shielding agent in 100 parts by weight of the sealing compound for liquid crystal display elements of the present invention is preferably 5 parts by weight, and the upper limit is preferably 80 parts by weight. When the content of the light-shielding agent is within this range, it is possible to exhibit more excellent light-shielding properties without lowering the adhesion of the obtained sealing compound for liquid crystal display elements to the substrate, or the strength or drawing properties after curing. The lower limit of the content of the sunscreen is more preferably 10 parts by weight, the upper limit is more preferably 70 parts by weight, the lower limit is more preferably 30 parts by weight, and the upper limit is more preferably 60 parts by weight.

The sealant 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, 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 use of a homogeneous disperser, homomixer, universal mixer, planetary mixer, kneader, A mixing machine such as a three-roll mill, a method of mixing a curable resin, a thermosetting agent, and a radical polymerization initiator or filler, etc.

By blending conductive fine particles in the sealing compound for liquid crystal display elements of the present invention, a vertical conduction material can be manufactured. 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, for example, metal balls, those having a conductive metal layer formed on the surface of resin fine particles, and the like can be used. Among them, a conductive metal layer formed on the surface of the resin particles is preferable because of the excellent elasticity of the resin particles, which enables conductive connection 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 for 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 inventive sealant for liquid crystal display elements is applied to one of two transparent substrates with electrodes such as ITO film to form a frame-shaped seal pattern; the tiny droplets of liquid crystal are drip-coated into the frame of the seal pattern The entire surface is a step of overlapping another substrate under vacuum; and a step of heating to harden the sealant. In addition, before the step of heating and hardening the sealant, a step of temporarily hardening the sealant by light irradiation may be performed.

According to the present invention, it is possible to provide a sealing compound for liquid crystal display elements that can achieve both storage stability and rapid curing properties at low temperatures. 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.

(Production of compound A having the structure shown in formula (1))

To 71 parts by weight of 1,4-bis(aminomethyl)cyclohexane and 190 parts by weight of bisphenol A diglycidyl ether, 500 propylene glycol monomethylether acetate (propylene glycol monomethylether acetate) was added Part by weight and 500 parts by weight of n-butanol were mixed and dissolved, and heated and stirred at 100°C for 3 hours. The obtained reaction mixture is solvent removed and dried, and the obtained solid is pulverized with a jet mill to obtain compound A (melting point 83°C) having the structure represented by the above formula (1). By ¹ H-NMR, ¹³ C-NMR, and FT-IR analysis, it was confirmed that the obtained compound A having the structure represented by the formula (1) has the structure represented by the above formula (3) (X is the above formula (2) The group represented by -1) (R ¹ and R ² are methyl groups)).

(Production of compound B with the structure shown in formula (1))

Except that 170 parts by weight of bisphenol F diglycidyl ether is used instead of 190 parts by weight of bisphenol A diglycidyl ether, the same method as the above "(Production of compound A having the structure represented by formula (1))" is used , The compound B (melting point 68°C) having the structure represented by the above formula (1) was obtained. By ¹ H-NMR, ¹³ C-NMR, and FT-IR analysis, it was confirmed that the obtained compound B having the structure represented by the formula (1) has the structure represented by the above formula (3) (X is the above formula (2) -1) The group represented by (R ¹ and R ² are hydrogen)).

(Production of compound C with the structure shown in formula (1))

Except for using 180 parts by weight of bisphenol E diglycidyl ether instead of 190 parts by weight of bisphenol A diglycidyl ether, the same method as the above "(Production of compound A having the structure represented by formula (1))" , The compound C (melting point 78°C) having the structure represented by the above formula (1) was obtained. By ¹ H-NMR, ¹³ C-NMR, and FT-IR analysis, it was confirmed that the obtained compound C having the structure represented by the formula (1) has the structure represented by the above formula (3) (X is the above formula (2) -1) The group represented by (one of R ¹ and R ² is methyl, and the other is hydrogen)).

(Production of compound D with the structure shown in formula (1))

Except for using 130 parts by weight of resorcinol diglycidyl ether instead of 190 parts by weight of bisphenol A diglycidyl ether, it is the same as the above "(Production of compound A having the structure represented by formula (1))" By the method, compound D (melting point 94°C) having the structure represented by the above formula (1) was obtained. By ¹ H-NMR, ¹³ C-NMR, and FT-IR analysis, it was confirmed that the obtained compound D having the structure represented by formula (1) has the structure represented by the above formula (3) (X is the above formula (2) -4) The base shown).

(Production of compound E with the structure shown in formula (1))

Except for the use of 180 parts by weight of biphenyl-4,4'-diyl bis(glycidyl ether) instead of 190 parts by weight of bisphenol A diglycidyl ether, it can be compared with the above "(with formula (1) (Production of compound A of structure)" in the same way, compound E (melting point 98°C) having the structure represented by the above formula (1) was obtained. By ¹ H-NMR, ¹³ C-NMR, and FT-IR analysis, it was confirmed that the obtained compound E having the structure represented by the formula (1) has the structure represented by the above formula (3) (X is the above formula (2) -3) The base shown).

(Production of compound F with the structure shown in formula (1))

Except that 247 parts by weight of bisphenol A epoxy resin is used instead of 190 parts by weight of bisphenol A diglycidyl ether, the same method as the above "(Production of compound A having the structure represented by formula (1))" is used, Compound F (melting point 109°C) having the structure represented by the above formula (1) was obtained. By ¹ H-NMR, ¹³ C-NMR, and FT-IR analysis, it was confirmed that the obtained compound F having the structure represented by the formula (1) has the structure represented by the above formula (3) (X is the above formula (2) The group represented by -1) (R ¹ and R ² are methyl groups)).

(Production of compound G having the structure shown in formula (1))

In addition to using 99 parts by weight of diaminophenylmethane instead of 71 parts by weight of 1,4-bis(aminomethyl)cyclohexane, it is used in accordance with the above "(Production of compound A having a structure represented by formula (1))" In the same way, compound G (melting point 97°C) having the structure represented by the above formula (1) was obtained. By ¹ H-NMR, ¹³ C-NMR, and FT-IR analysis, it was confirmed that the obtained compound G having the structure represented by formula (1) has the above formula (1) and X in the above formula (2-1) The structure of the group (R ¹ and R ² are methyl) shown in ).

(Production of compound H with the structure shown in formula (1))

In addition to using 71 parts by weight of 1,3-bis(aminomethyl)cyclohexane to replace 71 parts by weight of 1,4-bis(aminomethyl)cyclohexane, it can be combined with the above "(with formula (1) (Production of Compound A of the Structure Shown)" In the same way, Compound H (melting point 81°C) having the structure of the above formula (1) was obtained. By ¹ H-NMR, ¹³ C-NMR, and FT-IR analysis, it was confirmed that the obtained compound H having the structure represented by formula (1) has the structure represented by the above formula (4) (X is the above formula (2) The group represented by -1) (R ¹ and R ² are methyl groups)).

(Production of compound I with the structure shown in formula (1))

In addition to using 71 parts by weight of 1,3-bis(aminomethyl)cyclohexane to replace 71 parts by weight of 1,4-bis(aminomethyl)cyclohexane, it can be combined with the above "(with formula (1) Preparation of Compound B of the Structure Shown)" The same method was used to obtain Compound I (melting point 67°C) having the structure represented by the above formula (1). By ¹ H-NMR, ¹³ C-NMR, and FT-IR analysis, it was confirmed that the obtained compound I having the structure represented by the formula (1) has the structure represented by the above formula (4) (X is the above formula (2) -1) The group represented by (R ¹ and R ² are hydrogen)).

(Production of epoxy-imidazole addition compound)

To 20 parts by weight of 2-methylimidazole and 190 parts by weight of bisphenol A diglycidyl ether, 500 parts by weight of toluene and 500 parts by weight of n-butanol were added, mixed and dissolved, and heated and stirred at 70°C for 2 hours . The obtained reaction mixture is solvent-removed and dried, and the obtained solid is pulverized with a jet mill to obtain an epoxy-imidazole adduct compound.

(Examples 1-15, Comparative Examples 1, 2)

According to the blending ratios described in Tables 1 and 2, the materials were mixed using a planetary mixer (manufactured by Thinky, "Defoaming Taro"), and then mixed using a three-roll mill to prepare Example 1 ~15. The sealing compound for each liquid crystal display element of Comparative Examples 1 and 2.

<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 Tables 1 and 2.

(Storage stability)

For each sealing compound for liquid crystal display elements obtained in the examples and comparative examples, the initial viscosity immediately after 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 1.2, set to "○", if the rate of change of viscosity is greater than 1.2 and less than 1.5, set to "△", and if the rate of change is greater than 1.5, set to "×", The storage stability was evaluated.

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)

The sealants for liquid crystal display elements obtained in the examples and comparative examples were irradiated with ^{ultraviolet light of 100 mW/cm 2} for 30 seconds with a metal halide lamp, and then measured using an FT-IR measuring device (manufactured by Agilent Technologies, "UMA600") The reaction rate of the epoxy group when heated at 100°C for 40 minutes (the reduction rate of the peak value derived from the epoxy group). Set the epoxy group reaction rate of 90% or more to "○", set the reaction rate of less than 90% and 70% to "△", and set the reaction rate of less than 70% to "×" to evaluate the low-temperature hardening sex.

(Display performance of liquid crystal display element)

Disperse 1 part by weight of spacer fine particles (manufactured by Sekisui Chemical Industry Co., Ltd., "Micropearl SI-H050") in 100 parts by weight of each liquid crystal display element sealant obtained in the examples and comparative examples, on two rubbed wirings One of the film and the substrate with the transparent electrode is applied with a syringe so that the line width of the sealant is 1 mm, thereby forming a seal for the liquid crystal display element.

Then, drop a small drop of liquid crystal (manufactured by Chisso, "JC-5004LA") onto the entire surface of the sealant frame, and then immediately attach another color filter substrate with transparent electrodes, using metal halide The lamp was irradiated with 100 mW/cm ² ultraviolet rays (wavelength: 365 nm) to the sealant portion for 30 seconds, and then heated at 100° C. for 40 minutes to obtain a liquid crystal display element.

After performing an operation test for the obtained liquid crystal display element for 100 hours, it was visually confirmed that the liquid crystal alignment was disturbed in the vicinity of the sealing compound in a state where a voltage was applied at 80° C. for 1000 hours.

Alignment fuzziness is judged based on the color unevenness of the display part, and according to the degree of color unevenness, The case where color unevenness is not confirmed at all is evaluated as "◎", the case where slight color unevenness is confirmed as "○", and the case where color unevenness is slightly confirmed is evaluated as "△", which will clearly The case where color unevenness was confirmed was evaluated as "×", thereby evaluating low liquid crystal contamination.

Furthermore, the liquid crystal display elements evaluated as "◎" and "○" are of practically no problem level, "△" is the level that may cause problems depending on the display design of the liquid crystal display element, and "×" is intolerable The level of practical application.

[Industrial availability]

According to the present invention, it is possible to provide a sealant for liquid crystal display elements that can achieve both storage stability and rapid curing properties at low temperatures. 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.

Claims (7)

A sealant for liquid crystal display elements, comprising a curable resin and a thermosetting agent, characterized in that: the thermosetting agent contains a structure represented by the following formula (1) and having a primary amine group at both ends of the main chain Compound

In formula (1), X is a structure having an aromatic ring, n is an integer from 1 to 10, and * is the bonding position. For example, the sealing compound for liquid crystal display elements in the first item of the scope of patent application, wherein X in formula (1) is the following formulas (2-1), (2-2), (2-3), (2-4 ), or the structure shown in (2-5)

In the formula (2-1), R ¹ and R ² are each independently hydrogen or a methyl group, and in the formulas (2-1) to (2-5), * is a bonding position. The sealing compound for liquid crystal display elements according to the first or second item of the scope of patent application, which contains a compound having a structure represented by the following formula (3) as a compound having a structure represented by formula (1)

In formula (3), X is the same structure as X in formula (1), n is the same number as n in formula (1), and * is the bonding position. The sealing compound for liquid crystal display elements of the first or second item of the scope of patent application, which contains a compound having a structure represented by the following formula (4) as a compound having a structure represented by formula (1)

In formula (4), X is the same structure as X in formula (1), n is the same number as n in formula (1), and * is the bonding position. For example, the sealing compound for liquid crystal display elements of the first or second item of the scope of patent application, wherein the compound having the structure represented by formula (1) has a melting point of 60°C to 100°C. An up-and-down conduction material containing the sealant for liquid crystal display elements and conductive fine particles of the first, second, third, fourth, or fifth patent application range. 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.