TWI525181B - Liquid crystal drop method sealant, upper and lower conductive material and liquid crystal display element - Google Patents

Description

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

The present invention relates to a sealing compound for a liquid crystal dropping method which is excellent in photocurability and can suppress liquid crystal contamination. Moreover, the present invention relates to an upper and lower conductive material and a liquid crystal display element which are produced by using the sealing compound for liquid crystal dropping methods.

In recent years, as a method of manufacturing a liquid crystal display element such as a liquid crystal display unit, as disclosed in Patent Document 1 and Patent Document 2, from the viewpoints of shortening the station time (Tact Time) and optimizing the amount of liquid crystal used. A liquid crystal dropping method called a dropping method using a curing agent containing a curable resin, a photopolymerization initiator, and a thermosetting agent.

In the dropping method, first, a rectangular sealing pattern is formed by dispensing onto one of two transparent substrates with electrodes. Next, the liquid crystal droplets are dropped onto the entire surface of the transparent substrate in a state where the sealant is not cured, and the other transparent substrate is immediately superposed, and the sealing portion is temporarily hardened by irradiation with light such as ultraviolet rays. Thereafter, it is heated and subjected to main hardening at the time of liquid crystal annealing to produce a liquid crystal display element. When the substrate is bonded under reduced pressure, the liquid crystal display element can be manufactured with extremely high efficiency. At present, the dropping method is becoming the mainstream of the manufacturing method of the liquid crystal display element.

In addition, various mobile devices equipped with liquid crystal panels, such as mobile phones and portable game machines, are becoming popular, and the miniaturization of devices is the most demanding issue. As a small device The method of forming the film includes a narrow edge of the liquid crystal display unit. For example, the position of the sealing portion is placed under a black matrix (hereinafter also referred to as a narrow edge design).

However, since the sealant is disposed directly under the black matrix in the narrow edge design, if the dropping method is performed, the light irradiated by the sealant is blocked by light, and the light cannot reach the inside of the sealant to cause hardening. Insufficient problem. If the curing of the sealant is insufficient, the uncured sealant component is eluted into the liquid crystal to cause liquid crystal contamination.

Patent Document 3 discloses a photopolymerization initiator which is formulated with a high sensitivity in a sealant in order to improve the hardenability of the light-shielding portion. However, it is not possible to sufficiently photoharden the sealant of the light-shielding portion by merely arranging the high-sensitivity photopolymerization initiator. Further, Patent Document 4 discloses that a high-sensitivity photopolymerization initiator is composed of 9-oxosulfur The sensitizer composed of the compounds is combined and formulated. However, since such a sensitizer is used, there is a problem that liquid crystal contamination caused by the sealant is liable to occur.

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

Patent Document 2: International Publication No. 02/092718

Patent Document 3: International Publication No. 2011/002028

Patent Document 4: Japanese Laid-Open Patent Publication No. 2010-286640

An object of the present invention is to provide a sealing compound for a liquid crystal dropping method which is excellent in photocurability and can suppress liquid crystal contamination. Moreover, an object of the present invention is to provide an upper and lower conductive material and a liquid crystal display element using the sealing compound for liquid crystal dropping methods.

The present invention relates to a sealing agent for a liquid crystal dropping method, comprising a curable resin and a photopolymerization initiator, and the photopolymerization initiator contains a compound represented by the following formula (1) and an oxime ester compound, and the formula ( 1) The content ratio of the compound represented by the oxime ester compound is represented by the formula (1) by weight ratio: oxime ester compound = 1:3 to 1:100.

In the formula (1), R ¹ and R ² represent hydrogen or a -NR ³ ₂ group, and at least one of R ¹ and R ² is a -NR ³ ₂ group. R ³ represents hydrogen or an alkyl group having 1 to 4 carbon atoms. Each R ³ may be the same or different.

The present invention 1 is described in detail below.

The present inventors have found that a compound having a specific structure and an oxime ester compound can be used in combination as a photopolymerization initiator in a specific content ratio, whereby a liquid crystal dropping method which is excellent in photocurability and can suppress liquid crystal contamination can be obtained. The sealant, thereby completing the present invention 1.

The sealing agent for liquid crystal dropping methods of the present invention 1 contains a photopolymerization initiator. The photopolymerization initiator contains the compound represented by the above formula (1) and an oxime ester compound. When the compound represented by the above formula (1) and the oxime ester compound are used in combination, the sealing compound for a liquid crystal dropping method of the present invention has high sensitivity and excellent photocurability, and can suppress liquid crystal contamination. The compound represented by the above formula (1) functions not only as a photopolymerization initiator but also as a sensitizer.

In the formula (1), at least one of R ¹ and R ² is a -NR ³ ₂ group, and R ³ represents hydrogen or an alkyl group having 1 to 4 carbon atoms.

In the case where R ³ is an alkyl group, the alkyl group represented by the above R ³ is preferably a methyl group or an ethyl group.

The compound represented by the above formula (1) is preferably selected from the group consisting of 4,4'-bis(diethylamino)benzophenone and 4,4'-bis(dimethylamino)benzophenone, and At least one of the group consisting of 4-(dimethylamino)benzophenone.

The above-mentioned oxime ester-based compound is preferably 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzamide) in terms of high sensitivity and excellent photocurability. At least one of the compounds represented by the following formula (2) is more preferably a compound represented by the following formula (2) from the viewpoint of suppressing liquid crystal contamination.

In the formula (2), X represents an alkylene group having 1 to 6 carbon atoms.

In the above formula (2), examples of the alkylene group represented by X include a methylene group, an exoethyl group, a propyl group, an isopropyl group, an exobutyl group, a 1-methyl group, and a 1-ethyl group. Base ethyl, pentyl, hexyl and the like. Among them, a methylene group and an ethyl group are preferred.

In order to prevent liquid crystal contamination caused by the sealing compound for liquid crystal dropping methods, it is necessary to improve not only the photocurability of the sealing agent but also the ionic substance which causes the abnormality of the liquid crystal alignment to be eluted into the liquid crystal. Since the compound represented by the above formula (1) has an amine group in the molecule, if it is contained in an excessive amount in the sealant, liquid crystal contamination causing ionicity may occur. because Therefore, the content of the compound represented by the above formula (1) must be appropriately adjusted.

The content ratio of the compound represented by the above formula (1) to the above oxime ester compound is a compound represented by the formula (1) in a weight ratio: an oxime ester compound = 1:3 to 1:100. When the content ratio of the compound represented by the above formula (1) to the above-described oxime ester-based compound is in this range, the obtained sealing compound for liquid crystal dropping method is excellent in high sensitivity and photocurability, and can suppress liquid crystal contamination. The content ratio of the compound represented by the above formula (1) to the above oxime ester compound is preferably a compound represented by the formula (1): an oxime ester compound = 1:4 to 1:75, more preferably 1:5. ~1:50.

Regarding the content of the above photopolymerization initiator, relative to the weight of the curable resin 100 The lower limit is preferably 0.1 part by weight, and preferably the upper limit is 10 parts by weight. When the content of the photopolymerization initiator is less than 0.1 part by weight, the photopolymerization of the obtained liquid crystal dropping method sealant may not be sufficiently performed. When the content of the photopolymerization initiator is more than 10 parts by weight, a large amount of unreacted photopolymerization initiator remains, and the weather resistance of the obtained liquid crystal dropping method sealant is deteriorated, or storage stability is poor. Or, in the case of liquid crystal contamination. A more preferred lower limit of the content of the photopolymerization initiator is 0.2 parts by weight, and a more preferred upper limit is 8 parts by weight.

The sealing compound for liquid crystal dropping methods of the present invention 1 contains a curable resin.

The curable resin is preferably a resin having at least one (meth) acrylonitrile group in one molecule (hereinafter also referred to as "(meth)acrylic resin"). In terms of high reactivity, the (meth)acrylic resin preferably has two or more (meth)acrylonium groups in one molecule.

In the present specification, the above "(meth)acryloyl group means propylene fluorenyl group or methacryl fluorenyl group, and the above "(meth)acrylic acid" means acrylic acid or methacrylic acid.

Examples of the (meth)acrylic resin include an ester compound obtained by reacting (meth)acrylic acid with a compound having a hydroxyl group, and (meth)acrylic acid and a ring. An epoxy (meth) acrylate obtained by reacting an oxygen compound, an amine (meth) acrylate obtained by reacting an isocyanate with a (meth)acrylic acid derivative having a hydroxyl group, or the like. Among them, epoxy (meth) acrylate is preferred from the viewpoint of easiness of synthesis and the like.

In the present specification, the above "(meth) acrylate" means acrylate or methacrylate, and the above "epoxy (meth) acrylate" means that all epoxy groups in the epoxy resin are A compound obtained by reacting (meth)acrylic acid.

As the monofunctional one of the above ester compounds, for example, (meth) propylene is exemplified 2-hydroxyethyl acid, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, isobutyl (meth)acrylate, ( Tert-butyl methacrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isodecyl (meth) acrylate, (meth) acrylate ring Hexyl ester, 2-methoxyethyl (meth)acrylate, methoxyethylene glycol (meth) acrylate, 2-ethoxyethyl (meth) acrylate, tetrahydroanthracene (meth) acrylate Ester, benzyl (meth) acrylate, ethyl carbitol (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxy diethylene glycol (meth) acrylate, phenoxy Polyethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, (meth) acrylate 2, 2, 3,3-tetrafluoropropyl ester, (meth)acrylic acid 1H, 1H, 5H-octafluoropentyl ester, quinone imine (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate , (meth) propyl acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ( Base) n-octyl acrylate, isodecyl (meth)acrylate, isomyristyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate Ester, dicyclopentenyl (meth)acrylate, isodecyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, succinic acid 2 -(Meth)propenyloxyethyl ester, 2-(methyl)propenyloxyethyl hexahydrophthalate, 2-(methyl) Propylene methoxyethyl 2-hydroxypropyl phthalate, glycidyl (meth) acrylate, 2-(methyl) propylene methoxyethyl phosphate, and the like.

Further, as the bifunctional one of the above ester compounds, for example, 1,4- Butanediol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di Methyl) acrylate, 1,10-nonanediol di(meth) acrylate, 2-n-butyl-2-ethyl-1,3-propanediol di(meth) acrylate, dipropylene glycol di(a) Acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol (meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene Alcohol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene oxide addition bisphenol A di(meth)acrylate, ethylene oxide addition bisphenol A di(methyl) Acrylate, ethylene oxide addition bisphenol F di(meth) acrylate, dimethylol dicyclopentadienyl di(meth) acrylate, 1,3-butanediol di(methyl) Acrylate, neopentyl glycol di(meth)acrylate, ethylene oxide modified di(meth)acrylate isocyanate, 2-hydroxy-3-(methyl)(meth)acrylate Propylene methoxypropyl ester, carbonate diol di(meth) acrylate, polyether diol di(meth) acrylate, poly Glycol di (meth) acrylate, polycaprolactone glycol di (meth) acrylate, polybutadiene diol di (meth) acrylate.

Further, as the trifunctional or higher one of the above ester compounds, for example, new Pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, propylene oxide addition trimethylolpropane tri(meth)acrylate, ethylene oxide addition trishydroxyl Methylpropane tri(meth)acrylate, caprolactone modified trimethylolpropane tri(meth)acrylate, ethylene oxide addition isocyanuric acid tris(meth)acrylate, two new Pentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, di-trimethylolpropane tetra (meth) acrylate, neopentyl alcohol tetra (meth) acrylate , triglyceride (meth) acrylate, propylene oxide addition glycerol tri (meth) acrylate, phosphoric acid tris (A) Base) propylene methoxyethyl ester and the like.

Examples of the epoxy (meth) acrylate include those obtained by reacting an epoxy resin with (meth)acrylic acid in the presence of a basic catalyst according to a usual method.

Examples of the epoxy resin to be used as a raw material for synthesizing the above epoxy (meth) acrylate include bisphenol A type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type epoxy resin, and 2 , 2'-diallyl bisphenol A epoxy resin, hydrogenated bisphenol epoxy resin, propylene oxide addition bisphenol A epoxy resin, resorcinol epoxy resin, biphenyl ring Oxygen resin, thioether type epoxy resin, diphenyl ether type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, phenol novolak type epoxy resin, o-cresol novolac type epoxy Resin, dicyclopentadiene novolac type epoxy resin, biphenyl novolac type epoxy resin, naphthol novolac type epoxy resin, epoxy propylamine type epoxy resin, alkyl polyol type epoxy resin, rubber Modified epoxy resin, glycidyl ester compound, and the like.

Examples of the bisphenol A type epoxy resin include Epikote 828EL, Epikote 1004 (all manufactured by Mitsubishi Chemical Corporation), and Epiclon 850 (manufactured by DIC Corporation).

For example, Epikote 806 and Epikote 4004 (all manufactured by Mitsubishi Chemical Corporation) and the like are mentioned as a commercial product of the bisphenol F-type epoxy resin.

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

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

As a commercially available one of the above hydrogenated bisphenol type epoxy resins, for example, Epiclon can be cited. EXA7015 (manufactured by DIC Corporation) and the like.

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

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

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

For example, YSLV-50TE (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.) or the like can be mentioned as a commercially available one of the above-mentioned thioether type epoxy resins.

For example, YSLV-80DE (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.) and the like can be cited as a commercially available one of the above-mentioned diphenyl ether type epoxy resins.

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

Examples of the commercially available ones of the naphthalene type epoxy resins include Epiclon HP 4032 and Epiclon EXA-4700 (all manufactured by DIC Corporation).

As a commercial item of the above-mentioned phenol novolak type epoxy resin, Epiclon N-770 (made by the DIC company) etc. are mentioned, for example.

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

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

As a commercially available one of the above-mentioned biphenol novolak type epoxy resins, for example, NC-3000P can be cited. (made by Nippon Kayaku Co., Ltd.), etc.

As a commercial item of the above-mentioned naphthol novolac type epoxy resin, ESN-165S (made by Nippon Steel & Sumitomo Chemical Co., Ltd.), etc. are mentioned, for example.

For example, Epikote 630 (manufactured by Mitsubishi Chemical Corporation), Epiclon 430 (manufactured by DIC Corporation), TETRAD-X (manufactured by Mitsubishi Gas Chemical Co., Ltd.), and the like are mentioned as a commercially available one.

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

For example, YR-450, YR-207 (all manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), Epolead PB (manufactured by Daicel Chemical Industry Co., Ltd.), and the like are mentioned as a commercially available one of the rubber-modified epoxy resins.

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

For example, YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), XAC4151 (made by Asahi Kasei Co., Ltd.), Epikote 1031, and Epikote 1032 are mentioned as the other commercially available ones. (all manufactured by Mitsubishi Chemical Corporation), EXA-7120 (manufactured by DIC Corporation), TEPIC (manufactured by Nissan Chemical Co., Ltd.), and the like.

As described above, the above epoxy (meth) acrylate can be epoxy by a usual method. The resin is produced by reacting (meth)acrylic acid in the presence of a basic catalyst. Specifically, for example, 360 parts by weight of a resorcinol type epoxy resin (EX-201, manufactured by Nagase ChemteX Co., Ltd.) and 2 parts by weight of a p-methoxyphenol as a polymerization inhibitor are supplied while supplying air under reflux. , Resorcinol type epoxy acrylate was obtained by reacting 2 parts by weight of triethylamine as a reaction catalyst with 210 parts by weight of acrylic acid at 90 ° C for 5 hours.

As a commercial one of the above-mentioned epoxy (meth)acrylate, for example, the following are mentioned: EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRYL3703, EBECRYL3800, EBECRYL6040, EBECRYL LDX63182 (all manufactured by Daicel-Allnex), EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, EMA-1020 (both manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), Epoxy Ester M-600A, Epoxy Ester 40EM, Epoxy Ester 70PA, Epoxy Ester 200PA, Epoxy Ester 80MFA, Epoxy Ester 3002M, Epoxy Ester 3002A, Epoxy Ester 1600A, Epoxy Ester 3000M, Epoxy Ester 3000A, Epoxy Ester 200EA, Epoxy Ester 400EA (all manufactured by Kyoei Chemical Co., Ltd.), Denacol Acrylate DA-141, Denacol Acrylate DA-314, Denacol Acrylate DA-911 (both Nagase chemteX) Company manufacturing) and so on.

As described above, by isocyanate and (meth)acrylic acid having a hydroxyl group The (meth)acrylic acid amide obtained by the reaction, for example, can make the (meth)acrylic acid derivative having a hydroxyl group 2 equivalents to the tin amount in the presence of a catalyst by 1 equivalent of the compound having 2 isocyanate groups. Obtained by the reaction of the compound.

Examples of the above isocyanate include isophorone diisocyanate and 2,4. -toluene diisocyanate, 2,6-toluene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4,4'-diisocyanate (MDI), hydrogenated MDI, polymerization MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, benzodimethyl diisocyanate (XDI), hydrogenated XDI, diazonic acid diisocyanate, triphenylmethane Triisocyanate, tris(isocyanatophenyl) thiophosphate, tetramethylxylene diisocyanate, 1,6,10-undecane triisocyanate, and the like.

Further, as the above isocyanate, for example, chain extended isocyanate can also be used. a compound, the chain extended isocyanate compound by ethylene glycol, glycerin, sorbitol, trimethylolpropane, (poly)propylene glycol, carbonate diol, polyether diol, polyester diol, polyhexyl It is obtained by reacting a polyol such as a lactone diol with an excess of isocyanate.

As the (meth)acrylic acid derivative having a hydroxyl group, for example, a commercially available product of 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, or the like Mono (meth) acrylate, trishydroxyl of diols such as alcohol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, polyethylene glycol Ethylene (meth) acrylate such as mono (meth) acrylate or di(meth) acrylate or bisphenol A epoxy acrylate such as ethane, trimethylolpropane or glycerol .

Regarding the above (meth)acrylic acid amine ester, specifically, for example, the following may be used Formula: 134 parts by weight of trimethylolpropane, 0.2 parts by weight of BHT as a polymerization inhibitor, 0.01 parts by weight of dibutyltin dilaurate as a reaction catalyst, and 666 parts by weight of isophorone diisocyanate, at 60 ° C The mixture was reacted for 2 hours while stirring under reflux, and then 51 parts by weight of 2-hydroxyethyl acrylate was added thereto, and the mixture was refluxed while being air-injected, and the mixture was reacted at 90 ° C for 2 hours.

As a commercially available product of the above (meth)acrylic acid amide, for example, M- 1100, M-1200, M-1210, M-1600 (all manufactured by Toagosei Co., Ltd.), EBECRYL230, EBECRYL270, EBECRYL4858, EBECRYL8402, EBECRYL8804, EBECRYL8803, EBECRYL8807, EBECRYL9260, EBECRYL1290, EBECRYL12129, EBECRYL482, EBECRYL210, EBECRYL4827, EBECRYL6700, EBECRYL220, EBECRYL2220 (all manufactured by Daicel-Allnex), Artresin UN-9000H, Artresin UN-9000A, Artresin UN-7100, Artresin UN-1255, Artresin UN-330, Artresin UN-3320HB, Artresin UN-1200TPK, Artresin SH-500B (all manufactured by Gensal Industries, Inc.), U-122P, U-108A, U-340P, U-4HA, U-6HA, U-324A, U-15HA , UA-5201P, UA-W2A, U-1084A, U-6LPA, U-2HA, U-2PHA, UA-4100, UA-7100, UA-4200, UA-4400, UA-340P, U-3HA, UA -7200, U-2061BA, U-10H, U-122A, U-340A, U-108, U-6H, UA-4000 (all manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), AH-600, AT-600, UA -306H, AI-600, UA-101T, UA-101I, UA-306T, UA-306I (all manufactured by Kyoeisha Chemical Co., Ltd.).

The (meth)acrylic resin may also contain a partial (meth)acrylic modified epoxy resin from the viewpoint of improving adhesion and the like.

In the present specification, the above-mentioned partial (meth)acrylic acid-modified epoxy resin means a resin having one or more epoxy groups and (meth)acryloxyloxy groups in one molecule, for example, It is obtained by reacting a partial epoxy group of one or more epoxy resins with (meth)acrylic acid.

In order to improve the adhesiveness of the obtained sealing compound for liquid crystal dropping methods, it is preferable that the said curable resin further contains an epoxy resin. As the epoxy resin, for example, an epoxy resin or the like which is a raw material for synthesizing the above epoxy (meth) acrylate is used.

In the case where the sealing agent for liquid crystal dropping method of the present invention 1 contains the above-mentioned partial (meth)acrylic modified epoxy resin or the above epoxy resin, the ratio of (meth)acrylonitrile group to epoxy group is preferred. The resin is blended in a manner of 50:50 to 95:5. If the ratio of (meth) acrylonitrile is not When it is 50%, there is a case where a large amount of unhardened epoxy resin component remains even after the polymerization is completed, and liquid crystal contamination occurs. When the ratio of the (meth) propylene oxime group exceeds 95%, the obtained sealing compound for liquid crystal dropping methods may be inferior in adhesion.

The curable resin preferably has a hydrogen bond functional group such as an -OH group, a -NH- group or a -NH ₂ group in terms of suppressing liquid crystal contamination.

A preferred lower limit of the hydrogen bond functional group value of the above curable resin is 2 × 10 ^-3 mol/g, and a preferred upper limit is 5 × 10 ^-3 mol/g. When the hydrogen bond functional group value of the curable resin is less than 2 × 10 ^-3 mol/g, the adhesion of the obtained liquid crystal dropping method sealant may be inferior. When the hydrogen bond functional group value of the curable resin exceeds 5 × 10 ^-3 mol/g, the obtained liquid crystal dropping method sealant contaminates the liquid crystal.

In the present specification, when the compound having a hydrogen bond functional group is composed of one type (compound A only), the hydrogen bond functional group value is a value calculated by the following formula. .

Hydrogen bond functional group value (H _A ) (mol/g) = (number of hydrogen bond functional groups in one molecule of compound A) / (molecular weight of compound A)

Further, in the case of a mixture of a plurality of resins, the hydrogen bond functional group value can be calculated by partitioning the content per unit weight (weight fraction) of each compound having a hydrogen bond functional group. For example, when the weight fraction of the compound α is P _α , the hydrogen bond functional group in the case where the compound having a hydrogen bond functional group is composed of the compound A, the compound B, and the compound C is represented by the following formula: Said.

Hydrogen bond functional group value (H _ABC )=H _A P _A +H _B P _B +H _C P _C

The sealing agent for liquid crystal dropping method of the present invention 1 may further contain a sensitizer.

Preferably, the sensitizer has a sufficient light absorbing band in the ultraviolet-visible region, and therefore preferably contains a material selected from the group consisting of a benzophenone skeleton, an anthracene skeleton, an anthracene skeleton, a coumarin skeleton, and 9-oxosulfur a compound having at least one of a skeleton and a group consisting of a phthalocyanine skeleton, more preferably having a skeleton selected from the group consisting of an anthracene skeleton, an anthracene skeleton, and 9-oxosulfur a compound of at least one skeleton of a group consisting of skeletons.

Examples of the compound having the above benzophenone skeleton include the above formula (1). Examples of the compound having a benzophenone skeleton other than the compound represented by the compound include benzophenone and 2,4-dichlorobenzophenone.

Examples of the compound having the above anthracene skeleton include 9,10-dibutoxyanthracene, 9,10-dipropoxyanthracene, and 9,10-ethoxyanthracene.

Examples of the compound having the above fluorene skeleton include 2-ethyl hydrazine, 1-methyl hydrazine, 1,4-dihydroxy fluorene, and 2-(2-hydroxyethoxy) fluorene.

Examples of the compound having the above coumarin skeleton include 7-diethylamino-4-methylcoumarin.

As having the above 9-oxygen sulfur The compound of the skeleton may, for example, be 2,4-diethyl-9-oxosulfur 2-chloro-9-oxosulfur 4-isopropyl-9-oxosulfur 1-chloro-4-propyl-9-oxosulfur Wait.

Examples of the compound having the above phthalocyanine skeleton include phthalocyanine and the like.

Regarding the content of the above sensitizer, 100 weight relative to the above photopolymerization initiator Preferably, the lower limit is 0.5 parts by weight, and the upper limit is preferably 50 parts by weight. When the content of the sensitizer is less than 0.5 part by weight, the sensitizing effect may not be sufficiently exhibited. If the content of the above sensitizer exceeds 50 parts by weight, liquid crystal contamination may occur. The content of the above sensitizer The lower limit is preferably 1 part by weight, and more preferably the upper limit is 40 parts by weight.

The sealant for liquid crystal dropping method of the present invention 1 may further contain a heat hardener.

Examples of the above-mentioned thermosetting agent include an organic acid hydrazine, an imidazole derivative, an amine compound, a polyphenol compound, and an acid anhydride. Among them, organic acid hydrazine can be preferably used.

Examples of the organic acid cerium include diterpene sebacate, diammonium isophthalate, diammonium adipate, and diammonium malonate.

For example, SDH, ADH (all manufactured by Otsuka Chemical Co., Ltd.), Amicure VDH, Amicure VDH-J, and Amicure UDH (all manufactured by Ajinomoto Fine-Techno Co., Ltd.) and the like are exemplified as the commercially available ones.

The content of the above-mentioned thermosetting agent is preferably 1 part by weight, and preferably 50 parts by weight, based on 100 parts by weight of the curable resin. When the content of the above-mentioned heat curing agent is less than 1 part by weight, the obtained liquid crystal dropping method sealing agent may not be sufficiently thermally cured. When the content of the above-mentioned heat-hardening agent exceeds 50 parts by weight, the viscosity of the obtained sealing compound for liquid crystal dropping methods becomes high, and the coating property is deteriorated. A more preferable upper limit of the content of the above thermal curing agent is 30 parts by weight.

In order to improve the viscosity, improve the adhesion by the stress dispersion effect, improve the linear expansion ratio, and improve the moisture resistance of the cured product, the sealing agent for liquid crystal dropping method of the present invention preferably contains a filler.

Examples of the filler include talc, asbestos, silica, diatomaceous earth, bentonite, bentonite, calcium carbonate, magnesium carbonate, alumina, montmorillonite, zinc oxide, iron oxide, and magnesium oxide. Inorganic fillers such as tin oxide, titanium oxide, magnesium hydroxide, aluminum hydroxide, glass beads, tantalum nitride, barium sulfate, gypsum, calcium silicate, sericite activated clay, aluminum nitride, or the like, or An organic filler such as polyester microparticles, polyurethane microparticles, vinyl polymer microparticles, or acrylic polymer microparticles. These fillers may be used singly or in combination of two or more.

Regarding the content of the above filler, the sealant 100 for liquid crystal dropping method The lower limit is preferably 10 parts by weight, and preferably the upper limit is 70 parts by weight. When the content of the filler is less than 10 parts by weight, the effect of improving the adhesion or the like may not be sufficiently exhibited. When the content of the filler exceeds 70 parts by weight, the viscosity of the obtained sealing compound for liquid crystal dropping methods becomes high, and the coatability is deteriorated. A more preferred lower limit of the content of the above filler is 20 parts by weight, and a more preferred upper limit is 60 parts by weight.

The sealing agent for liquid crystal dropping method of the present invention 1 preferably contains a decane coupling agent. on The decane coupling agent mainly functions as an auxiliary agent for adhering a sealing agent to a substrate or the like well.

As the above decane coupling agent, the effect of improving adhesion to a substrate or the like is excellent. It is possible to suppress the flow of the curable resin into the liquid crystal by chemical bonding with the curable resin, and for example, γ-aminopropyltrimethoxydecane or γ-mercaptopropyltrimethoxydecane can be preferably used. Γ-glycidoxypropyltrimethoxydecane, γ-isocyanatepropyltrimethoxydecane, and the like. These decane coupling agents may be used singly or in combination of two or more.

The present invention provides a sealing agent for a liquid crystal dropping method, which comprises a curable resin and a photopolymerization initiator, and the photopolymerization initiator contains a compound represented by the following formula (2).

The invention 2 is described in detail below.

In the formula (2), X represents an alkylene group having 1 to 6 carbon atoms.

The present inventors have found that the use of an oxime ester compound having a specific structure as a photopolymerization initiator can provide a liquid crystal dropping method sealant which is excellent in photocurability and can suppress liquid crystal contamination, thereby completing the present invention 2.

The sealing agent for liquid crystal dropping methods of the present invention 2 contains a photopolymerization initiator. The photopolymerization initiator contains the oxime ester compound represented by the above formula (2). By using the oxime ester compound represented by the above formula (2), a sealing compound for a liquid crystal dropping method having high sensitivity and excellent photocurability can be obtained, and liquid crystal contamination can be suppressed.

In the above formula (2), examples of the alkylene group represented by X include a methylene group, an exoethyl group, a propyl group, an isopropyl group, an exobutyl group, a 1-methyl group, and a 1-ethyl group. Base ethyl, pentyl, hexyl and the like. Among them, a methylene group and an ethyl group are preferred.

The content of the photopolymerization initiator is preferably 0.1 part by weight, and preferably 10 parts by weight, based on 100 parts by weight of the curable resin. When the content of the photopolymerization initiator is less than 0.1 part by weight, the photopolymerization of the obtained liquid crystal dropping method sealant may not be sufficiently performed. When the content of the photopolymerization initiator is more than 10 parts by weight, a large amount of unreacted photopolymerization initiator remains, and the weather resistance of the obtained liquid crystal dropping method sealant is deteriorated, or storage stability is poor. Or, in the case of liquid crystal contamination. The above photopolymerization A more preferred lower limit of the content of the initiator is 0.2 parts by weight, and a more preferred upper limit is 5 parts by weight.

The sealing compound for liquid crystal dropping methods of the present invention 2 contains a curable resin.

The curable resin is preferably a resin having at least one (meth) acrylonitrile group in one molecule (hereinafter also referred to as "(meth)acrylic resin"). In terms of high reactivity, the (meth)acrylic resin preferably has two or more (meth)acrylonium groups in one molecule.

In the present specification, the above "(meth)acryloyl group means propylene fluorenyl group or methacryl fluorenyl group, and the above "(meth)acrylic acid" means acrylic acid or methacrylic acid.

As the (meth)acrylic resin, for example, (meth) propylene can be mentioned. An ester compound obtained by reacting an enoic acid with a compound having a hydroxyl group, an epoxy (meth) acrylate obtained by reacting (meth)acrylic acid with an epoxy compound, and an isocyanate having a hydroxyl group (methyl group) A (meth)acrylic acid amine ester or the like obtained by reacting an acrylic acid derivative. Among them, epoxy (meth) acrylate is preferred from the viewpoint of easiness of synthesis and the like.

In the present specification, the above "(meth) acrylate" means acrylate or methacrylate, and the above "epoxy (meth) acrylate" means that all epoxy groups in the epoxy resin are A compound obtained by reacting (meth)acrylic acid.

As the monofunctional one of the above ester compounds, for example, (meth) propylene is exemplified 2-hydroxyethyl acid, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, isobutyl (meth)acrylate, ( Tert-butyl methacrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isodecyl (meth) acrylate, (meth) acrylate ring Hexyl ester, 2-methoxyethyl (meth)acrylate, methoxyethylene glycol (meth) acrylate, 2-ethoxyethyl (meth) acrylate, tetrahydroanthracene (meth) acrylate Ester, benzyl (meth) acrylate, ethyl carbitol (meth) acrylate, phenoxy acetyl (meth) acrylate Ester, phenoxy diethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, (meth) acrylate 2 , 2,2-trifluoroethyl ester, 2,2,3,3-tetrafluoropropyl (meth)acrylate, 1H,1H,5H-octafluoropentyl (meth)acrylate, decyl imine (methyl) ) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ( N-octyl methacrylate, isodecyl (meth) acrylate, isomyristyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, 2-phenoxy (meth) acrylate Ethyl ester, dicyclopentenyl (meth)acrylate, isodecyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, succinic acid 2-(Methyl)propenyloxyethyl ester, 2-(methyl)propenyloxyethyl hexahydrophthalate, 2-(methyl)acryloxyethyl 2-hydroxypropyl Phthalate, glycidyl (meth)acrylate, 2-(meth)acryloxyethyl phosphate, and the like.

Further, as the bifunctional one of the above ester compounds, for example, 1,4- Butanediol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di Methyl) acrylate, 1,10-nonanediol di(meth) acrylate, 2-n-butyl-2-ethyl-1,3-propanediol di(meth) acrylate, dipropylene glycol di(a) Acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol (meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene Alcohol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene oxide addition bisphenol A di(meth)acrylate, ethylene oxide addition bisphenol A di(methyl) Acrylate, ethylene oxide addition bisphenol F di(meth) acrylate, dimethylol dicyclopentadienyl di(meth) acrylate, 1,3-butanediol di(methyl) Acrylate, neopentyl glycol di(meth)acrylate, ethylene oxide modified di(meth)acrylate isocyanate, 2-hydroxy-3-(methyl)(meth)acrylate Propylene methoxypropyl ester, carbonate diol di (a Acrylate, polyether diol di(meth) acrylate, polyester diol di(meth) acrylate, polycaprolactone diol di(meth) acrylate, polybutadiene diol II (Meth) acrylate, etc.

Further, as the trifunctional or higher one of the above ester compounds, for example, new Pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, propylene oxide addition trimethylolpropane tri(meth)acrylate, ethylene oxide addition trishydroxyl Methylpropane tri(meth)acrylate, caprolactone modified trimethylolpropane tri(meth)acrylate, ethylene oxide addition isocyanuric acid tris(meth)acrylate, two new Pentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, di-trimethylolpropane tetra (meth) acrylate, neopentyl alcohol tetra (meth) acrylate And triglyceride (meth) acrylate, propylene oxide addition glycerol tri(meth) acrylate, tris (meth) propylene methoxyethyl phosphate, and the like.

The epoxy (meth) acrylate is exemplified by a usual method. The epoxy resin and (meth)acrylic acid are obtained by reacting in the presence of a basic catalyst.

Epoxy which becomes a raw material for synthesizing the above epoxy (meth) acrylate Examples of the resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, 2,2'-diallyl bisphenol A type epoxy resin, and 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, two Cyclopentadiene type epoxy resin, naphthalene type epoxy resin, phenol novolak type epoxy resin, o-cresol novolac type epoxy resin, dicyclopentadiene novolac type epoxy resin, biphenol novolak type Epoxy resin, naphthol novolac type epoxy resin, epoxy propylamine type epoxy resin, alkyl polyol type epoxy resin, rubber modified epoxy resin, glycidyl ester compound, and the like.

As a commercially available one of the above bisphenol A type epoxy resins, for example, Epikote 828EL, Epikote 1004 (both manufactured by Mitsubishi Chemical Corporation), Epiclon 850 (manufactured by DIC Corporation), and the like.

For example, Epikote 806 and Epikote 4004 (all manufactured by Mitsubishi Chemical Corporation) and the like are mentioned as a commercial product of the bisphenol F-type epoxy resin.

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

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

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

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

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

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

For example, YSLV-50TE (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.) or the like can be mentioned as a commercially available one of the above-mentioned thioether type epoxy resins.

For example, YSLV-80DE (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.) and the like can be cited as a commercially available one of the above-mentioned diphenyl ether type epoxy resins.

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

Examples of the commercially available ones of the naphthalene type epoxy resins include Epiclon HP 4032 and Epiclon EXA-4700 (all manufactured by DIC Corporation).

As a commercial item of the above-mentioned phenol novolak type epoxy resin, Epiclon N-770 (made by the DIC company) etc. are mentioned, for example.

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

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

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

As a commercial item of the above-mentioned naphthol novolac type epoxy resin, ESN-165S (made by Nippon Steel & Sumitomo Chemical Co., Ltd.), etc. are mentioned, for example.

For example, Epikote 630 (manufactured by Mitsubishi Chemical Corporation), Epiclon 430 (manufactured by DIC Corporation), TETRAD-X (manufactured by Mitsubishi Gas Chemical Co., Ltd.), and the like are mentioned as a commercially available one.

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

For example, YR-450, YR-207 (all manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), Epolead PB (manufactured by Daicel Chemical Industry Co., Ltd.), and the like are mentioned as a commercially available one of the rubber-modified epoxy resins.

As a commercially available one of the above-mentioned glycidyl ester compounds, for example, Denacol EX-147 can be cited. (manufactured by Nagase ChemteX), etc.

For example, YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), XAC4151 (made by Asahi Kasei Co., Ltd.), Epikote 1031, and Epikote 1032 are mentioned as the other commercially available ones. (all manufactured by Mitsubishi Chemical Corporation), EXA-7120 (manufactured by DIC Corporation), TEPIC (manufactured by Nissan Chemical Co., Ltd.), and the like.

As described above, the above epoxy (meth) acrylate can be epoxy by a usual method. The resin is produced by reacting (meth)acrylic acid in the presence of a basic catalyst. Specifically, for example, 360 parts by weight of a resorcinol type epoxy resin (EX-201, manufactured by Nagase ChemteX Co., Ltd.) and 2 parts by weight of a p-methoxyphenol as a polymerization inhibitor are supplied while supplying air under reflux. Resorcinol type epoxy acrylate was obtained by reacting 2 parts by weight of triethylamine as a reaction catalyst with 210 parts by weight of acrylic acid at 90 ° C for 5 hours.

As a commercial one of the above-mentioned epoxy (meth)acrylate, for example, the following are mentioned: EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRYL3703, EBECRYL3800, EBECRYL6040, EBECRYL LDX63182 (all manufactured by Daicel-Allnex), EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, EMA-1020 (both manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), Epoxy Ester M-600A, Epoxy Ester 40EM, Epoxy Ester 70PA, Epoxy Ester 200PA, Epoxy Ester 80MFA, Epoxy Ester 3002M, Epoxy Ester 3002A, Epoxy Ester 1600A, Epoxy Ester 3000M, Epoxy Ester 3000A, Epoxy Ester 200EA, Epoxy Ester 400EA (all manufactured by Kyoei Chemical Co., Ltd.), Denacol Acrylate DA-141, Denacol Acrylate DA-314, Denacol Acrylate DA-911 (both Nagase chemteX) Company manufacturing) and so on.

As described above, by isocyanate and (meth)acrylic acid having a hydroxyl group The (meth)acrylic acid amide obtained by the reaction, for example, can make the (meth)acrylic acid derivative having a hydroxyl group 2 equivalents to the tin amount in the presence of a catalyst by 1 equivalent of the compound having 2 isocyanate groups. Obtained by the reaction of the compound.

Examples of the above isocyanate include isophorone diisocyanate and 2,4. -toluene diisocyanate, 2,6-toluene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4,4'-diisocyanate (MDI), hydrogenated MDI, polymerization MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, benzodimethyl diisocyanate (XDI), hydrogenated XDI, diazonic acid diisocyanate, triphenylmethane triisocyanate, thio Tris(isocyanatophenyl) phosphate, tetramethylxylene diisocyanate, 1,6,10-undecane triisocyanate, and the like.

Further, as the above isocyanate, for example, chain extended isocyanate can also be used. a compound, the chain extended isocyanate compound by ethylene glycol, glycerin, sorbitol, trimethylolpropane, (poly)propylene glycol, carbonate diol, polyether diol, polyester diol, polyhexyl It is obtained by reacting a polyol such as a lactone diol with an excess of isocyanate.

As the (meth)acrylic acid derivative having a hydroxyl group, for example, a commercially available product of 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, or the like Mono (meth) acrylate, trishydroxyl of diols such as alcohol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, polyethylene glycol Ethylene (meth) acrylate such as mono (meth) acrylate or di(meth) acrylate or bisphenol A epoxy acrylate such as ethane, trimethylolpropane or glycerol .

Regarding the above (meth)acrylic acid amine ester, specifically, for example, the following may be used Formula: 134 parts by weight of trimethylolpropane, 0.2 parts by weight of BHT as a polymerization inhibitor, 0.01 parts by weight of dibutyltin dilaurate as a reaction catalyst, and 666 parts by weight of isophorone diisocyanate, at 60 ° C The mixture was reacted for 2 hours while stirring under reflux, and then 51 parts by weight of 2-hydroxyethyl acrylate was added thereto, and the mixture was refluxed while being air-injected, and the mixture was reacted at 90 ° C for 2 hours.

As a commercially available product of the above (meth)acrylic acid amide, for example, M- 1100, M-1200, M-1210, M-1600 (all manufactured by Toagosei Co., Ltd.), EBECRYL230, EBECRYL270, EBECRYL4858, EBECRYL8402, EBECRYL8804, EBECRYL8803, EBECRYL8807, EBECRYL9260, EBECRYL1290, EBECRYL5129, EBECRYL4842, EBECRYL210, EBECRYL4827, EBECRYL6700, EBECRYL220, EBECRYL2220 (both manufactured by Daicel-Allnex), Artresin UN-9000H, Artresin UN-9000A, Artresin UN-7100, Artresin UN-1255, Artresin UN-330, Artresin UN-3320HB, Artresin UN-1200TPK, Artresin SH -500B (all manufactured by Gensei Industrial Co., Ltd.), U-122P, U-108A, U-340P, U-4HA, U-6HA, U-324A, U-15HA, UA-5201P, UA-W2A, U-1084A , U-6LPA, U-2HA, U-2PHA, UA-4100, UA-7100, UA-4200, UA-4400, UA-340P, U-3HA, UA-7200, U-2061BA, U-10H, U -122A, U-340A, U-108, U-6H, UA-4000 (all manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), AH-600, AT-600, UA-306H, AI-600, UA-101T, UA -101I, UA-306T, UA-306I (all manufactured by Kyoeisha Chemical Co., Ltd.) and the like.

The above (meth)acrylic resin may also contain a viewpoint of improving adhesion and the like. Partial (meth)acrylic modified epoxy resin.

In the present specification, the above-mentioned partial (meth)acrylic acid-modified epoxy resin means a resin having one or more epoxy groups and (meth)acryloxyloxy groups in one molecule, for example, It is obtained by reacting a partial epoxy group of one or more epoxy resins with (meth)acrylic acid.

In order to improve the adhesion of the obtained sealant for liquid crystal dropping method, the above hardening The resin preferably further contains an epoxy resin. As the epoxy resin, for example, an epoxy resin or the like which is a raw material for synthesizing the above epoxy (meth) acrylate is used.

The sealing agent for liquid crystal dropping method of the present invention 2 contains the above-mentioned partial (meth) propylene In the case of an acid-modified epoxy resin or the above epoxy resin, it is preferred to blend each resin so that the ratio of the (meth)acryl fluorenyl group to the epoxy group is 50:50 to 95:5. When the ratio of the (meth)acrylonitrile group is less than 50%, there is a case where a large amount of unhardened epoxy resin component remains even after the completion of the polymerization, and liquid crystal contamination occurs. When the ratio of the (meth) propylene oxime group exceeds 95%, the obtained sealing compound for liquid crystal dropping methods may be inferior in adhesion.

The curable resin preferably has a hydrogen bond functional group such as an -OH group, a -NH- group or a -NH ₂ group in terms of suppressing liquid crystal contamination.

A preferred lower limit of the hydrogen bond functional group value of the above curable resin is 2 × 10 ^-3 mol/g, and a preferred upper limit is 5 × 10 ^-3 mol/g. When the hydrogen-bonding functional group value of the curable resin less than 2 × 10 ^-3 mol / g, there is obtained a liquid crystal dropping method has become the sealing agent to conditions of the poor adhesive property. When the hydrogen bond functional group value of the curable resin exceeds 5 × 10 ^-3 mol/g, the obtained liquid crystal dropping method sealant contaminates the liquid crystal.

In the present specification, when the compound having a hydrogen bond functional group is composed of one type (compound A only), the hydrogen bond functional group value is a value calculated by the following formula. .

Hydrogen bond functional group value (H _A ) (mol/g) = (number of hydrogen bond functional groups in one molecule of compound A) / (molecular weight of compound A)

Further, in the case where the compound having a hydrogen bond functional group is composed of a mixture of a plurality of resins, the hydrogen bond functional group value may be based on the content per unit weight of each compound having a hydrogen bond functional group (weight Rate) is calculated by allocation. For example, when the compound having a hydrogen bond functional group is composed of the compound A, the compound B, and the compound C, the hydrogen bond functional group value is represented by the following formula.

Hydrogen bond functional group value (H _ABC )=H _A P _A +H _B P _B +H _C P _C

(Further, P _α represents the weight fraction of compound α)

The sealing agent for liquid crystal dropping method of the present invention 2 preferably contains a sensitizer. By containing the above sensitizer, a sealing agent for a liquid crystal dropping method having higher sensitivity and excellent photocurability can be obtained.

Preferably, the sensitizer has a sufficient light absorbing band in the ultraviolet-visible region, and therefore preferably contains a material selected from the group consisting of a benzophenone skeleton, an anthracene skeleton, an anthracene skeleton, a coumarin skeleton, and 9-oxosulfur a compound having at least one of a skeleton and a group consisting of a phthalocyanine skeleton, more preferably having a skeleton selected from the group consisting of an anthracene skeleton, an anthracene skeleton, and 9-oxosulfur a compound of at least one skeleton of a group consisting of skeletons.

Examples of the compound having the above benzophenone skeleton include benzophenone, 2,4-dichlorobenzophenone, and 4,4'-bis(dimethylamino)benzophenone, 4, 4'-bis(diethylamino)benzophenone, 4-(dimethylamino)benzophenone, and the like.

Examples of the compound having the above anthracene skeleton include 9,10-dibutoxyanthracene, 9,10-dipropoxyanthracene, and 9,10-ethoxyanthracene.

Examples of the compound having the above fluorene skeleton include 2-ethyl hydrazine and 1-methyl group. Anthracene, 1,4-dihydroxyindole, 2-(2-hydroxyethoxy)-anthracene, and the like.

Examples of the compound having the above coumarin skeleton include 7-diethylamino-4-methylcoumarin.

As having the above 9-oxygen sulfur The compound of the skeleton may, for example, be 2,4-diethyl-9-oxosulfur 2-chloro-9-oxosulfur 4-isopropyl-9-oxosulfur 1-chloro-4-propyl-9-oxosulfur Wait.

Examples of the compound having the above phthalocyanine skeleton include phthalocyanine and the like.

Among the sensitizers, the liquid crystal dropping method sealant obtained is particularly excellent in hardenability of the light-shielding portion, and is preferably selected from 4,4'-bis(dimethylamino)diphenyl. At least one of a group consisting of ketone, 4,4'-bis(diethylamino)benzophenone, and 4-(dimethylamino)benzophenone.

Regarding the content of the above sensitizer, 100 weight relative to the above photopolymerization initiator Preferably, the lower limit is 2 parts by weight, and the upper limit is preferably 50 parts by weight. When the content of the sensitizer is less than 2 parts by weight, the sensitizing effect may not be sufficiently exhibited. If the content of the above sensitizer exceeds 50 parts by weight, liquid crystal contamination may occur. A more preferred lower limit of the content of the above sensitizer is 5 parts by weight, and a more preferred upper limit is 40 parts by weight.

Regarding the content of the above sensitizer, the sealing agent as a whole for the liquid crystal dropping method, A preferred lower limit is 0.01% by weight, and a preferred upper limit is 2% by weight. When the content of the sensitizer is less than 0.01% by weight, the sensitizing effect may not be sufficiently exhibited. If the content of the above sensitizer exceeds 2% by weight, liquid crystal contamination may occur. A more preferred lower limit of the content of the above sensitizer is 0.03% by weight, more preferably an upper limit of 1.5% by weight, and still more preferably a lower limit of 0.05% by weight.

The sealant for liquid crystal dropping method of the present invention 2 preferably contains a heat hardener.

Examples of the above-mentioned thermosetting agent include an organic acid hydrazine, an imidazole derivative, an amine compound, a polyphenol compound, and an acid anhydride. Among them, organic acid hydrazine can be preferably used.

Examples of the organic acid cerium include diterpene sebacate, diammonium isophthalate, diammonium adipate, and diammonium malonate.

For example, SDH, ADH (all manufactured by Otsuka Chemical Co., Ltd.), Amicure VDH, Amicure VDH-J, and Amicure UDH (all manufactured by Ajinomoto Fine-Techno Co., Ltd.) and the like are exemplified as the commercially available ones.

The content of the above-mentioned thermosetting agent is preferably 1 part by weight, and preferably 50 parts by weight, based on 100 parts by weight of the curable resin. When the content of the above-mentioned heat curing agent is less than 1 part by weight, the obtained liquid crystal dropping method sealing agent may not be sufficiently thermally cured. When the content of the above-mentioned heat-hardening agent exceeds 50 parts by weight, the viscosity of the obtained sealing compound for liquid crystal dropping methods becomes high, and the coating property is deteriorated. A more preferable upper limit of the content of the above thermal curing agent is 30 parts by weight.

In order to improve the viscosity, improve the adhesion by the stress dispersion effect, improve the linear expansion ratio, and further improve the moisture resistance of the cured product, the sealing agent for liquid crystal dropping method of the present invention 2 preferably contains a filler.

Examples of the filler include talc, asbestos, silica, diatomaceous earth, bentonite, bentonite, calcium carbonate, magnesium carbonate, alumina, montmorillonite, zinc oxide, iron oxide, and magnesium oxide. Inorganic fillers such as tin oxide, titanium oxide, magnesium hydroxide, aluminum hydroxide, glass beads, tantalum nitride, barium sulfate, gypsum, calcium silicate, sericite activated clay, aluminum nitride, or polyester microparticles, polyurethane microparticles An organic filler such as a vinyl polymer microparticle or an acrylic polymer microparticle. These fillers may be used singly or in combination of two or more.

Regarding the content of the above filler, the sealant 100 for liquid crystal dropping method The lower limit is preferably 10 parts by weight, and preferably the upper limit is 70 parts by weight. When the content of the filler is less than 10 parts by weight, the effect of improving the adhesion or the like may not be sufficiently exhibited. When the content of the filler exceeds 70 parts by weight, the viscosity of the obtained sealing compound for liquid crystal dropping methods becomes high, and the coatability is deteriorated. A more preferred lower limit of the content of the above filler is 20 parts by weight, and a more preferred upper limit is 60 parts by weight.

The sealing agent for liquid crystal dropping method of the present invention 2 preferably contains a decane coupling agent. on The decane coupling agent mainly functions as an auxiliary agent for adhering a sealing agent to a substrate or the like well.

As the above decane coupling agent, the effect of improving adhesion to a substrate or the like is excellent. It is possible to suppress the flow of the curable resin into the liquid crystal by chemical bonding with the curable resin, and for example, γ-aminopropyltrimethoxydecane or γ-mercaptopropyltrimethoxydecane can be preferably used. Γ-glycidoxypropyltrimethoxydecane, γ-isocyanatepropyltrimethoxydecane, and the like. These decane coupling agents may be used singly or in combination of two or more.

Sealant for liquid crystal dropping method of the present invention 1 and the present invention 2 (hereinafter The method of the "liquid crystal dropping method sealing agent of the present invention" is exemplified by the following methods, such as a homogeneous phase disperser, a homomixer, a universal mixer, a planetary mixer, a kneader, and a three-roll mill. An additive such as a curable resin, a photopolymerization initiator, and a decane coupling agent to be added as needed is mixed.

The preferred lower limit of the viscosity of the sealant for liquid crystal dropping method of the present invention measured by the E-type viscometer at 25 ° C and 1 rpm is 50,000 Pa s, and the upper limit is preferably 500,000 Pa ‧ . If the viscosity is less than 50,000 Pa‧s or more than 500,000 Pa‧s, there is a sealing agent for liquid crystal dropping method. The workability when coating on a substrate is deteriorated. A better upper limit for the above viscosity is 400,000 Pa‧s.

By disposing the conductive fine particles with the sealing agent for liquid crystal dropping method of the present invention, Manufacture the upper and lower conductive materials. Moreover, the above-described upper and lower conductive materials containing the sealing compound for liquid crystal dropping method of the present invention and conductive fine particles are also one of the inventions.

As the conductive fine particles, a metal ball or a surface of the resin fine particles can be used. The surface is formed with a conductive metal layer or the like. Among them, it is preferable that the conductive metal layer is formed on the surface of the resin fine particles by the excellent elasticity of the resin fine particles, and the conductive connection can be realized without damaging the transparent substrate or the like.

Further, the sealing agent for liquid crystal dropping method of the present invention or the upper and lower sides of the present invention are used. A liquid crystal display element manufactured by a material is also one of the inventions.

As a method of manufacturing the liquid crystal display element of the present invention, for example, there may be mentioned The method of the next step: one of two transparent substrates, such as a glass substrate with an electrode such as an ITO film or a polyethylene terephthalate substrate, is applied by screen printing, dispenser coating, or the like. In the liquid crystal dropping method of the present invention, a rectangular sealing pattern is formed by a sealant or the like; and the droplets of the liquid crystal are dripped and applied to the entire surface of the transparent substrate in an uncured state in a liquid crystal dropping method or the like according to the present invention. a step of immediately superposing another substrate; and a step of irradiating a portion of a seal pattern such as a sealing compound for a liquid crystal dropping method of the present invention with ultraviolet light or the like to temporarily cure the sealant; and heating the temporarily hardened sealant to form a hardened portion. step.

According to the present invention, it is possible to provide a sealing compound for a liquid crystal dropping method which is excellent in photocurability and can suppress liquid crystal contamination. Moreover, according to the present invention, it is possible to provide a vertical conduction material and a liquid crystal display element which are produced by using the sealing compound for liquid crystal dropping methods.

1‧‧‧Sealant

2‧‧‧Black matrix

3‧‧‧LCD

Fig. 1 is a cross-sectional view schematically showing a liquid crystal display element produced by using the sealant obtained in the examples and the comparative examples in a state without a light-shielding portion.

Fig. 2 is a cross-sectional view schematically showing a liquid crystal display element produced by using the sealant obtained in the examples and the comparative examples in a state in which a light shielding portion is provided.

The invention is illustrated in more detail below by way of examples, but the invention is not limited to the examples.

(Examples 1 to 10, Comparative Examples 1 to 12)

According to the blending ratios shown in Tables 1 and 2, each material was mixed using a planetary mixer (manufactured by Thinky Co., Ltd., "Defoaming Stirring"), and further mixed using a three-roll mill to prepare Example 1~ 10. The sealing agent for liquid crystal dropping method of Comparative Examples 1 to 12.

In addition, the "compound represented by the formula (3)" and the "compound represented by the formula (4)" described in Tables 1 and 2 mean compounds represented by the following formulas (3) and (4), respectively.

<evaluation>

Each of the sealing compounds for liquid crystal dropping methods obtained in Examples 1 to 10 and Comparative Examples 1 to 12 was subjected to the following evaluation. The results are shown in Tables 1 and 2.

(photohardenability)

First, a substrate (A) obtained by vapor-depositing a half surface of a Corning glass having a thickness of 0.7 mm and a substrate (B) obtained by vapor-depositing a front surface are prepared. Then, in 100 parts by weight of each of the sealing compounds for liquid crystal dropping methods obtained in Examples 1 to 10 and Comparative Examples 1 to 12, spacer fine particles ("Micropearl SI-H050", 5 μm) manufactured by Sekisui Chemical Co., Ltd.) were used. The sealant is applied to the central portion of the substrate A (the boundary between the chromium vapor deposition portion and the non-vapor deposition portion), and after bonding the substrate B, the sealant is sufficiently squeezed, and a metal halide lamp is used from the substrate A side. Ultraviolet rays of 100 mW/cm ^{2 were} irradiated for 30 seconds.

Thereafter, the substrates A and B were peeled off using a cutter, and the spectrum of the sealant on the direct ultraviolet irradiation portion (position 1) and the point (position 2) at a distance of 50 μm from the edge of the direct ultraviolet irradiation portion (position 2) was measured by a micro-IR method. And the conversion ratio of the acrylonitrile group in the sealant was determined by the following method based on each spectrum. Specifically, the peak area of 815 to 800 cm ^-1 was defined as the peak area of the acrylonitrile group, and the peak area of 845 to 820 cm ^{-1 was} defined as the reference peak area, and the conversion ratio of the acrylonitrile group was calculated according to the following formula.

The conversion ratio of the acrylonitrile group = {1 - the peak area of the propylene sulfhydryl group after ultraviolet irradiation / the reference peak area after the ultraviolet ray irradiation) / (the peak area of the acryl thiol group before the ultraviolet irradiation / the reference peak area before the ultraviolet irradiation) )}×100

(liquid crystal contamination 1)

In 100 parts by weight of each of the sealing compounds for liquid crystal dropping methods obtained in Examples 1 to 10 and Comparative Examples 1 to 12, 1 part by weight of fine particles ("Micropearl SI-H050" manufactured by Sekisui Chemical Co., Ltd.) was dispersed. The liquid crystal dropping method is used as a sealant, and is applied to one of two substrates having a rubbed alignment film and a transparent electrode by means of a dispenser in such a manner that the line width of the sealant is 1 mm.

Then, a droplet of liquid crystal (manufactured by Chisso Co., Ltd., "JC-5004LA") was dropped on the entire surface of the sealant of the substrate with the transparent electrode, and immediately attached to another color filter with a transparent electrode. The substrate was irradiated with a 100 mW/cm ² ultraviolet ray for 30 seconds using a metal halide lamp to be hardened, and further heated at 120 ° C for 1 hour to obtain a liquid crystal display element.

Regarding the liquid crystal display element, the application position of the sealant is controlled by the dispenser, and the liquid crystal display element (without the light-shielding portion) in which the light is completely irradiated to the sealant is formed, and the black color filter substrate is covered with 50% of the line width. Two types of liquid crystal display elements (with light-shielding portions) coated with a sealant are applied in a matrix. As shown in FIG. 1 , in the case where the sealant 1 has no light-shielding portion, the sealant 1 is completely exposed to light, and on the other hand, the liquid crystal display element having the light-shielding portion of the sealant 1 is in contact with the liquid crystal 3 as shown in FIG. 2 . The portion of the sealant 1 is shielded by the black matrix 2 and is completely out of light.

With respect to the liquid crystal display element obtained, it was visually confirmed that the liquid crystal alignment in the vicinity of the sealant after the voltage was applied at 80 ° C for 1,000 hours was disordered.

The alignment chaos is judged by the uneven color of the display part, according to the degree of color unevenness, When there is no color unevenness, it is set to "◎", and when there is a slight color unevenness, it is set to "○", and when there is a slight color unevenness, it is set to "△", and a large number of colors are uneven. The liquid crystal contamination was evaluated for "x".

In addition, the liquid crystal display elements evaluated as "◎" and "○" are at a level that is practically problem-free.

(liquid crystal contamination 2)

In the same manner as in the above-mentioned "(liquidus contamination property 1)", the respective liquid crystal dropping method sealants obtained in Examples 1 to 10 and Comparative Examples 1 to 12 were used to produce a color filter covering 50% of the line width. A liquid crystal display element (having a light shielding portion) to which a sealant is applied as a black matrix of a light sheet substrate.

With respect to the liquid crystal display element obtained, it was visually confirmed that the liquid crystal alignment in the vicinity of the sealant after the voltage was applied in a dry atmosphere at 90 ° C for 1,000 hours was disordered.

It is considered that "the liquid crystal contamination 2" is more severely heated than the "liquid crystal contamination 1", and therefore the fluidity of the ionic substance is improved, so that liquid crystal alignment disorder is more likely to occur.

The alignment disorder is judged by the uneven color of the display portion, and the case where the colorlessness is completely uneven is set to "◎" according to the degree of color unevenness, and the case where the color unevenness is slightly set is "○", When there is a slight color unevenness, it is set to "△", and when there is a large amount of color unevenness, it is set to "x" to evaluate liquid crystal contamination.

In addition, the liquid crystal display elements evaluated as "◎" and "○" are at a level that is practically problem-free.

(Examples 11 to 20, Comparative Examples 13, 14)

According to the blending ratios shown in Table 3, each material was mixed using a planetary mixer (manufactured by Thinky Co., Ltd., "Defoaming Stirling"), and then mixed using a three-roll mill to prepare Examples 11 to 20, and compared. The sealing agent for liquid crystal dropping method of Examples 13 and 14.

In addition, the "compound represented by the formula (3)", the "compound represented by the formula (4)", the "compound represented by the formula (5)", and the "compound represented by the formula (6)" described in Table 3 are respectively intended. The compounds represented by the following formulas (3), (4), (5), and (6).

<evaluation>

Each of the sealing compounds for liquid crystal dropping methods obtained in Examples 11 to 20 and Comparative Examples 13 and 14 was subjected to the following evaluation. The results are shown in Table 3.

(photohardenability)

Each of the liquid crystal dropping method sealants obtained in Examples 11 to 20 and Comparative Examples 13 and 14 was applied onto a glass substrate at about 5 μm, and a glass substrate of the same size was superposed on the substrate, and second, a metal halide lamp was used. Light of 100 mW/cm ² was irradiated for 10 seconds. The photocurability was evaluated by measuring the amount of change before and after the irradiation of light from the peak of the acrylonitrile group by using an infrared spectroscopic device ("FTS3000" manufactured by BIORAD Co., Ltd.). The case where the peak derived from the acrylonitrile group is reduced by 93% or more after the light irradiation is set to "◎", and the peak derived from the acrylonitrile group after light irradiation is reduced by 85% or more and is not 93%. The case where the peak derived from the acrylonitrile group is reduced by 75% or more and does not reach 85% after the light irradiation is set to "Δ", and the decrease of the peak derived from the acrylonitrile group after the light irradiation is less than 75% is set as "X" was used to evaluate photocurability.

(liquid crystal contamination)

In 100 parts by weight of each of the sealing compounds for liquid crystal dropping methods obtained in Examples 11 to 20 and Comparative Examples 13 and 14, 1 part by weight of fine particles ("Micropearl SI-H050" manufactured by Sekisui Chemical Co., Ltd.) was dispersed. The liquid crystal dropping method is used as a sealant, and is applied to one of two substrates having a rubbed alignment film and a transparent electrode by means of a dispenser in such a manner that the line width of the sealant is 1 mm.

Then, a droplet of liquid crystal (manufactured by Chisso Co., Ltd., "JC-5004LA") was dropped on the entire surface of the sealant of the substrate with the transparent electrode, and immediately attached to another color filter with a transparent electrode. The substrate was irradiated with a 100 mW/cm ² ultraviolet ray for 30 seconds using a metal halide lamp to be hardened, and further heated at 120 ° C for 1 hour to obtain a liquid crystal display element.

Regarding the liquid crystal display element, the application position of the sealant is controlled by the dispenser, and the liquid crystal display element (without the light-shielding portion) in which the light is completely irradiated to the sealant is formed, and the black color filter substrate is covered with 50% of the line width. Two types of liquid crystal display elements (with light-shielding portions) coated with a sealant are applied in a matrix. As shown in FIG. 1 , in the case where the sealant 1 has no light-shielding portion, the sealant 1 is completely exposed to light, and on the other hand, the liquid crystal display element having the light-shielding portion of the sealant 1 is in contact with the liquid crystal 3 as shown in FIG. 2 . The portion of the sealant 1 is shielded by the black matrix 2 and is completely out of light.

With respect to the liquid crystal display element obtained, it was visually confirmed that the liquid crystal alignment in the vicinity of the sealant after the voltage was applied at 80 ° C for 1,000 hours was disordered.

The alignment chaos is judged by the uneven color of the display part, according to the degree of color unevenness, When there is no color unevenness, it is set to "◎", and when there is a slight color unevenness, it is set to "○", and when there is a slight color unevenness, it is set to "△", and a large number of colors are uneven. The liquid crystal contamination was evaluated for "x".

In addition, the liquid crystal display elements evaluated as "◎" and "○" are at a level that is practically problem-free.

[Industrial availability]

According to the present invention, it is possible to provide a sealing compound for a liquid crystal dropping method which is excellent in photocurability and can suppress liquid crystal contamination. Moreover, according to the present invention, it is possible to provide a vertical conduction material and a liquid crystal display element which are produced by using the sealing compound for liquid crystal dropping methods.

Claims (1)

A sealing agent for a liquid crystal dropping method, comprising a curable resin and a photopolymerization initiator, wherein the photopolymerization initiator contains a compound represented by the following formula (1) and an oxime ester compound, and the oxime ester system The compound is at least one of 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzhydrylhydrazine) and a compound represented by the following formula (2) By, In the formula (1), R ¹ and R ² represent hydrogen or a -NR ³ ₂ group, and at least one of R ¹ and R ² is a -NR ³ ₂ group; and R ³ represents hydrogen or an alkyl group having 1 to 4 carbon atoms; Base; each R ³ may be the same or different; In the formula (2), X represents an alkylene group having 1 to 6 carbon atoms.