TW201209144A - Sealant for liquid crystal dropping method - Google Patents

Abstract

The purpose of the present invention is to provide a sealant for a liquid crystal dropping method, with which adhesion and humidity resistance of the cured product are excellent and there is virtually no liquid crystal contamination. The present invention is a sealant for a liquid crystal dropping method, which comprises a curable resin, a fluorine compound, and a photopolymerization initiator and/or thermosetting agent. The curable resin contains 50 wt% or more of a fully (meth)acrylic-modified epoxy resin obtained by reacting all of the epoxy groups in a starting epoxy resin with (meth)acrylic acid. The fluorine compound has reactive functional groups capable of reacting with the curable resin and contains 1.0 to 9.0 mass% of fluorine. The fluorine compound content is 0.1 to 5 parts by weight per 100 parts by weight of the curable resin.

Description

[Technical Field] The present invention relates to a sealing agent for a liquid crystal dropping method, which is excellent in adhesion and moisture resistance of a cured product, and hardly causes liquid crystal contamination. [Prior Art] In recent years, a method of manufacturing a liquid crystal display element such as a liquid crystal display unit has been gradually changed from a conventional vacuum injection method to, for example, Patent Document 1, from the viewpoint of shortening the takt time and optimizing the amount of liquid crystal. In the liquid crystal dropping method of the dropping method disclosed in Patent Document 2, a light-and-heat-hardening type sealant containing a photocurable resin, a photopolymerization initiator, a thermosetting resin, and a thermosetting agent is used in the dropping method. In the dropping method, first, a rectangular sealing pattern is formed on one of two transparent substrates with electrodes by dispensing. Next, in a state where the sealant is not cured, fine droplets of the liquid crystal are dropped onto the entire surface of the transparent substrate, and the other transparent substrate is immediately superposed, and the sealing portion is irradiated with ultraviolet light or the like to be pre-hardened. Thereafter, heating is performed during liquid crystal annealing to form a liquid crystal display element by performing main hardening. The liquid crystal display (4) can be manufactured with extremely high efficiency as long as the substrate is bonded under reduced pressure. At present, this dropping method has become a mainstream liquid crystal display element manufacturing method. As a result, a (hydroxyl) acrylate-modified epoxy resin having a hydroxyl group is used as a curable resin for a dripping method sealant because it is used for both photohardening and thermosetting, and The polarity is higher and the liquid phase is lower than the liquid phase, so the contamination of the liquid crystal can be effectively prevented. However, the hydrophilicity of the hardened tree will be improved by having a hydroxyl group, so there will be a decrease in the leak resistance of the sealed 201209144 agent. If the liquid crystal display element is driven after exposure to high temperature and high humidity, a liquid crystal display element will be produced. The problem of reduced reliability such as unevenness in color is not displayed. In order to improve the moisture resistance of the cured product of the sealant, it has been considered to use an inorganic filler, but in order to make the wettability of the cured product of the sealant excellent, it is necessary to blend a large amount of the inorganic filler, if a large amount of the inorganic filler is blended, Problems such as decreased adhesion of the sealant. Patent Document 1: JP-A-2001-133794 Patent Document 2: International Publication No. 2//No. 92,718 Booklet [Invention] It is an object of the present invention to provide a sealant for a liquid crystal dropping method, which is then Sexual and hardened materials have excellent moisture resistance and hardly cause liquid crystal contamination. The present invention is a liquid crystal dropping method sealing agent comprising a curable tree fluorinated s material, a photopolymerization initiator and/or a thermal hardener; the curable resin contains a complete (meth)acrylic modified epoxy resin 5% by weight or more, the complete (fluorenyl) acrylic modified epoxy resin is obtained by reacting all epoxy groups in the raw material epoxy resin with (meth)acrylic acid; the fluorine compound has ι and the hardening The reactive functional group in which the resin is reacted has an X gas content of 1 · 〇 9.0% by mass; and the content of the fluorine compound based on the weight of the curable resin is 0.1 to 5 parts by weight. The invention is described in detail below. The present inventors attempted to incorporate a fluorine compound into a sealant as a method of improving the wettability of a cured product of a sealant for liquid helium dripping. However, in order to prevent the contamination of the liquid crystal, it is necessary to provide the curable resin with a sufficient hydrophilicity of 201209144. As a result, there is a problem in that the highly hydrophilic curable resin is inferior in compatibility with the fluorine compound and cannot be sufficiently mixed to become cloudy. It is considered to be liquid crystal contamination caused by the fluorine compound itself. After further intensive studies, the present inventors have found that the present invention has a fluorine-containing compound having a reactive functional group reactive with a curable resin and having a fluorine content of 1.0 to 9.0% by mass, as long as it is in the range of a minimum of two. Even if the hydrophilic hydrophilic resin is sufficiently mixed, it does not cause liquid crystal contamination, and the moisture resistance of the cured product can be sufficiently improved. The sealing compound for liquid crystal dropping methods of this invention contains a hardening resin. The curable resin contains 5 % by weight or more of a wholly (fluorenyl) acrylate-modified cyclic oxime resin, and the complete (meth) acrylic acid-modified epoxy resin is used to make all of the epoxy groups in the raw material of the epoxy resin. It is formed by reacting with (meth)propionic acid. Since the above fully (meth)propene-modified epoxy resin has a warp group, the polarity is high and the compatibility with the liquid crystal is low. By using the content of the complete (fluorenyl) acrylic acid-modified epoxy resin in the curable resin as % by weight', when the liquid crystal display element is produced by the dropping method using the sealing compound for liquid crystal dropping method of the present invention Will pollute the liquid crystal. The curable resin preferably contains 6% by weight or more of the above-mentioned completely (meth)-glycolic acid-modified epoxy resin, more preferably 70% by weight or more, more preferably 8% by weight or more. . In the present specification, the term "(meth)acrylic acid" means propylene fosphate or propylene terephthalate. Among them, the 'methacryl oxime-modified epoxy resin is preferred because it has superior moisture resistance to the cured product. The above fully (meth) acryl-modified epoxy resin can be prepared, for example, by the following method 201209144: methacrylic acid and an epoxy resin are reacted in the presence of an inert catalyst in accordance with a general method. The epoxy resin which is a raw material of the yttrium-based (f-based) acrylic acid-modified epoxy resin is not particularly limited, and examples thereof include a double-prepared A-type epoxy resin, a double-aged F-type epoxy resin, and a double-twisted epoxy resin. , 2,2, _ diallyl bismuth A type epoxy resin, hydrogenated biguanide type epoxy resin, propylene oxide addition (four) type A epoxy resin, isophthalene type epoxy resin, biphenyl type ring Oxygen resin, sulfide type epoxy resin, diphenyl surface type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, benzoquinone varnish type epoxy resin, neighboring age expectation ^ ' Month paint type epoxy resin, dicyclopentadiene secret varnish type epoxy resin, Lianben Pan I month paint type oxy-resin, naphthalene benzoquinone varnish type epoxy resin, epoxy propyl amine type epoxy resin, The hospital-based polyol type epoxy resin, rubber modified type oxygen resin, epoxy propylene compound, and bismuth A type episulfide resin. Among the above-mentioned double-anti-type A-type epoxy resins, 丽ΕΡΙΚΟΤΕ te 828EL, ΕΡΙΚΟΤΕ 1〇〇4 (both rabbit-萁儿)

(White is manufactured by Mitsubishi Chemical Corporation), EPICLON 850-S (manufactured by DIC Corporation), and the like. The above bisphenol F type epoxy resin in the city

As a commercial item of the bait fine T, EPIKOTE 06 'EPIKOTE 4004 (all manufactured by Mitsubishi Chemical Corporation) and the like can be cited. Among the above bisphenol S type epoxy resins

1 faint person, such as EPICLON EXA1514 (manufactured by DIC Corporation). Among the commercially available ones of the 2,2'-di-propylidene-type A-type epoxy resins, RE-8100 (manufactured by Nippon Kayaku Co., Ltd.) and the like can be mentioned. Among the above-mentioned nitrogen-added double-aged epoxy resins, 201209144 EPICLON EXA7015 (manufactured by DIC Corporation) and the like can be cited. The above-mentioned oxidized propylene-addition type A-type epoxy resin is commercially available, and EP-4000S (made by Adeka Co., Ltd.) etc. are mentioned. The commercially available one of the above-mentioned resorcinol-type epoxy resins is EX-201 (manufactured by Nagase ChemteX Co., Ltd.). The commercially available ones of the above-mentioned biphenyl type epoxy resins include EPIKOTE YX-4000H (manufactured by Mitsubishi Chemical Corporation). The commercially available one of the above-mentioned sulfide-type epoxy resins is YSLV-50TE (manufactured by Nippon Steel Chemical Co., Ltd.). The commercially available one of the above-mentioned diphenyl ether type epoxy resins may, for example, be YSLV-8OODE (manufactured by Shinkai Iron Chemical Co., Ltd.). The commercially available one of the above-mentioned dicyclopentadiene type epoxy resins may, for example, be EP-4088S (made by Adeka Co., Ltd.). Examples of the naphthalene type epoxy resin include EPICLON HP4032 and EPICLON EXA-4700 (all manufactured by DIC Corporation). The commercially available ones of the phenol novolac type epoxy resins include EPICLON N-770 (manufactured by DIC Corporation). The commercially available ones of the above o-cresol novolac type epoxy resins include EPICLON N-67 0-EXP-S (manufactured by DIC Corporation). 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 may, for example, be NC-3000P (manufactured by Nippon Kayaku Co., Ltd.). The commercially available one of the naphthol phenol novolak type epoxy resins is exemplified by 7 201209144 ESN-165S (manufactured by Nippon Steel Chemical Co., Ltd.). Among the above-mentioned epoxy propylamine type epoxy resins, 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 can be given. The commercially available ones of the above-mentioned alkyl polyol type epoxy resins include ZX-1542 (manufactured by Nippon Steel Chemical Co., Ltd.), EPICLON 726 (manufactured by DIC Corporation), EPOLIGHT 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.), and DENACOL. EX-611 (manufactured by Nagase ChemteX Co., Ltd.). Among the above-mentioned rubber-modified epoxy resins, YR-450, YR-207 (all manufactured by Nippon Steel Chemical Co., Ltd.), EPOLEAD PB (manufactured by DAICEL Chemical Industry Co., Ltd.), and the like can be given. Among the above-mentioned glycidyl ester compounds, DENACOL EX-147 (manufactured by Nagase ChemteX Co., Ltd.) and the like can be mentioned. Among the above-mentioned bisphenol A type episulfide resins, EPIKOTE YL-7000 (manufactured by Mitsubishi Chemical Corporation) and the like can be mentioned. Other commercially available ones of the above-mentioned epoxy resins include YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Nippon Steel Chemical Co., Ltd.), XAC4 15 1 (made by Asahi Kasei Corporation), EPIKOTE 1031, EPIKOTE. 1032 (all manufactured by Mitsubishi Chemical Corporation), EXA-7120 (made by DIC Corporation), TEPIC (manufactured by Daicel Chemical Co., Ltd.), and the like. Among the above-mentioned complete (meth)acrylic modified epoxy resins, EBECRYL 860, EBECRYL 3200, EBECRYL 3201, EBECRYL 3412, EBECRYL 3600, EBECRYL 3700, EBECRYL 3701, EBECRYL 3702, EBECRYL 3703, s 8 201209144 EBECRYL 3708, EBECRYL 3800, EBECRYL 6040, EBECRYL RDX63182, KRM8287 (all manufactured by DAICEL CYTEC), EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, EMA-1020 (all Xinzhongcun Chemical Industry Co., Ltd.), epoxy ester 40EM, epoxy ester 70PA, epoxy ester 80MFA, epoxy ester 200EA, epoxy ester 200PA, epoxy ester 400EA, epoxy ester 1600A, epoxy ester 3000A, epoxy Ester 3000M, epoxy ester 3002A, epoxy ester 3002M, epoxy ester Μ-600Α (all manufactured by Kyoeisha Chemical Co., Ltd.), DENACOL acrylate DA-141, DENACOL acrylate DA-314, DENACOL acrylate DA - 911 (all manufactured by Nagase ChemteX), etc. The curable resin preferably further contains a resin having an epoxy group. The epoxy group-containing resin is not particularly limited, and examples thereof include an epoxy resin as a raw material for synthesizing the above-mentioned complete (meth)acrylic acid-modified epoxy resin, or an epoxy resin in a part of the raw material epoxy resin. A (meth)acrylic modified epoxy resin obtained by reacting a group with (fluorenyl) acrylic acid. Among them, a partial (fluorenyl) acrylic modified epoxy resin is preferred, and a part of the methacrylic modified epoxy resin is more excellent because of its excellent moisture resistance. In the present specification, the above-mentioned partial (fluorenyl) acrylic acid-modified epoxy resin refers to a resin having one or more epoxy groups and (fluorenyl) acryloyloxy group in one molecule. The above-mentioned partial (meth)acrylic acid-modified epoxy resin can be obtained, for example, by reacting an epoxy group which is a part of an epoxy resin having two or more epoxy groups with (mercapto)acrylic acid. When the curable resin contains the epoxy group-containing resin, the ratio of the ratio of the (meth)acryl fluorenyloxy group to the epoxy group 201209144 in the entire curable resin is preferably a ratio of the epoxy group. It is 3G Mo %. When the ratio of the above epoxy groups is more than 30 mol%, the solubility of the liquid crystal of the sealant becomes high, causing liquid crystal contamination, and the display performance of the obtained liquid crystal display element is deteriorated. A more preferable upper limit of the ratio of the above epoxy groups is 2% by mole. The sealing compound for liquid crystal dropping methods of this invention contains a fluorine compound. By blending a fluorine compound, the moisture resistance of the cured product can be remarkably enhanced. The fluorinated port material ' has a reactive functional group (hereinafter also simply referred to as "reactive functional group") which can react with the curable resin. By having the above-mentioned reactive functional group, it is possible to bind the chaotic compound to the curable resin at the time of curing, and it is possible to prevent liquid crystal contamination from the fluorine compound. In the present specification, the above-mentioned reactive functional group means a functional group which can be reacted with the above-mentioned curable resin by light or light. The reactive functional group may, for example, be a functional group having a double bond such as a (meth) acryloyloxy group or a styrene group which undergoes a radical polymerization reaction or a Michael addition reaction (10) chael addition reaction. Or a cyclical nucleus such as an epoxy group or an oxetane group (〇xetanyl g_p) which undergoes a nucleophilic addition reaction by a curing agent or the like. Wherein ' is preferably a (meth) acryloyloxy group. Further, in the present specification, the above (meth) acryloyloxy group means an acryloyloxy group or a methacryloxycarbonyl group. The above I compound is preferably! In the molecule, there are two or more reactive functional groups (that is, the above-described gas compound is bifunctional or more, and the elution into the liquid crystal can be further suppressed. The lower limit of the fluorine content of the fluorine compound is 1 〇, and the upper limit is 9. If the content of the fluorine compound is less than 1% by mass, the effect of improving the moisture resistance of the cured product is hardly confirmed in 201209144, and if it exceeds Η% by mass, the compatibility with the above-mentioned curable resin is obtained. It is difficult to achieve a sufficient moisture resistance improving effect by blending the compound into a sealant: the preferred lower limit of the gas content is 3. 〇 mass%, and the preferred upper limit is The lower limit of 8〇 is 4.〇% by mass, and the upper limit is 7.5. Further, the fluorine content in the present specification means the mass ratio of I atom in the fluorine compound (that is, in the following manner) The molecular weight of the fluorine atom is calculated by the molecular weight of the fluorine compound xl00. The above-mentioned compound preferably has a hydrophilic functional group in addition to the above reactive functional group. #The above gas compound has hydrophilicity g Since the base 'is exhibits the property of agglomerating on the surface of the sealant, the surface of the sealant can be modified to further improve the moisture resistance of the cured product. The hydrophilic functional group is not particularly limited, and examples thereof include a base and an interesting a group, a fluorenyl group, a phosphonium group, an amine group, a decyl group, a transamination group, a thiol group, a thioether group, etc. The SP value of the above fluorine compound is preferably 17 Å or more. If the above-mentioned gasification is equivalent to the SP value When the amount is less than 17., the compatibility with the above-mentioned curable resin is deteriorated, and :: the fluorine compound is blended into the sealant to achieve a sufficient moisture-improving effect. The fluorine value of the above fluorine compound is better. The above is more than 20.0. In addition, the _SP value in this specification refers to the solubility parameter obtained from the following equation using the Fedor's push algorithm. Solubility parameter (%) = (Σ Ecoh/ Σ V) 1/2 Among the above fluorine compounds, a compound represented by the following formula (1) is preferred (example 201209144, for example, OMNOVA company 劁袢+士#

a compound of the formula PF-3320) or a commercially available compound of the DIC △ R 〇 〇 〇 s s s s ( , , , , , , , , , , , , , , , , 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 与 与 与 与 与 与 与 与It is excellent in moisture absorption resistance. The balance between the two is very good, so it is especially good.

In the above formula (1), n represents an integer of 1 to 20. The content of the fluorine compound is 0.1 part by weight based on 1 part by weight of the curable resin, and the upper limit is 5 parts by weight. If the content of the above compound is less than 1 part by weight, the effect of sufficiently improving the moisture resistance of the cured product cannot be obtained. When the content of the fluorine compound exceeds 5 parts by weight, it is difficult to mix with the curable resin, and there is a problem that the liquid crystal display element is not uniform in color due to liquid crystal contamination. A preferred lower limit of the content of the above fluorine compound is 0.2 part by weight, a preferred upper limit is 4 parts by weight, a still lower limit is 0.5 part by weight, and a more preferred upper limit is 3 parts by weight. The sealing compound for liquid crystal dropping methods of the present invention contains a photopolymerization initiator and/or a thermal curing agent. It is preferable that the curable resin contains a photopolymerization initiator when photocurable, and contains a thermosetting agent when it has thermosetting property, and contains a photopolymerization initiator and a thermosetting agent when it has photocurability and thermosetting property. By. The photopolymerization initiator is not particularly limited, and for example, a dimercapto ketone compound, an acetophenone compound, a mercapto phosphine oxide system 12 201209144 compound, a titanocene compound, an oxime ester can be preferably used. A compound, a benzoin ether compound, a 9-oxysulfur D star, or the like. Further, among the above-mentioned photopolymerization initiators, IRGACURE 184, IRGACURE 369, IRGACURE 379, IRGACURE 651, IRGACURE 819, IRGACURE 907, IRGACURE 2959, IRGACURE OXEOl, and Lucirin TPO (all manufactured by BASF Japan) ), benzoin decyl ether, benzoin ethyl ether, benzoin isopropyl ether (all manufactured by Tokyo Chemical Industry Co., Ltd.), and the like. Among them, IRGACURE 651, IRGACURE 907, benzoin isopropyl domain, and Lucirin TPO are preferred because of the wide absorption wavelength region. These photopolymerization initiators may be used singly or in combination of two or more. The content of the photopolymerization initiator is not particularly limited, and is preferably 〇·1 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 sealant may not be sufficiently performed. When the content of the photopolymerization initiator is more than 1 part by weight, the unreacted photopolymerization initiator remains largely, and the weather resistance of the obtained sealant may be deteriorated. A more preferred lower limit of the content of the photopolymerization initiator is 1 part by weight, and a more preferred upper limit is 5 parts by weight. The above-mentioned thermosetting agent is not particularly limited, and examples thereof include organic acid 肼 肼 and ° m. A derivative, an amine compound, a polyvalent benzoquinone compound, an acid anhydride, or the like. Among them, a solid organic acid hydrazine can be preferably used. The above solid organic acid hydrazine is not particularly limited, and examples thereof include 1,3 - bis(indenylethyl)-5-isopropylethylcarboate (1,3 - bis(hydrazino carboethyl) - 5 - Isopropyl hydantoin), diterpene azelaic acid, isoindole 13 201209144 diterpene diacetate, diammonium adipate, malonic acid, etc., for example, AJICURE VDH, AJICURE UDH (all are Ajinomoto Fine-Techno Co., Ltd., SDH, IDH, ADH (all manufactured by Otsuka Chemical Co., Ltd.), etc. The sealing agent for liquid crystal dropping method of the present invention may further contain an organic peroxide compound or a thermal radical such as an azo compound. Polymerization initiator. The above thermal radical polymerization initiator may preferably use a lower limit of a half hour temperature of 10 hours of 80. (The upper limit is 150. (The: The above-mentioned organic peroxide-based compound, specifically, for example, a ketone peroxide compound such as methyl ethyl ketone peroxide, or a bis- 2 (three-stage) A peroxy ketal compound such as butyl-oxy)cyclohexane or an alkylperoxy ester compound such as tributyl butyl peroxybutyrate or a dimercapto peroxide such as dilaurinyl peroxide a compound, a peroxydicarbonic acid curable compound such as peroxydicarbonate (2-ethylhexyl) carbonate, or a peroxycarbonic acid I-based compound such as peroxyisopropyl carbonate third-grade butyl vinegar, a di-tertiary butyl peroxide Examples of the hydroperoxide compound such as a dialkyl peroxide compound or a tertiary pentyl hydroperoxide. Specific examples of the azo compound include 2, 2, and an azobis [(2). Oil-soluble azotium 5 such as water-soluble oxime, such as imidazoline-2-yl)propane]disulfate dihydrate, and [[cyano-1-methyl)azo]carbamamine The content of the thermal radical polymerization initiator is not particularly limited, and the preferred lower limit is 0.01% by weight, and the preferred upper limit is 30% by weight. In order to improve the viscosity 'stress dispersion effect, Me has good adhesion, change, linear expansion coefficient, and further improve the wettability, the 201209144 liquid crystal dropping method of the present invention uses 脔4 as the 丨^ The sealant preferably contains a filler. The above fillers are not classified. ^ Oxide oxide, Shixia thin soil Y n can be exemplified by talc, asbestos, smectite, montmorillonite, carbonic acid, carbonic acid, titanium oxide oxide. , magnesium hydroxide, zinc oxide, iron oxide, magnesium oxide, tin oxide, antimony, s #., wind alumina, glass beads, tantalum nitride, barium sulfate, gypsum, calcium citrate, scorpion夂 酿 颗粒 颗粒 颗粒 颗粒 颗粒 颗粒 颗粒 颗粒 颗粒 颗粒 颗粒 颗粒 颗粒 颗粒 颗粒 颗粒 颗粒 颗粒 颗粒 颗粒 颗粒 颗粒 颗粒 颗粒 颗粒 颗粒 颗粒 颗粒 颗粒 颗粒 颗粒 颗粒 颗粒 颗粒 颗粒 颗粒 颗粒 颗粒 颗粒 颗粒 颗粒 颗粒 颗粒 颗粒 颗粒 颗粒 颗粒 颗粒 颗粒 颗粒 颗粒It is not particularly limited, and the lower limit is preferably 5 parts by weight, and the upper limit is 4 parts by weight, based on the hardening fragrant portion, and if the filler is added to the weight of the c' Fully obtained:: True: the effect brought by the above filler The amount (4) 4 〇 weight = the adhesiveness or the descriptive property of the sealing agent for liquid crystal dropping method. The lower limit of the content of the above-mentioned filling is ι 〇, and more than 35 parts by weight. The sealant preferably contains the above-mentioned oxime coupling agent of Shi Xi Yuan Coupling 1 and mainly functions as a bonding aid for adhering well to the sealing agent and the substrate. The above-mentioned decane coupling agent is not particularly limited, and is improved by The effect of the adhesion of the substrate or the like is excellent, and the curable resin can be prevented from flowing out into the liquid crystal by chemical bonding with the curable resin. Therefore, for example, r-aminopropyltrimethoxydecane, r can be preferably used. - Mercaptopropyltrimethoxy oxime: r-glycidoxypropyltrimethoxy sylvestre, isocyanurate propyl decyloxy decane, etc. "The decane coupling agents can be used alone or And 15 201209144 use two or more. The sealing agent for liquid crystal dropping method of the present invention can also be used as a reactive diluent for adjusting the viscosity, and for adjusting the gap of the panel: a spacer such as a bead, 3 - p - - Tian and An additive such as a hardener such as a ruthenium group, a ruthenium or a ruthenium-based urea, a stress relieving agent, an antifoaming agent, or a polymerization inhibitor. The method for producing the sealing agent for a liquid crystal dropping method of the present invention is not particularly limited. For example, a method such as a homogenizer, a homomixer, a planetary mixer, a kneader, a two-roll mill, or the like may be used, and the curable resin and fluorine may be used. Addition of an additive such as a compound, a photopolymerization initiator, and/or a thermosetting agent, and a decane coupling agent to be added as needed. The preferred lower limit of the glass transition temperature (Tg) of the sealing agent for liquid crystal dropping method of the present invention after hardening 80: (:, the upper limit is preferably 15 〇〇 c ^ If the Tg is less than 80 C, the moisture resistance (high temperature and high humidity resistance) of the obtained liquid crystal display element may be deteriorated. If the above Tg exceeds 15 (TC, sometimes too straight, with In addition, the above-mentioned Tg is a value measured by a DMA method at a temperature increase rate of 5. (: / min, frequency 10 Hz. However, a large amount of sample is required for the Tg measurement by the DMA method. Therefore, in the case where only a small amount of sample can be obtained, it is preferable to carry out the measurement under the conditions of the temperature increase rate 丨〇〇c / min by the DSC method. In general, the Tg measured by the DSC method is more expensive. The Tg measured by the DMA method is lower by about 30 C. Therefore, in the case where the Tg is measured by the DSC method, the preferred lower limit of the Tg of the sealing agent for liquid crystal dropping method of the present invention after curing is 50 ° C, preferably the upper limit. According to the present invention, it is possible to provide a sealant for a liquid crystal dropping method, which is excellent in adhesion property and moisture resistance of a cured product, and hardly causes liquid crystal contamination. [Embodiment] In the present invention, the present invention is not limited to the above examples. (Example 1) A bisphenol A type epoxy acrylate ("EBECRYL 3700", manufactured by DAICel CYTEC Co., Ltd.), which is a curable resin, is used. Complete (mercapto) acrylic modification Epoxy resin) 30 parts by weight, caprolactone modified bisphenol A type epoxy acrylate vinegar (DAICEL CYTEC company, "EBECRYL 3708", complete (meth) acrylic modified epoxy resin) 30 parts by weight, and 25 parts by weight of a partially modified bisphenol f-type epoxy resin ("KRM8287" manufactured by DAICEL CYTEC Co., Ltd.), and reacted with PF-3320 (a compound of the above formula (1) manufactured by 〇MNOVA Co., Ltd. as a fluorine compound. The functional group (bifunctional) and the fluorine content were 7.5% by mass. The SP value was 19.5. The fluorine content and the SP value were the average values of the polymers. 1 part by weight, and 2 parts by weight of 2,2-dimethoxy-2-phenylacetophenone ("IRGACURE 65 1", manufactured by BASF Japan Co., Ltd.) as a photopolymerization initiator 6 parts by weight of a bismuth sebacate ("SDH" manufactured by Otsuka Chemical Co., Ltd.) as a thermal curing agent, and 25 parts by weight of cerium oxide ("SO-C1" manufactured by ADMATECHS Co., Ltd.) as a filler, as a decane couple R-glycidoxypropyltrimethoxy sulphate ("KBM-403", manufactured by ShinEtsu Silicones Co., Ltd.) 2 parts by weight, core-shell acrylate copolymer microparticles as a stress relieving agent (Ganz 17 parts by weight of "F351" manufactured by Chemicals Co., Ltd. was blended with a planetary stirring machine (Awatori-Rentaj_, manufactured by THINKY Co., Ltd.), and then uniformly mixed with a ceramic three-roll mill to obtain a sealant. (Examples 2 to 1 and Comparative Examples 1 to 11) A sealant was obtained in the same manner as in Example 1 except that the materials to be used and the blending amount were as shown in Table 2. Fluorine compound A, by the following Prepared by the method. Add the fluorine compound 3〇〇§ shown in the following formula (2-丨) to a 50〇mL four-necked flask equipped with a putter, a thermometer, a Daimler condenser, and a dropping funnel. 5.62 g of 2-hydroxyethyl methacrylate, 36 36 g of triethylamine and 0.015 g of butyl hydroxy fluorene were dissolved in hexafluorodimethyl 3 〇g, and the solution was dropped into the flask under nitrogen atmosphere. After aging at 50 ° C for 2 hours, a perfluoroalkane solvent (3M company, PF-5080, a component of the main component cj丨8), 300 g, and 200 g of pure water were added to the flask to perform liquid separation. The recovered components of the lower layer were recovered. After washing the recovered components twice, they were washed 3 times with methanol 2 〇〇g, washed twice with 200 g of hexane, and stripped at 65 ° C and 267 Pa for 2 hours. The colorless transparent fluorine compound a shown in the following formula (2-2) is obtained. 0 0 FC-CCFOCFa^O^OCF^iF (2-i) iFa cf3 average of e+f=1〇〇H2C=C—COC2H4〇 C-<CFOCF2%<CF2〇CF)rfi〇C2H4〇6-0=CH2 (2·2) CF3 CF3 The fluorine compound B' used in Comparative Example 7 was prepared by the following method. 201209144 Fluorine xylene 1 00g, bisphenol A Epoxy resin (manufactured by Sakamoto Chemical Co., Ltd., RE-310S) 15.8 g, triphenylphosphine ruthenium. 12 g was placed in a 500 mL glass separable flask equipped with a mixing and reflux condenser, and kept at l2〇. °C, while stirring, the fluorine-containing carboxylic acid (Fluorolink CIO, d + e = 14, weight average molecular weight of about 1400) 50 g «dropped by the following formula (3) was dropped into the following formula. The reaction was allowed to proceed for 24 hours under i2〇t. After the reaction, after returning to room temperature, it was reprecipitated in toluene. The precipitate was dissolved in hexafluoro-m-xylene, and the solution was further washed with water until the conductivity of the extracted water was 3.0/1 S/cm or less. After completion of the washing, the organic layer was subjected to azeotropic dehydration to remove water, and then the solvent was removed under reduced pressure to obtain a fluorine compound B. 〇

I II H0CCF20—(CF2CF20)d-(CF20)—CF2C〇H (3) <Evaluation:> The sealants obtained in the examples and the comparative examples were subjected to the following evaluations. The results are shown in Tables 1 and 2. (1) Compatibility The machine sacrifices mixed hard — •...~, machine. When the object is in the state of the object, the person who is transparent is rated as "〇", and the person who is slightly suspended but still transparent is rated as △"", and the person who is unclear and unmixable is rated as "χ". Further, since the sealant obtained in Comparative Example 1 was not a fluorine-containing compound, the compatibility of the sealant was not evaluated. 201209144 (2) Glass transition temperature The sealing agent obtained in the examples and the comparative examples was irradiated with ultraviolet rays of 3 〇〇〇mJ/cm2, and then 120. (: After heating for 60 minutes, it was completely cured, and a film having a thickness of 300 // m was obtained as a test piece. A dynamic viscoelasticity measuring device ("DVA-200" manufactured by IT Corporation) was used, at _80~2〇 (The dynamic viscoelasticity of the obtained test piece was measured at rc and 1 Hz, and the maximum temperature of the loss tangent (tan5) was determined as the glass transition temperature (Tg). (3) Water absorption rate was obtained in the examples and comparative examples. After the sealant was irradiated with ultraviolet rays of 3 〇〇〇mJ/cm2, it was completely cured by heating at 60 °C for 60 minutes, and a film of .5 g and a thickness of 100 Å was used as a test piece. The obtained test piece was subjected to 12 TC. The PCT test at 100% RH and 1 atm was used for 2 hours, and the ratio of the weight change before and after the pCT test was measured as the water absorption rate. (4) The liquid crystal specific resistance was evaluated by measuring the specific resistance of the liquid crystal to the liquid crystal contamination caused by the sealant. The sealing agent 〇lg obtained in the examples and the comparative examples was added to a 2 〇ml sample vial to irradiate ultraviolet rays of 3000 mJ/cm 2 , and then 0.5 g of TN liquid crystal ("JC - 5001LA" manufactured by Chins Co., Ltd.) was added thereto, and the measurement was carried out at 12 Torr. <^ The specific resistance of the liquid crystal after heating for 6 minutes. With respect to the sealant obtained in Comparative Example 1, the liquid crystal specific resistance value was rated as "〇" or higher than the value of the sealant using Comparative Example 1, and was lower than the value of the sealant using Comparative Example 1. (5) Subsequent to the sealant obtained in the examples and comparative examples, 1 part by weight, 20 201209144 Polymer beads with an average particle size of 5 " m in a planetary mixer 3 parts by weight of "Micropearl SP" manufactured by Sekisui Chemical Co., Ltd., and made a uniform dispersion. Take a very small amount to the center of Corning glass 1737 (20mmx50mmxl.lmmt), and laminate the same type of glass onto it. After the liquid crystal dropping method was applied to the ultraviolet ray of 300 〇mJ/cm 2 with a sealant, the test piece was obtained by 12 (Γ: heating 6 〇. Using a tensiometer, the test piece was measured on the test piece of the wilderness ( The comparison unit is N/cm2). Next, the pill is a j. The strength value is 15 or more, and the rating is 〇"', the number is less than 150, and the evaluation is "X test 21 201209144 I official case 1〇| u> CO 〇<;0 to (NJ 1 1 4. 5 I 1 1 1 1 1 CM CO (Μ 10 CSI η 00 〇| 20, 0 | 5. 0 <3 00 d 0) h* r- 〇〇I苜Example 9| 10 CO g in M 1 丨2.7 | 1 1 1 1 1 CM Μ 10 CSI ο 00 〇〇6 Ν 3. 0 〇CO CD CO 0 0 I Official Example 8 | 10 CO 〇C5 in (SJ 1 - 1 1 1 1 1 (Si <D CM 卜 c> CD 〇 〇 · Μ Μ Μ r r r ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( 1 0 0 IExample 7 I r> 〇C5 tn N 1 10 6 1 1 1 1 1 M to CM U> Μ r> CO 咩〇pv 〇6 Ν (0 tft d Ο 00 0) ΰ in N Ο 0 I) Example 6 | U) ¢0 〇<0 in CM 1 6 1 1 1 1 1 W to CM r* U> CM n 00 〇〇6 Ν d 0 | 93. 5 1 U) n Ο 0 I Official Example 5 (A CO g in N tn tr 1 1 1 1 1 1 <Si to CM ** (Λ CM n CO u> 〆Lu" 5. 0 <3 •cr σ> 10 0 0 I Example 4 I 10 Π Ο CO m N w 1 1 1 1 I 1 M (0 N h* r- ΙΑ CM n GO lf> One 1 19.0 | 3. 0 〇to CO σ> i 1 79 1 0 0 I Official Example 3 I 10 (0 ο Λ in N o 1 1 1 1 1 1 W CD 04 h' U> N r> CO 咩10 丨 19. 〇丨r« τ~· 0 (0 ,· σ> 0 σ> 0 0 I苜Example 2 I CO Ο ο (Ω CM ID d 1 \ 1 1 1 1 N 1 M Γν CM CO in 〆体〇0> 0. 5 6 0 00 in σ> 0) n N 〇0 I official example 1 I If) CO ο <0 m (SJ d 1 1 1 1 1 1 W CO U b tf> N n CO 咩ΙΛ 丨19, 〇 I r- 严6 〇σ» w σ> 卜o CO 0 〇| Bisphenol A type qi acrylate 1 defensive Elf rU pair <r blister do P PF-3320 | | RS-72 1 I Fe compound A 1 1 gas compound B 1 R-08 1 | F—477 | F-489 | 1 枨 枨 II呦1枨~ 1 CVJ CVi 1 eric acid diterpenoid 1 1T - 琛 ft ft ft Propyl trimethyl δ ϊ 砂 sand now 1 1 core - foreign Yi propionic acid copolymer microparticles 1 1 dioxide oxidized 1 軏 s tot ISD material (3⁄43⁄4 mn £ coffee 4H<(D m sauce s- ij #( ¢1 Wish Q〇雅Η {崎却屮®<R Zhao 3 1 Gas content (% by mass) 1 | Hydrophilic 莒 energy base | I spfi | 咖hill ΙΡΠ i 53⁄4 如 mm 1相相性 ι 1 Τβ(Χ) 1 I water absorption φ (%> ι 1 liquid crystal than electric Ρ and ι 1 connected to bodhisattic I hardening resin s chemical inclusion 1 cooked hardening thorn 1 1 chopping coupling 剌 1 | stress 锃 and 剌 | 1 1料1 fe compound composition (parts by weight) Comments ms 201209144 1Comparative Example 11 1 〇〇C0 sd 1 i 1 1 1 1 CSI CM Μ r- in CM z Body tD body 〇σί 1— r· do GO 5 3. 35 | X o 1 Comparative example ιο |£> CO ο ο tc CSJ 1 1 1 1 1 1 r· 6 CM (f> CM r> 1—in w to CO mr· yield d 0 \fj pj σ> 0) τ- cvi X o 1 Comparative Example 9 (0 C0 ο CO w C\J 1 1 1 1 1 d 1 CJ <D r ΙΟ 0J W GO 戚严6 0 ω od 〇〇 in oi X 0 |Comparative Example 8 to « ο C0 to N 1 1 1 1 6 1 1 CM <P CM h· (Ω N «> Deer»— Τ Ο 0 CO a (0 Bu X 0 |Comparative Example 7 <0 ο ο to N 1 i 1 Production 6 1 1 1 OJ (0 CM r* ΙΟ M CO l"_〇· 5 I m 1 — ώ Production — *— 6 X Oa 00 2. 41 | o 0 |Comparative Example 6 ¢0 ο C9 t£> CM 1 1 r- 6 1 1 1 1 W Φ N r» CM Γ0 00 Body ο Κ φ 〇 〇 csi r· 6 X 芍CD 00 (0 σ> T-oo | Comparative Example 5 ΙΟ TO ο \D CM 1 o 1 1 1 1 1 CM Φ r- Strict 10 CSJ to m ο Body 20. 0 1 Factory" X to 〇i GO ( 0 r- r· X 0 |Comparative Example 4 to <0 ο <0 to CM 1 ID 1 1 1 1 1 N <ύ CM 1Ω N c»> 00 Body ο κ W 20. 0 J φ to X Let CO σ> JN rr· X o I Comparative Example 3 ID « ο η 10 N o r- 1 i 1 1 1 1 Φ W τ- in N o eo body u> 卜 'body Ο β) »- r- X r- (ΝΪ 00 NWX 0 I Comparative Example 2 to o S ID (V) 10 1 1 1 1 1 1 CM (0 MU) CM «* > to body i/> 1 body 1 19. 0 I > 0 to X CD r- OD t- (0 r* X 0 I Comparative Example 1 to <0 ο €0 ID N 1 1 1 1 1 1 1 CM Φ W in N t*> 00 IIIIII \i) r- 00 ID r* ro I o Avoid «φ< IS! t iH «t overflow m Lithium-ion city Ε! 5 riJitl <r s with ttS. Li. mi | PF—3320 | RS-72 1 fe compound A ] 1 fe compound BI | R-08 | 丨F— 477 | F-48Q 1 1 Secret Wff\] fr枨\mim ,1 CSJ CSI 1 azelaic acid dioxane trap 1 1丫一冢&propenylpropyltrimethyl gas-based sand is II core-external acrylic ruthenium copolymer 撖 ΐ I II gasification chopping I sclerosing elk i butterfly { On 妇钽屮m<R l£Sc gas content (% of the ear) | Hydrophilic function® with or without I spfa | # ifnll wi 1| ifi idjg em paid s compatibility I Tgi^c) | ) Liquid crystal than electric sister I Bodhisattva I Hardening resin gas compound 1 Thermal hardening stroke 1 1 Chopping coupling agent 1 I stress sputum agent | I 埴 I I gas compound composition (Heman) » 8Κ 23 201209144 [Industrial Applicability] According to the present invention, it is possible to provide a sealing agent for a liquid crystal dropping method which is excellent in the wettability of the adhesion and the cured product, and which hardly causes liquid crystal contamination. [Simple description of the diagram] None [Key component symbol description] None 24

Claims (1)

201209144 VII. Patent application scope: 1. A sealing agent for liquid crystal dropping method, comprising a curable resin, a fluorine compound, a photopolymerization initiator and/or a thermal hardener; the curable resin contains complete (methyl) propylene glycol The modified epoxy resin is 5% by weight or more, and the complete (meth)acrylic modified epoxy resin is obtained by reacting all epoxy groups in the raw material epoxy resin with (mercapto)acrylic acid. The reactive functional group capable of reacting with the curable resin has a fluorine content of 1.0 to 9.0% by mass; and the fluorine compound is added in an amount of 0.1 to 5 parts by weight based on 1 part by weight of the curable resin. 3 Rain 2_ As in the sealing agent for liquid crystal dropping method of claim 1, the reactive group having two or more reactive groups with the curable resin is contained in one molecule. 3. A sealant for liquid crystal dropping method according to the scope of the patent application, which has a hydrophilic functional group in addition to the reactivity s which can react with a curable resin. 4. If the gas compound in item i of the patent application scope has an sp value of 17 or more. "going with a sealant" to vaporize it. The compound is a compound represented by the following formula, ..., a sealant, Integer of 20 5. In the liquid crystal of patent application 帛i, OCH2CF3 25 (1)