TW202003776A - Sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element - Google Patents

Abstract

The purpose of the present invention is to provide a sealant for a liquid crystal display element, the sealant having excellent adhesiveness, moisture permeation prevention, and liquid crystal contamination resistance. Another purpose of the present invention is to provide a vertical conduction material and a liquid crystal display element, which are obtained using the sealant for a liquid crystal display element. The present invention is: (A) a sealant for a liquid crystal display element, the sealant containing a curable resin and a radical polymerization initiator, wherein the curable resin is a (meth)acrylic compound having a hydrogen-bonding functional group value of 0.0030 mol/g or greater and a molecular weight of 500-1200, not having an epoxy group, and having three or more aromatic rings per molecule; and/or (B) a sealant for a liquid crystal display element, the sealant containing a partial (meth)acrylic modified epoxy resin that has a hydrogen-bonding functional group value of 0.0030 mol/g or greater and a molecular weight of 500-1200, and having three or more aromatic rings per molecule.

Description

Sealant for liquid crystal display element, upper and lower conduction materials, and liquid crystal display element

The present invention relates to a sealant for liquid crystal display elements excellent in adhesiveness, moisture permeability resistance, and low liquid crystal contamination. In addition, the present invention relates to an upper and lower conduction material and a liquid crystal display element formed by using the sealant for liquid crystal display elements.

In recent years, as a method of manufacturing a liquid crystal display element such as a liquid crystal display unit, from the viewpoint of shortening the lead time and optimizing the amount of liquid crystal used, the use of a sealant as disclosed in Patent Document 1 and Patent Document 2 This is called the liquid crystal dropping method of the drop processing method. In the drop processing method, first, a frame-like sealing pattern is formed by dispensing glue on one of the two substrates with electrodes. Secondly, the droplets of liquid crystal are dropped into the sealing frame of the substrate in a state where the sealant is not hardened, another substrate is superposed under vacuum, and the sealant is hardened to manufacture a liquid crystal display element. At present, the drop processing method has become the mainstream of manufacturing methods of liquid crystal display elements.

However, in today's era where various mobile devices with LCD panels, such as mobile phones and portable game consoles, have become popular, miniaturization of devices is the most sought-after issue. As a method of miniaturization, a narrow edge of the liquid crystal display portion can be cited, for example, the position of the sealing portion is arranged under the black matrix (hereinafter, also referred to as "narrow edge design"). With this narrow edge design, in the liquid crystal display element, the distance from the pixel area to the sealant becomes shorter, and the display unevenness caused by the contamination of the liquid crystal by the sealant becomes easy to occur. Especially in recent years, the high viewing angle of liquid crystal display elements has continued to develop. However, when a conventional sealant is used in a high viewing angle liquid crystal display element, there is a problem that liquid crystal contamination is likely to occur.

In addition, with the popularization of tablet terminals or mobile terminals, liquid crystal display elements are gradually required to have reliability in humidity resistance when driven in a high-temperature and high-humidity environment, and the sealant is further required to prevent water from infiltrating from the outside. For this reason, it is necessary to improve the adhesion of the sealant to the substrate and the like, and to improve the moisture permeability of the sealant. However, with the narrow edge design, the line width of the applied sealant becomes thinner, and even in the case of thinning the line, it is difficult to obtain a sealant excellent in both adhesiveness and moisture permeability. Prior technical literature Patent Literature

Patent Document 1: Japanese Patent Laid-Open No. 2001-133794 Patent Literature 2: International Publication No. 02/092718

[Problems to be solved by the invention]

An object of the present invention is to provide a sealant for liquid crystal display elements excellent in adhesiveness, moisture permeability resistance, and low liquid crystal contamination. In addition, an object of the present invention is to provide an upper and lower conduction material and a liquid crystal display element using the sealant for a liquid crystal display element. [Technical means to solve the problem]

The present invention is a sealant for a liquid crystal display element, which contains a curable resin and a radical polymerization initiator, the curable resin contains: (A) (meth)acrylic compound, the valence of its hydrogen-bonding functional group 0.0030 mol/g or more, molecular weight of 500 or more and 1200 or less, no epoxy group, 3 or more aromatic rings in one molecule, and/or (B) part (meth)acrylic modified epoxy resin, which The valence of the hydrogen-bonding functional group is 0.0030 mol/g or more, the molecular weight is 500 or more and 1200 or less, and it has three or more aromatic rings in one molecule. Moreover, the invention of another aspect is a sealing compound for liquid crystal display elements which contains a curable resin and a radical polymerization initiator. The said curable resin contains the following formula (1) and has 3 in 1 molecule The compound of the above aromatic ring, and/or the compound represented by the following formula (3) and having 3 or more aromatic rings in one molecule.

In formula (1), R ¹ each independently represents a hydrogen atom or a methyl group, R ² represents a divalent aromatic group represented by the following formula (2-1) or (2-2), and R ³ represents carbon number 2 A divalent aliphatic group of above and below 15 or a divalent aromatic group which is the same as or different from R ² , n is 1 or more and 3 or less.

In formula (2-1), R ⁴ represents a linear or branched alkylene group having a carbon number of 1 or more and 4 or less, and p is 0 or more and 3 or less. In formula (2-2), q is 0 or more and 3 or less. In formulas (2-1) and (2-2), * represents the bonding position. The aromatic rings in the formulas (2-1) and (2-2) are all or part of the hydrogen atoms may be substituted.

In formula (3), R ⁵ represents a hydrogen atom or a methyl group, R ⁶ represents a divalent aromatic group represented by the following formulas (4-1) and (4-2), and R ⁷ represents a carbon number of 1 or more and 20 The following divalent aliphatic group or the same or different divalent aromatic group as R ^{6 has} m of 1 or more and 3 or less.

In formula (4-1), R ⁸ represents a linear or branched alkylene group having a carbon number of 1 or more and 4 or less, and p is 0 or more and 3 or less. In formula (4-2), q is 0 or more and 3 or less. In formulas (4-1) and (4-2), * represents the bonding position. The aromatic rings in formulas (4-1) and (4-2) are all or part of the hydrogen atoms may be substituted.

The present invention is described in detail below. Hereinafter, the (A) (meth)acrylic compound is also referred to as "(meth)acrylic compound of the present invention", and the valence of the (A) (meth)acrylic compound having a hydrogen-bonding functional group is 0.0030 mol/g or more, molecular weight is 500 or more and 1200 or less, does not have an epoxy group, and has 3 or more aromatic rings in one molecule. In addition, hereinafter, the (B) part (meth)acrylic modified epoxy resin is also referred to as "part (meth)acrylic modified epoxy resin of the present invention", and the (B) part (meth)acrylic acid The modified epoxy resin has a hydrogen bonding functional group valence of 0.0030 mol/g or more, a molecular weight of 500 or more and 1200 or less, and has 3 or more aromatic rings in one molecule.

The present inventors found that by using "a compound having a valence and molecular weight of a hydrogen-bonding functional group in a specific range and having a specific structure" as a curable resin, adhesion, moisture permeability resistance, and The sealing compound for liquid crystal display elements excellent in low liquid crystal contamination property completes this invention. Furthermore, in recent years, although the use of highly polarized liquid crystals has increased in response to the higher viewing angle of liquid crystal display elements, the sealant for liquid crystal display elements of the present invention is low even for such highly polarized liquid crystals. The liquid crystal contamination is still excellent.

The sealing compound for liquid crystal display elements of this invention contains curable resin. The curable resin contains the (meth)acrylic compound of the present invention and/or a part of the (meth)acrylic modified epoxy resin of the present invention. By containing the (meth)acrylic compound of the present invention and/or part of the (meth)acrylic modified epoxy resin of the present invention, the sealant for liquid crystal display elements of the present invention becomes adhesive, moisture-proof, and low Those with excellent liquid crystal contamination. Furthermore, in this specification, the above-mentioned "(meth)acrylic acid" means acrylic acid or methacrylic acid, and the above-mentioned "(meth)acrylic compound" means a compound having a (meth)acryloyl group. "(Meth)acryloyl" means acryloyl or methacryloyl. In addition, the above-mentioned "partially (meth)acrylic acid modified epoxy resin" means a product obtained by reacting an epoxy group of a part of an epoxy compound having two or more epoxy groups with (meth)acrylic acid in one molecule. Compounds with more than one epoxy group and (meth)acryloyl group in each molecule."

The lower limit of the valence of the hydrogen-bonding functional group of the (meth)acrylic compound of the present invention and the partially (meth)acrylic modified epoxy resin of the present invention is 0.0030 mol/g. When the valence of the above hydrogen-bonding functional group is 0.0030 mol/g or more, the sealant for liquid crystal display elements of the present invention is excellent in low liquid crystal contamination even for highly polarized liquid crystals. The lower limit of the valence of the above hydrogen-bonding functional group is preferably 0.040 mol/g. In addition, in this specification, the "valence number of the hydrogen-bonding functional group" means the value obtained by dividing the number of hydrogen-bonding functional groups in the molecule of the compound 1 by the weight average molecular weight of the compound. In the case of a compound having a molecular weight distribution (that is, a compound containing multiple components of different molecular weights), the number of hydrogen-bonding functional groups mentioned above means hydrogen bonding in 1 molecule of the component (main component) with the largest proportion The number of sexual functional groups. In addition, in this specification, the "weight average molecular weight" is measured by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent, and is a value obtained by polystyrene conversion. As the column used when measuring the weight average molecular weight converted from polystyrene by GPC, for example, Shodex LF-804 (manufactured by Showa Denko) and the like can be cited.

Examples of the hydrogen-bonding functional group include a hydroxyl group, an amine group, a carboxyl group, and a mercapto group. Among them, the hydroxyl group is preferred.

The (meth)acrylic compound of the present invention and the partially (meth)acrylic modified epoxy resin of the present invention have a lower molecular weight of 500 and an upper limit of 1200. When the molecular weight is 500 or more, the sealing compound for liquid crystal display elements of the present invention is excellent in low liquid crystal contamination. When the molecular weight is 1200 or less, the sealing compound for liquid crystal display elements of the present invention has excellent coating properties. The preferred lower limit of the above molecular weight is 600, and the preferred upper limit is 1100. In addition, in this specification, the above "molecular weight" refers to the molecular weight obtained from the structural formula when referring to a compound of a specific molecular structure, but for a compound with a wide distribution of polymerization degree and a compound whose modification site is not specified, there are It is expressed by weight average molecular weight.

The (meth)acrylic compound of the present invention and part of the (meth)acrylic modified epoxy resin of the present invention have three or more aromatic rings in one molecule. By using the (meth)acrylic compound of the present invention having three or more aromatic rings in one molecule and/or a part of the (meth)acrylic modified epoxy resin of the present invention, the sealant for liquid crystal display elements of the present invention In the case of thinning and coating, it is also excellent in moisture permeability resistance. Moreover, from the viewpoint of making the molecular weight within the above range, the (meth)acrylic compound of the present invention and the partially (meth)acrylic modified epoxy resin of the present invention preferably have 10 or less aromatic rings per molecule. Examples of the aromatic ring include benzene ring, naphthalene ring, and onion ring. Among them, a benzene ring is preferred. In addition, the (meth)acrylic compound of the present invention and the partially (meth)acrylic modified epoxy resin of the present invention preferably have three or more conjugated six-membered rings in one molecule. For example, benzene rings are counted as one conjugated six-membered ring, naphthalene rings are counted as two conjugated six-membered rings, and onion rings are counted as three conjugated six-membered rings. In addition, the number of aromatic rings or conjugated six-membered rings in one molecule, in the case of compounds with molecular weight distribution (that is, compounds containing multiple components of different molecular weights), means the component with the largest content ratio ( Main component) The number of aromatic rings or conjugated six-membered rings in one molecule.

As the (meth)acrylic compound of the present invention, specifically, the compound represented by the above formula (1) is preferable.

The compound represented by the above formula (1) can be suitably produced by the following method. That is, first, propylene oxide ether or resorcinol propylene oxide ether having a bisphenol skeleton is reacted with a compound having two aromatic hydroxyl groups in one molecule, thereby obtaining a compound having three or more aromatic rings in one molecule Two epoxy compounds. Next, all the epoxy groups of the diepoxide compound having three or more aromatic rings in one molecule are reacted with (meth)acrylic acid by a conventional method and in the presence of an alkaline catalyst, thereby obtaining the above formula ( 1) The compound represented. When R ³ in the above formula (1) is to be a divalent aromatic group different from R ² , for the propylene oxide ether having the bisphenol skeleton or the resorcinol propylene oxide ether, and the above 1 Compounds having two aromatic hydroxyl groups in the molecule may be used as long as they have different divalent aromatic groups. Furthermore, when using a compound obtained by the condensation reaction of (meth)acrylic acid with propylene oxide ether having the bisphenol skeleton or the resorcinol propylene oxide ether, because of the presence of by-products However, it is difficult to make the valence of the hydrogen-bonding functional group more than 0.030 mol/g. Therefore, the use of commercially available epoxy (meth)acrylates with such compounds cannot be used as the (meth)acrylic compound of the present invention.

Examples of the propylene oxide ether having the bisphenol skeleton include bisphenol A propylene oxide ether, bisphenol B propylene oxide ether, bisphenol E propylene oxide ether, and bisphenol F propylene oxide ether.

Examples of compounds having two aromatic hydroxyl groups in one molecule include bisphenol A, bisphenol B, bisphenol E, bisphenol F, resorcinol, catechol, hydroquinone, and 4,4′- Dihydroxybiphenyl, etc.

The partially (meth)acrylic modified epoxy resin of the present invention is specifically a compound represented by the above formula (3).

The compound represented by the above formula (3) can be suitably produced by the following method. That is, the propylene oxide ether having the bisphenol skeleton or the resorcinol propylene oxide ether is reacted with the compound having two aromatic hydroxyl groups in one molecule to obtain three or more aromatic compounds in one molecule The second ring of epoxy compounds. Using conventional methods and in the presence of an alkaline catalyst, one epoxy group of a diepoxide compound having three or more aromatic rings in one molecule is reacted with (meth)acrylic acid, whereby the above formula (3) can be obtained The compound represented. When R ⁷ in the above formula (3) is to be a divalent aromatic group different from R ⁶ , for the propylene oxide ether having the bisphenol skeleton or the resorcinol dioxide propylene oxide, and the above 1 Compounds having two aromatic hydroxyl groups in the molecule may be used as long as they have different divalent aromatic groups. Furthermore, when using a compound obtained by the condensation reaction of (meth)acrylic acid with propylene oxide ether having the bisphenol skeleton or the resorcinol propylene oxide ether, because of the presence of by-products However, it is difficult to make the valence of the hydrogen-bonding functional group more than 0.030 mol/g. Therefore, the use of commercially available partially (meth)acrylic modified epoxy resins with such compounds cannot be used as the partially (meth)acrylic modified epoxy resins of the present invention.

The above curable resins may contain other curable resins in addition to the (meth)acrylic compound of the present invention and/or part of the (meth)acrylic modified epoxy resin of the present invention, as long as they do not hinder the purpose of the present invention. . When the other curable resin is contained, the (meth)acrylic compound of the present invention represented by the above formula (1) and/or part of the (meth)acrylic acid of the present invention represented by the above formula (1) in 100 parts by weight of the curable resin The preferred lower limit of the content of the quality epoxy resin is 5 parts by weight, and the preferred upper limit is 80 parts by weight. When the content of the (meth)acrylic compound of the present invention and/or part of the (meth)acrylic modified epoxy resin of the present invention is within this range, the resulting sealant for liquid crystal display elements becomes adhesive and moisture-proof , And those with low liquid crystal pollution are more excellent. The more preferable lower limit of the content of the (meth)acrylic compound of the present invention and/or the partially (meth)acrylic modified epoxy resin of the present invention is 10 parts by weight, and the more preferable upper limit is 50 parts by weight.

As the other curable resin described above, a compound having an epoxy group (hereinafter, also referred to as "other epoxy compound") other than the partially (meth)acrylic modified epoxy resin of the present invention can be suitably used.

Examples of the other epoxy compounds include bisphenol A epoxy resin, bisphenol S epoxy resin, resorcinol epoxy resin, biphenyl epoxy resin, and sulfide ring. Oxygen resin, diphenyl ether epoxy resin, dicyclopentadiene epoxy resin, naphthalene epoxy resin, phenol novolac epoxy resin, o-cresol novolac epoxy resin, dicyclopentadiene Novolac epoxy resin, biphenol novolac epoxy resin, naphthol novolac epoxy resin, glycidylamine epoxy resin, alkyl polyol epoxy resin, rubber modified epoxy resin, Epoxy propyl ester compounds, etc. In addition, as the above-mentioned other epoxy compounds, as some (meth)acrylic modified epoxy resins other than the (meth)acrylic modified epoxy resins of the present invention, by using such epoxy compounds A compound obtained by reacting a part of epoxy groups with (meth)acrylic acid.

In addition, regarding the above-mentioned curable resin, as the above-mentioned other curable resin, the (meth)acrylic compound of the present invention and some (meth)acrylic modified epoxy resins of the present invention (meth) ) Acrylic compounds. Examples of the other (meth)acrylic compounds include (meth)acrylate compounds, epoxy (meth)acrylates, urethane (meth)acrylates, and the like. Among them, epoxy (meth)acrylate is preferred. In addition, from the viewpoint of reactivity, the other (meth)acrylic compound preferably has two or more (meth)acryloyl groups in one molecule. In addition, in this specification, the above "(meth)acrylate" means acrylate or methacrylate, and the above "epoxy (meth)acrylate" means that all epoxy groups in the epoxy compound are (Meth)acrylic acid reacts to form a compound.

Examples of monofunctional compounds in the (meth)acrylate compound 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 methacrylate, dicyclopentenyl (meth)acrylate, benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxy (meth)acrylate Ethyl acetate, 2-butoxyethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, methoxyethylene glycol (meth)acrylate, methoxypolyethylene glycol ( Methacrylates, phenoxydiethylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, ethyl carbitol ( Methacrylic acid ester, (meth)acrylic acid 2,2,2-trifluoroethyl, (meth)acrylic acid 2,2,3,3-tetrafluoropropyl ester, (meth)acrylic acid 1H,1H,5H -Octafluoropentyl ester, amide imine (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, 2-(meth)acrylic acid succinic acid Acetyloxyethyl, hexahydrophthalic acid 2-(meth)acrylic acid ethyl ester, phthalic acid 2-(meth)acrylic acid ethyl acetate 2-hydroxypropyl ester, phosphoric acid 2- (Meth)acrylic acid ethyl ester, (meth)acrylic acid glycidyl ester, etc.

In addition, examples of the bifunctional compounds in the (meth)acrylate compound 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 di (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 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 dicyclopentadiene di(meth)acrylate, ethylene oxide modified isocyanurate di(meth)acrylate, (meth)acrylic acid 2-Hydroxy-3-(meth)acryloxypropyl ester, carbonate diol di(meth)acrylate, polyether diol di(meth)acrylate, polyester diol di(meth) Acrylic ester, polycaprolactone diol di(meth)acrylate, polybutadiene diol di(meth)acrylate, etc.

In addition, examples of the trifunctional or higher among the (meth)acrylate compounds include trimethylolpropane tri(meth)acrylate and ethylene oxide addition trimethylolpropane tri(methyl ) Acrylate, propylene oxide addition trimethylolpropane tri(meth)acrylate, caprolactone modified trimethylolpropane tri(meth)acrylate, ethylene oxide addition isocyanurate Acid tri (meth) acrylate, glycerol tri (meth) acrylate, propylene oxide addition glycerol tri (meth) acrylate, neopentaerythritol tri (meth) acrylate, triphosphate (meth) Acryloyloxyethyl, di-trimethylolpropane tetra(meth)acrylate, neopentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dineopentyl Tetraol hexa (meth) acrylate, etc.

Examples of the epoxy (meth)acrylates include those obtained by reacting the other epoxy compounds with (meth)acrylic acid in the presence of an alkaline catalyst according to a conventional method.

The above-mentioned (meth)acrylate amine ester can be obtained, for example, by reacting a (meth)acrylic acid derivative having a hydroxyl group and an isocyanate compound in the presence of a tin amount of a catalyst.

Examples of the isocyanate compound include isophorone diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and diisocyanate. Phenylmethane-4,4'-diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, stubble diisocyanate ( XDI), hydrogenated XDI, urethane diisocyanate, triphenylmethane triisocyanate, tris(isocyanate phenyl)thiophosphate, tetramethyl stubble diisocyanate, 1,6,11-undecane triisocyanate, etc. .

In addition, as the isocyanate compound, an isocyanate compound having an extended chain obtained by the reaction of a polyol and an excess of isocyanate compound can also be used. Examples of the above-mentioned polyols include ethylene glycol, propylene glycol, glycerin, sorbitol, trimethylolpropane, carbonate diol, polyether diol, polyester diol, and polycaprolactone diol.

Examples of the (meth)acrylic acid derivatives having hydroxyl groups include hydroxyalkyl mono(meth)acrylates, mono(meth)acrylates of glycols, and mono(meth)acrylic acid of triols. Ester or di (meth) acrylate, epoxy (meth) acrylate, etc. Examples of the hydroxyalkyl mono(meth)acrylate include, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, (Meth)acrylic acid 4-hydroxybutyl ester, etc. Examples of the above-mentioned glycols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and polyethylene glycol. Examples of the triols include trimethylolethane, trimethylolpropane, and glycerin. Examples of the epoxy (meth)acrylate include bisphenol A epoxy acrylate.

Examples of the commercially available among the (meth)acrylic acid amine esters include: (meth)acrylic acid amine esters manufactured by East Asia Synthetic Co., Ltd., (Meth) acrylates manufactured by Daicel Zhanxin Co., Ltd. Amino (meth)acrylate manufactured, Amino (meth)acrylate manufactured by Shin Nakamura Chemical Industry Company, Amino (meth)acrylate manufactured by Kyoeisha Chemical Company, etc. Examples of the amine (meth)acrylate manufactured by the above-mentioned East Asia Synthesizer include M-1100, M-1200, M-1210, and M-1600. Examples of the amine (meth)acrylates produced by the above-mentioned Daicel Zhanxin include: 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, etc. As the (meth)acrylic acid amine ester manufactured by the above root industrial company, for example, Artresin UN-330, Artresin SH-500B, Artresin UN-1200TPK, Artresin UN-1255, Artresin UN-3320HB, Artresin UN-7100, Artresin UN-9000A, Artresin UN-9000H, etc. Examples of the amine (meth)acrylate manufactured by the above-mentioned Shin Nakamura Chemical Industry Company include: 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, etc. Examples of the amine (meth)acrylates manufactured by the Kyoeisha Chemical Company include: AH-600, AI-600, AT-600, UA-101I, UA-101T, UA-306H, UA-306I, UA －306T etc.

The sealing agent for liquid crystal display elements of this invention contains a radical polymerization initiator. Examples of the radical polymerization initiator include a photoradical polymerization initiator that generates radicals by light irradiation, and a thermal radical polymerization initiator that generates radicals by heating.

等。 作為上述光自由基聚合起始劑，具體而言例如可列舉：1－羥基環己基苯基酮、2－苄基－2－二甲胺基－1－（4－𠰌啉基苯基）－1－丁酮、2－（二甲胺基）－2－（（4－甲基苯基）甲基）－1－（4－（4－𠰌啉基）苯基）－1－丁酮、2,2－二甲氧基－1,2－二苯基乙烷－1－酮、雙（2,4,6－三甲基苯甲醯基）苯基氧化膦、2－甲基－1－（4－甲基噻吩基）－2－𠰌啉基丙烷－1－酮、1－（4－（2－羥基乙氧基）－苯基）－2－羥基－2－甲基－1－丙烷－1－酮、1－（4－（苯硫基）苯基）－1,2－辛二酮2－（O－苯甲醯基肟）、2,4,6－三甲基苯甲醯基二苯基氧化膦等。 上述光自由基聚合起始劑可單獨使用，亦可組合兩種以上而使用。Examples of the photo radical polymerization initiator include benzophenone-based compounds, acetophenone-based compounds, acylphosphine oxide-based compounds, titanocene-based compounds, oxime ester-based compounds, and benzoin. Ether compounds, 9-oxygen sulfur 𠮿

Wait. Specific examples of the photo-radical polymerization initiator include 1-hydroxycyclohexyl phenyl ketone and 2-benzyl-2-dimethylamino-1-(4-(4-aminophenyl)phenyl)- 1-Butanone, 2-(Dimethylamino)-2-((4-methylphenyl)methyl)-1-(4-(4-𠰌olinyl)phenyl)-1-butanone, 2,2-Dimethoxy-1,2-diphenylethane-1-ketone, bis(2,4,6-trimethylbenzyl)phenylphosphine oxide, 2-methyl-1 －(4-Methylthienyl)－2－𠰌olinylpropane-1-ketone, 1-(4-(2-hydroxyethoxy)-phenyl)-2-hydroxy-2-methyl-1- Propane-1-ketone, 1-(4-(phenylthio)phenyl)-1,2-octanedione 2-(O-benzyl oxime), 2,4,6-trimethylbenzyl Acyl diphenyl phosphine oxide and so on. The above-mentioned photo-radical polymerization initiator may be used alone or in combination of two or more.

Examples of the above-mentioned thermal radical polymerization initiator include azo compounds, organic peroxides, and the like. Among them, from the viewpoint of suppressing liquid crystal contamination, an initiator composed of an azo compound (hereinafter, also referred to as "azo initiator") is preferable, and a polymer azo compound is more preferable Initiator (hereinafter, also referred to as "polymer azo initiator"). The above-mentioned thermal radical polymerization initiator may be used alone or in combination of two or more. In addition, in this specification, the above-mentioned "polymer azo compound" means having an azo group, generating a radical capable of hardening a (meth)acryloyl group by heat, and having a number average molecular weight of 300 The above compounds.

The preferable lower limit of the number average molecular weight of the above polymer azo compound is 1,000, and the preferable upper limit is 300,000. By setting the number average molecular weight of the above-mentioned polymer azo compound to be in this range, it is possible to prevent adverse effects on the liquid crystal, and it can be easily mixed into the curable resin. The lower limit of the number average molecular weight of the above-mentioned polymer azo compound is more preferably 5,000, the more preferably the upper limit is 100,000, the more preferably the lower limit is 10,000, and the more preferably the upper limit is 90,000. In addition, in this specification, the said number average molecular weight is measured by the gel permeation chromatography (GPC) using tetrahydrofuran as a solvent, and it is the value calculated by polystyrene conversion. As the column for measuring the number average molecular weight obtained by polystyrene conversion by GPC, for example, Shodex LF-804 (manufactured by Showa Denko) and the like can be cited.

Examples of the polymer azo compound include a structure in which a plurality of units such as polyalkylene oxide or polydimethylsiloxane are bonded via an azo group. The polymer azo compound having a structure in which a plurality of units such as polyalkylene oxide is bonded via an azo group is preferably a polyethylene oxide structure. Specific examples of the polymer azo compound include 4,4'-azobis (4-cyanovaleric acid) and polyalkylene glycol polycondensate, or 4,4'-azo Condensation polymers of bis(4-cyanovaleric acid) and polydimethylsiloxane with terminal amine groups. Examples of the commercially available polymer azo initiators include VPE-0201, VPE-0401, VPE-0601, VPS-0501, and VPS-1001 (all manufactured by FUJIFILM Wako Pure Chemical). In addition, examples of azo initiators other than polymers include V-65 and V-501 (all manufactured by FUJIFILM Wako Pure Chemical Co., Ltd.) and the like.

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

The lower limit of the content of the radical polymerization initiator is preferably 0.01 part by weight, and the upper limit is preferably 10 parts by weight with respect to 100 parts by weight of the curable resin. By setting the content of the above radical polymerization initiator within this range, the obtained sealing compound for liquid crystal display elements becomes one that suppresses contamination of liquid crystals and is more excellent in storage stability or curability. The more preferable lower limit of the content of the radical polymerization initiator is 0.1 part by weight, and the more preferable upper limit is 5 parts by weight.

The sealing compound for liquid crystal display elements of this invention may contain a thermosetting agent. Examples of the thermosetting agent include organic acid hydrazine, imidazole derivatives, amine compounds, polyphenol compounds, and acid anhydrides. Among them, the organic acid hydrazine is preferably used. The above-mentioned thermosetting agents may be used alone or in combination of two or more.

Examples of the organic acid hydrazide include, for example, sebacic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide, and malonic acid dihydrazide. Examples of the commercially available organic acid hydrazide include organic acid hydrazide manufactured by Otsuka Chemical Co., Ltd., organic acid hydrazide manufactured by Ajinomoto Fine-Techno, and organic acid hydrazide manufactured by Japan Finechem. Examples of the organic acid hydrazide manufactured by Otsuka Chemical Co., Ltd. include SDH and ADH. Examples of the organic acid hydrazide manufactured by the aforementioned Ajinomoto Fine-Techno Company include Amicure VDH, Amicure VDH-J, Amicure UDH, Amicure UDH-J and the like. Examples of the organic acid hydrazide manufactured by Japan Finechem Co., Ltd. include MDH and the like.

The lower limit of the content of the thermosetting agent is preferably 1 part by weight, and the upper limit is preferably 50 parts by weight with respect to 100 parts by weight of the curable resin. By setting the content of the above-mentioned thermosetting agent within this range, it is possible to obtain a more excellent thermosetting property without deteriorating the coating properties, storage stability, and the like of the obtained sealant for liquid crystal display elements. The more preferable upper limit of the content of the above-mentioned thermosetting agent is 30 parts by weight.

The sealant for liquid crystal display elements of the present invention preferably contains a filler in order to increase the viscosity, further improve the adhesion by the stress dispersion effect, improve the linear expansion rate, and improve the moisture resistance of the cured product.

As the above-mentioned filler, an inorganic filler or an organic filler can be used. Examples of the inorganic fillers include silica, talc, glass beads, asbestos, gypsum, diatomaceous earth, bentonite, bentonite, montmorillonite, sericite, activated clay, alumina, zinc oxide, and 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. Examples of the organic filler include polyester fine particles, polyurethane fine particles, ethylene polymer fine particles, acrylic polymer fine particles, and the like. These fillers may be used alone or in combination of two or more.

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 setting the content of the filler to be in this range, it is possible to improve the adhesion and other effects without deteriorating the coating properties and the like. The more preferable lower limit of the content of the filler is 20 parts by weight, and the more preferable upper limit is 60 parts by weight.

The sealing agent for liquid crystal display elements of this invention may contain a silane coupling agent. The above-mentioned silane coupling agent mainly has a role as an adhesion aid for good adhesion of the sealant and the substrate.

As the above-mentioned silane coupling agent, for example, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanide can be suitably used. Acid propyl trimethoxy silane and so on. These silane coupling agents have an excellent effect of improving adhesion to substrates and the like, and chemical bonding with curable resins can suppress the outflow of curable resins into liquid crystals. The above-mentioned silane coupling agent may be used alone or in combination of two or more.

The preferable 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 0.1 part by weight, and the preferable upper limit is 10 parts by weight. With the content of the above-mentioned silane coupling agent being in this range, the effect of suppressing the generation of liquid crystal contamination and improving the adhesion is more excellent. The lower limit of the content of the silane coupling agent is more preferably 0.3 part by weight, and the upper limit is more preferably 5 parts by weight.

The sealing compound for liquid crystal display elements of this invention may contain a light-shielding agent. By containing the above-mentioned light-shielding agent, the sealing agent for liquid crystal display elements of this invention can be used suitably as a light-shielding sealing agent.

Examples of the light-shielding agent include iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, and resin-coated carbon black. Among them, titanium black is preferred.

The above-mentioned titanium black is a substance having a higher transmittance for light in the vicinity of the ultraviolet region, especially light with a wavelength of 370 nm to 450 nm, compared to the average transmittance for light with a wavelength of 300 nm to 800 nm. That is, the above-mentioned titanium black is a light-shielding agent having the property of giving light-shielding properties to the sealing agent for liquid crystal display elements of the present invention by sufficiently shielding the light of the wavelength in the visible light region, and on the other hand, making the wavelength near the ultraviolet region Light penetration. Therefore, by using light with a wavelength (370 nm or more and 450 nm or less) whose transmittance is improved by the titanium black, as the photo radical polymerization initiator, the present invention can be further increased. The photocurability of the sealing compound for liquid crystal display elements of the invention. Furthermore, on the other hand, as the light-shielding agent contained in the sealant for liquid crystal display elements of the present invention, a material with high insulation is preferable, and as the 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, and more preferably 4 or more. The higher the light-shielding property of the titanium black, the better. The OD value of the titanium black does not particularly preferably have an upper limit, but is usually 5 or less.

The above-mentioned titanium black has sufficient effects even if it is not surface-treated, but it can also be used on the surface of which is treated with an organic component such as a coupling agent, or made of silicon oxide, titanium oxide, germanium oxide, aluminum oxide, zirconium oxide, magnesium oxide, etc. Titanium black surface-treated with inorganic components. Among them, those treated with organic components are preferable in terms of further improvement in insulation. In addition, the liquid crystal display element manufactured by using the sealing agent for liquid crystal display elements of the present invention doped with the above titanium black as a light-shielding agent has sufficient light-shielding properties, so there is no leakage of light and a high contrast ratio can be achieved. Liquid crystal display element with excellent image display quality.

Examples of the commercially available titanium black mentioned above include titanium black manufactured by Mitsubishi Materials Co., Ltd., and titanium black manufactured by Ako Chemical Co., Ltd., and the like. Examples of the titanium black manufactured by Mitsubishi Materials include 12S, 13M, 13M-C, 13R-N, and 14M-C. Examples of the titanium black manufactured by Ako Chemical Co., Ltd. include Tilack D and the like.

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

The primary particle diameter of the above-mentioned opacifier is not particularly limited as long as the distance between the substrates of the liquid crystal display element is less than, the lower limit is preferably 1 nm, and the upper limit is preferably 5000 nm. By setting the primary particle diameter of the above-mentioned light-shielding agent within this range, it is possible to produce a more excellent light-shielding property without deteriorating the coating properties of the obtained sealant for liquid crystal display elements. The preferred lower limit of the primary particle size of the above-mentioned opacifier is 5 nm, the more preferred upper limit is 200 nm, the further preferred lower limit is 10 nm, and the further preferred upper limit is 100 nm. In addition, the primary particle diameter of the said sunscreen agent can be measured using NICOMP 380ZLS (made by PARTICLE SIZING SYSTEMS) to disperse the said sunscreen agent in a solvent (water, organic solvent, etc.).

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. By setting the content of the light-shielding agent within this range, it is possible to exert more excellent light-shielding properties without greatly reducing the adhesiveness, strength after curing, and drawability of the obtained sealant for liquid crystal display elements. The lower limit of the content of the above-mentioned opacifier is more preferably 10 parts by weight, the more preferable upper limit is 70 parts by weight, the more preferable lower limit is 30 parts by weight, and the more preferable upper limit is 60 parts by weight.

The sealing agent for liquid crystal display elements of the present invention may further contain additives such as a stress relaxation agent, a reactive diluent, a shaker, a spacer, a hardening accelerator, a defoaming agent, a leveling agent, a polymerization inhibitor and the like as necessary.

Examples of the method for producing the sealant for liquid crystal display elements of the present invention include, for example, a mixer such as a homogenizer, a homomixer, a universal mixer, a planetary mixer, a kneader, and a three-roll kneader. , A method of mixing radical polymerization initiators and additives such as silane coupling agent added as needed.

By blending conductive fine particles in the sealant for liquid crystal display elements of the present invention, a vertical conduction material can be manufactured. Such a top-to-bottom conductive 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.

As the conductive fine particles, a metal ball, a conductive metal layer formed on the surface of the resin fine particles, or the like can be used. Among them, those having a conductive metal layer formed on the surface of the resin microparticles can be electrically connected by the excellent elasticity of the resin microparticles without damaging the transparent substrate or the like, which is preferable.

A liquid crystal display element using the sealing compound for liquid crystal display elements of the present invention or the upper and lower conduction materials of the present invention is also one of the present invention. The sealant for a liquid crystal display element of the present invention is excellent in low liquid crystal contamination even when the liquid crystal display element of the present invention is formed by using highly polarized liquid crystal. Specific examples of the highly polarized liquid crystal include those using liquid crystal molecules having polar groups. Examples of the polar group include a fluorine group, a chlorine group, and a cyano group.

In addition, as the liquid crystal display device of the present invention, a liquid crystal display device with a narrow edge design is preferred. Specifically, the width of the frame portion around the liquid crystal display portion is preferably 2 mm or less. Furthermore, the coating width of the sealing compound for liquid crystal display elements of this invention when manufacturing the liquid crystal display element of this invention is preferably 1 mm or less.

The sealing agent for liquid crystal display elements of this invention can be suitably used for the manufacture of a liquid crystal display element by the liquid crystal drop processing method. As a method of manufacturing the liquid crystal display element of the present invention by the liquid crystal drop processing method, for example, the following methods can be cited. First, a step of forming a frame-shaped seal pattern by applying the sealant for liquid crystal display elements of the present invention to a substrate by screen printing, dispenser coating, or the like. Then, the following steps are carried out: droplets of liquid crystal are applied dropwise to the entire surface of the frame of the sealing pattern in a state where the sealing agent for liquid crystal display elements of the present invention is uncured, and the other substrate is immediately overlapped. Thereafter, a liquid crystal display element can be obtained by performing a step of photo-curing the sealant by irradiating the seal pattern portion with light such as ultraviolet light. In addition to the step of photo-curing the sealant, a step of heating the sealant to harden it is also performed. [Effect of invention]

According to the present invention, it is possible to provide a sealant for liquid crystal display elements which is excellent in adhesiveness, moisture permeability resistance, and low liquid crystal contamination. 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 sealant for a liquid crystal display element.

Hereinafter, the present invention will be described in more detail by citing examples, but the present invention is not limited to these examples.

(Curing resin A) bisphenol F dioxypropylene ether (manufactured by Mitsubishi Chemical Corporation, "EXA-830CRP") 780 parts by weight, bisphenol F 250 parts by weight, and methyl isobutyl ketone as a solvent are added to the reaction flask 250 parts by weight and 0.5 parts by weight of triphenylphosphine as a catalyst were stirred at 120°C for 8 hours using a heating bag to react. To the resulting solution, 216 parts by weight of acrylic acid, 2 parts by weight of triethylamine as a reaction catalyst, and 2 parts by weight of p-methoxyphenol as a polymerization inhibitor were added, and the mixture was stirred at 90°C for 5 hours to react. The obtained reactant was filtered by a column to obtain curable resin A. From ¹ H-NMR and ¹³ C-NMR, it was confirmed that the curable resin A contained the compound represented by the above formula (1) (R ¹ is a hydrogen atom, R ² and R ³ were represented by the formula (2-1) Group (R ⁴ is methylene, p is 0), n is 1) as the main component. The weight average molecular weight of the obtained curable resin A was 1100, and the valence of the hydrogen-bonding functional group (hydroxyl group) was 0.0036 mol/g.

(Curable resin B) 550 parts by weight of resorcinol dioxypropylene ether, 136 parts by weight of resorcinol (manufactured by Tokyo Chemical Industry Co., Ltd.), and 250 parts by weight of methyl isobutyl ketone as a solvent were added to the reaction flask 5. As a catalyst, 0.5 parts by weight of triphenylphosphine, use a heating bag to stir at 120°C for 8 hours to make it react. To the resulting solution, 216 parts by weight of acrylic acid, 2 parts by weight of triethylamine as a reaction catalyst, and 2 parts by weight of p-methoxyphenol as a polymerization inhibitor were added, and the mixture was stirred at 90°C for 5 hours to react. The obtained reactant was filtered by a column to obtain curable resin B. From ¹ H-NMR and ¹³ C-NMR, it was confirmed that the curable resin B contained the compound represented by the above formula (1) (R ¹ is a hydrogen atom, R ² and R ³ were represented by the formula (2-2) The basis (q is 0), n is 1) as the main component. The weight average molecular weight of the obtained curable resin B was 700, and the valence of the hydrogen-bonding functional group (hydroxyl group) was 0.0057 mol/g.

(Curing resin C) 780 parts by weight of bisphenol F propylene oxide ether, 136 parts by weight of resorcinol, 250 parts by weight of methyl isobutyl ketone as a solvent, and triphenylphosphine as a catalyst were added to the reaction flask 0.5 parts by weight was stirred at 120°C for 8 hours using a heating bag to react. To the resulting solution, 216 parts by weight of acrylic acid, 2 parts by weight of triethylamine as a reaction catalyst, and 2 parts by weight of p-methoxyphenol as a polymerization inhibitor were added, and the mixture was stirred at 90°C for 5 hours to react. The obtained reactant was filtered by a column to obtain curable resin C. From ¹ H-NMR and ¹³ C-NMR, it was confirmed that the curable resin C contained the compound represented by the above formula (1) (R ¹ is a hydrogen atom, and R ² was a group represented by the formula (2-1) (R ⁴ is a methylene group, p is 0), R ³ is a group represented by formula (2-2) (q is 0), and n is 1) as a main component. The weight average molecular weight of the obtained curable resin C was 1100, and the valence of the hydrogen-bonding functional group (hydroxyl group) was 0.0036 mol/g.

(Curing resin D) 780 parts by weight of bisphenol F propylene oxide ether, 250 parts by weight of bisphenol F, 250 parts by weight of methyl isobutyl ketone as a solvent, and 0.5 parts of triphenylphosphine as a catalyst are added to the reaction flask The parts by weight were stirred at 120°C for 8 hours using a heating bag to react. To the resulting solution, 90 parts by weight of acrylic acid, 2 parts by weight of triethylamine as a reaction catalyst, and 2 parts by weight of p-methoxyphenol as a polymerization inhibitor were added, and stirred at 90°C for 5 hours to react. The obtained reactant was filtered using a column to obtain curable resin D. From ¹ H-NMR and ¹³ C-NMR, it was confirmed that the curable resin D contained the compound represented by the above formula (3) (R ⁵ is a hydrogen atom, R ⁶ and R ⁷ were represented by the formula (4-1) Group (R ⁸ is methylene, p is 0), m is 1) as the main component. The weight average molecular weight of the obtained curable resin D was 900, and the valence of the hydrogen-bonding functional group (hydroxyl group) was 0.0033 mol/g.

(Curing resin E) 780 parts by weight of bisphenol F propylene oxide ether, 136 parts by weight of resorcinol, 250 parts by weight of methyl isobutyl ketone as a solvent, and triphenylphosphine as a catalyst were added to the reaction flask 0.5 parts by weight was stirred at 120°C for 8 hours using a heating bag to react. To the resulting solution, 90 parts by weight of acrylic acid, 2 parts by weight of triethylamine as a reaction catalyst, and 2 parts by weight of p-methoxyphenol as a polymerization inhibitor were added, and stirred at 90°C for 5 hours to react. The obtained reactant was filtered using a column to obtain curable resin E. From ¹ H-NMR and ¹³ C-NMR, it was confirmed that the curable resin E contained the compound represented by the above formula (3) (R ⁵ is a hydrogen atom, and R ⁶ was a group represented by the formula (4-1) (R ⁸ is a methylene group, p is 0), R ⁷ is a group represented by the formula (4-2) (q is 0), and m is 1) as a main component. The weight average molecular weight of the obtained curable resin E was 800, and the valence of the hydrogen-bonding functional group (hydroxyl group) was 0.0038 mol/g.

(Curable resin F) As the curable resin F, ethylene oxide-modified bisphenol A dimethacrylate (manufactured by Hitachi Chemical Co., Ltd., "FANCRYL FA-321M", number of aromatic rings in 1 molecule is 2, weight average molecular weight 900, no Hydrogen bonding functional group).

(Curable resin G) Add 550 parts by weight of resorcinol dioxypropylene ether, 216 parts by weight of acrylic acid, 2 parts by weight of triethylamine as a reaction catalyst, and p-methoxyphenol 2 as a polymerization inhibitor in the reaction flask The parts by weight were stirred at 90°C for 5 hours to react. The obtained reactant was filtered by a column to obtain curable resin G. From ¹ H-NMR and ¹³ C-NMR, it was confirmed that the curable resin G contained a group corresponding to R ¹ in the above formula (1) being a hydrogen atom, and R ² being a group represented by formula (2-2) (q is 0) The compound with n being 0 is the main component. The weight average molecular weight of the obtained curable resin G was 400, and the valence of the hydrogen-bonding functional group (hydroxyl group) was 0.0050 mol/g.

(Curing resin H) 780 parts by weight of bisphenol F propylene oxide ether, 216 parts by weight of acrylic acid, 2 parts by weight of triethylamine as a reaction catalyst, and 2 parts by weight of p-methoxyphenol as a polymerization inhibitor were added to the reaction flask The reaction mixture was stirred at 90°C for 5 hours. The obtained reactant was filtered by a column to obtain curable resin H. From ¹ H-NMR and ¹³ C-NMR, it was confirmed that the curable resin H contained a group corresponding to R ⁵ in the above formula (3) being a hydrogen atom, and R ⁶ being a group represented by the formula (4-1) (R ⁸ Compounds that are methylene and p is 0) and m are 0 are the main components. The weight average molecular weight of the obtained curable resin H was 400, and the valence of the hydrogen-bonding functional group (hydroxyl group) was 0.0025 mol/g.

(Curing resin I) In a reaction flask, 745 parts by weight of 4,4'-bis(glycidoxypropyl)bisphenol, 233 parts by weight of 4,4'-dihydroxybiphenyl, and methyl isocyanate as a solvent 250 parts by weight of butyl ketone and 0.5 parts by weight of triphenylphosphine as a catalyst were stirred at 120°C for 8 hours using a heating bag to react. The obtained reactant was filtered by a column to obtain curable resin I. From ¹ H-NMR and ¹³ C-NMR, it was confirmed that the curable resin I contained the compound represented by the following formula (5) as a main component. The weight average molecular weight of the obtained curable resin I was 800, and the valence of the hydrogen-bonding functional group (hydroxyl group) was 0.0025 mol/g.

(Curable resin J) 550 parts by weight of resorcinol dioxypropylene ether, 148 parts by weight of 1,6-hexanediol, 250 parts by weight of methyl isobutyl ketone as a solvent, and a catalyst were added to the reaction flask 0.5 parts by weight of triphenylphosphine was stirred at 120°C for 8 hours using a heating bag to make it react. To the resulting solution, 216 parts by weight of acrylic acid, 2 parts by weight of triethylamine as a reaction catalyst, and 2 parts by weight of p-methoxyphenol as a polymerization inhibitor were added, and the mixture was stirred at 90°C for 5 hours to react. The obtained reactant was filtered by a column to obtain a curable resin J. From ¹ H-NMR and ¹³ C-NMR, it was confirmed that the curable resin J contained the compound represented by the above formula (1) (R ¹ is a hydrogen atom, and R ² was a group represented by the formula (2-2) (q Is 0), R ³ is a cyclohexane group, and n is 1) as a main component. The weight average molecular weight of the obtained curable resin J was 800, and the valence of the hydrogen-bonding functional group (hydroxyl group) was 0.0050 mol/g.

(Examples 1 to 5, Comparative Examples 1 to 5) According to the blending ratio described in Table 1, each material was stirred using a planetary mixer (Thinky Corporation, "Defoaming Taro"), and then evenly mixed using a ceramic three-roller mixer to prepare Example 1 Sealants for liquid crystal display elements of ~5 and Comparative Examples 1~5.

<Evaluation> The following evaluation was performed about each sealing compound for liquid crystal display elements obtained in the Example and the comparative example. The results are shown in Table 1.

(Adhesiveness) 1 part by weight of spacer particles (manufactured by Sekisui Chemical Co., Ltd., "Micropearl SP-2050") with an average particle diameter of 5 μm is uniformly dispersed in each liquid crystal obtained in Examples and Comparative Examples using a planetary mixer 100 parts by weight of a sealant for display elements. Take a very small amount of the sealant in which the spacer particles are dispersed to the center of the glass substrate (20 mm × 50 mm × thickness 0.7 mm), and overlay the same type of glass substrate on it. The sealant for liquid crystal display elements was pressed and spread, and after irradiating 3000 mJ/cm ² of ultraviolet rays with a metal halide lamp, it was heated at 120° C. for 1 hour to harden the sealant to obtain a subsequent test piece. With respect to the obtained adhesive test piece, the adhesive strength was measured using a tensiometer. The case where the following strength is 3.5 kg/cm ² or more is set to "◎", the case where 3.0 kg/cm ² or more and less than 3.5 kg/cm ² is set to "○", and the case where 2.5 kg/cm ² or more is not set The case where it reached 3.0 kg/cm ² was set to “△”, and the case where the adhesion strength did not reach 2.5 kg/cm ² was set to “×”, thereby evaluating the adhesion.

(Moisture-proof property) The sealing compound for each liquid crystal display element obtained in the Example and the comparative example was apply|coated to the smooth release film so that thickness might become 200-300 micrometers using a coater. Next, after irradiating 3000 mJ/cm ² of ultraviolet rays with a metal halogen lamp, the sealant was cured by heating at 120° C. for 1 hour to obtain a film for measuring moisture permeability. A cup for moisture permeability test is prepared by the method of moisture permeability test method (cup method) according to JIS Z 0208, the obtained membrane for moisture permeability measurement is installed, and it is put into a constant temperature of 80°C and 90%RH The moisture permeability is measured in a constant humidity oven. Set the value of the obtained moisture permeability to less than 60 g/m ² ･24hr, and set it to “○”, and set it to 61 g/m ² ･24hr or more and less than 80 g/m ² ･24hr. "△", the case where 81 g/m ² ･24hr or more was set as "×", and the moisture permeability was evaluated.

(Low liquid crystal contamination) Using a dispenser, the sealant for each liquid crystal display element obtained in Examples and Comparative Examples was applied to two pieces of rubbed alignment film and transparent in a square frame One of the substrates of the electrodes forms a sealing pattern. The sealant for liquid crystal display elements was dripped inside the formed seal pattern. Next, droplets of liquid crystals containing "liquid crystal molecules with cyano groups as polar groups" (manufactured by Tokyo Chemical Industry Co., Ltd., "4-pentyl-4-biphenylnitrile") are added dropwise and applied to the transparent electrode The entire surface of the sealant of the substrate overlaps with another substrate in a vacuum. After the vacuum is released, a metal halogen lamp is used to irradiate 3000 mJ/cm ² of ultraviolet rays on the sealed portion of the outer frame. At this time, masking is performed so that the dropped sealant for liquid crystal display elements is not irradiated with ultraviolet rays. Then, it heated at 120 degreeC for 1 hour, hardened the sealing compound for liquid crystal display elements, and obtained the liquid crystal display element. For the obtained liquid crystal display element, the liquid crystal contamination property was judged based on the unevenness around the dropped sealant. The case where there is no unevenness at all is set to "◎", the case where the unevenness is not obvious is set to "○", the case where there is little unevenness is set to "△", and the case where there is much unevenness is set to "×" To evaluate the low liquid crystal contamination.

[產業上之可利用性][Table 1]

[Industry availability]

According to the present invention, it is possible to provide a sealant for liquid crystal display elements which is excellent in adhesiveness, moisture permeability resistance, and low liquid crystal contamination. 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 sealant for a liquid crystal display element.

no

no

Claims (6)

A sealant for liquid crystal display elements, which contains a hardening resin and a radical polymerization initiator, The above-mentioned curable resin contains: (A) (meth)acrylic compound whose hydrogen-bonding functional group has a valence of 0.0030 mol/g or more, a molecular weight of 500 or more and 1200 or less, does not have an epoxy group, and is in 1 molecule Have more than 3 aromatic rings; and/or (B) part (meth)acrylic modified epoxy resin, the valence of its hydrogen-bonding functional group is 0.0030 mol/g or more, and the molecular weight is 500 or more and 1200 or less, There are three or more aromatic rings in one molecule. The sealing compound for a liquid crystal display element according to claim 1, which contains the compound represented by the following formula (1) as the (A) (meth)acrylic compound, and the hydrogen of the (A) (meth)acrylic compound The valence of the bonding functional group is 0.0030 mol/g or more, the molecular weight is 500 or more and 1200 or less, does not have an epoxy group, and has 3 or more aromatic rings in one molecule,

In formula (1), R ¹ each independently represents a hydrogen atom or a methyl group, R ² represents a divalent aromatic group represented by the following formula (2-1) or (2-2), and R ³ represents carbon number 2 A divalent aliphatic group of above 15 and below or a divalent aromatic group which is the same as or different from R ² , n is 1 or more and 3 or less,

In formula (2-1), R ⁴ represents a linear or branched alkylene group having carbon number of 1 or more and 4 or less, and p is 0 or more and 3 or less; in formula (2-2), q is 0 or more And 3 or less; in formulas (2-1) and (2-2), * represents the bonding position; the aromatic rings in formulas (2-1) and (2-2) are all or part of the hydrogen atoms can also be replace. The sealant for a liquid crystal display element according to claim 1 or 2, which contains the compound represented by the following formula (3) as the (B) part (meth)acrylic modified epoxy resin, the (B) part The (meth)acrylic modified epoxy resin has a hydrogen bonding functional group with a valence of 0.0030 mol/g or more, a molecular weight of 500 or more and 1200 or less, and three or more aromatic rings in one molecule.

In formula (3), R ⁵ represents a hydrogen atom or a methyl group, R ⁶ represents a divalent aromatic group represented by the following formulas (4-1) and (4-2), and R ⁷ represents a carbon number of 1 or more and 20 The following divalent aliphatic group or the same or different divalent aromatic group as R ⁶ , m is 1 or more and 3 or less,

In formula (4-1), R ⁸ represents a linear or branched alkylene group having a carbon number of 1 or more and 4 or less, and p is 0 or more and 3 or less; in formula (4-2), q is 0 or more And 3 or less; in formulas (4-1) and (4-2), * represents the bonding position; the aromatic rings in formulas (4-1) and (4-2) are all or part of the hydrogen atoms can also be replace. A sealant for a liquid crystal display element, comprising a curable resin and a radical polymerization initiator, the curable resin containing a compound represented by the following formula (1) and having 3 or more aromatic rings in one molecule, and/or the following The compound represented by the formula (3) and having 3 or more aromatic rings in one molecule,

In formula (1), R ¹ each independently represents a hydrogen atom or a methyl group, R ² represents a divalent aromatic group represented by the following formula (2-1) or (2-2), and R ³ represents carbon number 2 A divalent aliphatic group of above 15 and below or a divalent aromatic group which is the same as or different from R ² , n is 1 or more and 3 or less,

In formula (2-1), R ⁴ represents a linear or branched alkylene group having carbon number of 1 or more and 4 or less, and p is 0 or more and 3 or less; in formula (2-2), q is 0 or more And 3 or less; in formulas (2-1) and (2-2), * represents the bonding position; the aromatic rings in formulas (2-1) and (2-2) are all or part of the hydrogen atoms can also be replace,

In formula (3), R ⁵ represents a hydrogen atom or a methyl group, R ⁶ represents a divalent aromatic group represented by the following formulas (4-1) and (4-2), and R ⁷ represents a carbon number of 1 or more and 20 The following divalent aliphatic group or the same or different divalent aromatic group as R ⁶ , m is 1 or more and 3 or less,

In formula (4-1), R ⁸ represents a linear or branched alkylene group having a carbon number of 1 or more and 4 or less, and p is 0 or more and 3 or less; in formula (4-2), q is 0 or more And 3 or less; in formulas (4-1) and (4-2), * represents the bonding position; the aromatic rings in formulas (4-1) and (4-2) are all or part of the hydrogen atoms can also be replace. A top-to-bottom conductive material containing the sealing agent for liquid crystal display elements described in claim 1, 2, 3, or 4 and conductive fine particles. A liquid crystal display element is obtained by using the sealing compound for liquid crystal display elements described in claim 1, 2, 3, or 4 or the top and bottom conduction materials described in claim 5.