TW201242986A - Liquid crystal sealing agent, fabricating method of liquid crystal display panel using the same and liquid crystal display panel - Google Patents

Abstract

The object of this invention is to provide a liquid crystal sealing agent good in storage stability and able to form a sealing part with slim line width. The liquid crystal sealing agent includes: (1) a (meth)acrylic modified epoxy resin having an epoxy group and a (meth)acrylic group in a molecular, (2) a curing agent and (3) a photo initiator, wherein the component (2) is two or more curing agents selected from a group consisting of a poly phenol curing agent with a soften point of 50 to 90 DEG C, a secondary polythiol curing agent with a melting point of 23 DEG C or less, and a primary polyamine with a melting point of 60 to 180 DEG C. The content of the component (2) is 4 to 30 part by mass based on 100 parts by mass of the liquid crystal sealing agent.

Description

[Technical Field] The present invention relates to a liquid crystal sealing agent, a method of manufacturing a panel using the same, and a liquid crystal display panel. Item [Prior Art] In recent years, as a mobile phone or a personal computer, you can use a liquid crystal display panel. The liquid crystal display panel has the following structure: a liquid-correcting material (hereinafter = 2 liquid crystal) of two flip-chip substrates of the = electrode and is sealed by a liquid crystal sealing agent. a; for the pre-film production method [manufacturing method of liquid crystal display panel - liquid crystal dropping method. The liquid crystal dropping method is the following method: (1): Yes = coating the liquid crystal sealing agent to form a frame; (2) in the month = ::== two = making liquid; hardened liquid crystal sealing agent. For example, in the above: first: =: etc. (4) After hardening, in (4) Step 2::: Sexual disc (four) agent 'has been proposed to contain both UV curing. 2). The resin component is contained in the above-mentioned resin composition. The above-mentioned resin component is added together with a hardening agent for ultraviolet light=two agents and a heat curing agent. Starting from the viewpoint of workability, the liquid crystal sealing agent is desirably set to - 4 201242986 liquid type. However, when the above resin component and the curing agent are contained in one liquid, the components are reacted at the time of storage. Therefore, it has been proposed to formulate a powder type = hardener in a one-liquid type liquid crystal sealing agent. The powdery chemical is reacted with the resin composition in the form of a solid solution. That is, it is possible to suppress the reaction between the resin composition and the curing agent during storage, and the storage stability is improved.曰 曰 曰 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶The sealing member in the liquid crystal panel is thinned. From the viewpoint of making the (4) member thinner, it is preferred that the liquid crystal sealing agent does not contain a large amount of powder component. If a large amount of powder is included, the line width at the time of coating is affected by the particle size of the powder. When the powder component is contained, the viscosity is liable to rise, and it is difficult to form the liquid crystal sealing material in a straight line. Therefore, it is difficult to form a sealing member having a thin line width. SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the invention is to provide a liquid crystal sealing agent which is capable of having a fine line width wire sealing member and excellent storage stability. As described above, in order to thin the sealing member, it is important to reduce the amount of the powder component in the liquid helium and the sealant. On the other hand, if the liquid crystal sealant = hardener is reduced, the hardenability of the occupational fat component is reduced. In addition, it is also considered that the powdery hardener is exchanged for a hardener or a softener having a low softening point, but the storage stability is likely to decrease at 201242986.r. The present inventors focused on the combination of the components of the hardener. The present inventors have found that at least two selected from the group consisting of a solid primary polyamine hardener, a polyphenol hardener having a softening point of a predetermined range, and a secondary polythiol which is liquid at room temperature and When these compounds are combined, the storage stability becomes good. Further, it has been found that the amount of the powder component can be reduced, so that the coating stability becomes good. The present invention is based on such findings. A first invention of the present invention relates to a liquid crystal sealing agent.液晶] A liquid crystal sealing agent containing (1) a (meth)acrylic modified epoxy resin containing an epoxy group and a (meth)acrylic group in the molecule, and (2) a curing agent. (3) A photoinitiator, and the above component (2) is selected from the group consisting of a softening point of 50 ° C to 90 °. (: a polyphenol hardener, a secondary polythiol hardener having a melting point of 23 Å or less, and two or more hardeners in a group consisting of a primary polyamine hardener having a melting point of 6 〇 t 18 (rc) And a liquid crystal sealing agent as described in [2], wherein the liquid crystal sealing agent is the same as the above liquid crystal sealing agent, and the liquid crystal sealing agent is contained in an amount of 4 parts by mass to the above-mentioned liquid crystal sealing agent. 100 parts by mass, containing 5 parts by mass to 95 parts by mass of the above component (1) and 0.01 parts by mass to 5 parts by mass of the above component (3). [3] The liquid crystal sealing film as described in [1] or [2] The agent further contains 1 part by mass to 50 parts by mass of the (fluorenyl) endoate monomer and/or oligomer with respect to 10 parts by mass of the liquid crystal sealing agent. [4] [1] to [ The liquid crystal sealing agent according to any one of the above aspects, further comprising an epoxy resin having two or more epoxy groups in the molecule, wherein the epoxy resin 6 201242986 is selected from the group consisting of bisphenol type epoxy resins and biphenyl type epoxy resins. At least one bifunctional or trifunctional ring of a group consisting of a resin, a diphenyl ether type epoxy resin, and a diphenol type epoxy resin The liquid crystal sealing agent according to any one of [1] to [4], which has a softening point temperature of 5 〇〇 c 12 (rc) measured by a ball method And a liquid crystal sealing agent according to any one of [1] to [5], wherein the liquid crystal sealing agent is sealed with respect to the above liquid crystal. A liquid crystal sealing agent according to any one of the above-mentioned liquid crystal sealing agents, wherein the liquid crystal sealing agent is the same as the above liquid crystal sealing agent. The liquid crystal sealing agent according to any one of [1] to [7], which is used for the liquid crystal sealing agent of any one of [1] to [7]. The liquid crystal display panel manufactured by the liquid crystal dropping method. The second invention of the present invention relates to a method of manufacturing a liquid crystal display panel. [9] A method of manufacturing a liquid crystal display panel, comprising the steps of: preparing a substrate and The liquid crystal according to any one of [1] to [8] is used on a substrate on the opposite substrate. The sealant forms a seal pattern; in a state where the seal pattern is not cured, liquid crystal is dropped on the seal pattern region of the substrate or another substrate paired with the substrate; and the one substrate is overlapped with the other substrate And after the above-mentioned sealing pattern is photocured, it is thermally hardened. 7 201242986 !·. .1 [10] The manufacturing method of the liquid crystal display panel as described in [9], wherein the step of forming the seal pattern is used The liquid crystal sealing agent does not form a dummy pattern and only forms the above-described sealing pattern. The third invention of the present invention relates to a liquid crystal display panel. [11] A liquid crystal display panel comprising: a display substrate, a counter substrate paired with the substrate, inserted into the display substrate and the opposite facing surface, and filled in the display substrate and: a sealing agent Hardened matter. The liquid crystal which is read by the ur item [Effects of the Invention] According to the present invention, it is possible to provide a liquid-liquid S = which is a storage pattern having a storage stability and a shaft enthalpy and which can form a fine line width. Japanese and Japanese, sealant. 1 ·Liquid crystal sealant

And (3) the first initiator. The liquid crystal encapsulant t / more W in the molecule has two upper epoxy groups containing ((4) thin monomer and / or oligomer filler Μ (7) epoxy resin hard dielectric k Μ particles, (4) (1 (F-based) acrylic modified epoxy resin (methyl) acrylic acid modified epoxy resin epoxy resin epoxy (10) (methyl) (10) acid-based Wei base modified resin can be 8 201242986 A (mercapto)acrylic modified epoxy resin obtained by reacting a resin with (meth)acrylic acid in the presence of, for example, a basic catalyst is obtained. The epoxy resin produced as a raw material has two or more rings in the molecule. The emulsion-based bifunctional or higher epoxy resin may be, for example, a mixture of bisphenol and phenol F, 2,2'-diallyl bisphenol A, bisphenol AD and phenanthrene, and phenol. Epoxy resin; phenol novolak type, indophenol phenol, blue sub-type Γ 秘 秘 秘 以及 以及 以及 以及 以及 以及 以及 以及 以及 以及 以及 ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; The amount of the epoxy tree (4) functional group of the material is not particularly limited, and the polyfunctional epoxy resin of the type of methacrylic acid is highly modified by (meth)acrylic acid. The cross-linking of the cured product of the dense epoxy resin is preferably a bifunctional ring drop. Therefore, the epoxy resin which is a raw material is compared with the epoxy resin of the age-type epoxy resin = ζ = double phase and double F-type. The crystallinity is lower than that of an epoxy resin such as biphenyl phthalate, and the coating stability is more excellent. In the case of a base grease, it is preferred to use an It ratio of 1 or more, preferably 2 or less. The epoxy group contains an ancient %, and the modified acid is easily dissolved in the liquid crystal 4 (/-based epoxy resin is too high, the epoxy group contains ^ ® '(Methyl)acrylic acid modification rate is sometimes low in moisture resistance. ά-, (Yinji) propylene fosic acid modified epoxy resin 9 201242986 (fluorenyl) acrylic acid modified epoxy resin weight average The molecular weight may be from about 300 to about 500. The weight average molecular weight of the (fluorenyl) acrylic acid modified epoxy resin is determined by Gel Permeation Chromatography (GPC). (Meth)acrylic acid modified ring The oxygen resin has an epoxy group and a (meth)acrylic group in the molecule, and thus contains a liquid crystal dense of the (mercapto)acrylic modified epoxy resin. The amount of the (meth)acrylic modified epoxy resin is preferably set to 5 parts by mass to 95 parts by mass, more preferably set to 100 parts by mass of the liquid crystal sealing agent. When the amount is less than the lower limit, the resin component in the month b# sealing member is small, and the sealing property of the liquid crystal is insufficient. There is a possibility that the amount of other components is relatively small, and the hardenability is insufficient. • The epoxy resin having a ring-shaped enthalpy in the molecule is included in the liquid crystal sealing agent of the present invention, and may have an intramolecular content as needed. Epoxy resin with a % of soil. Examples of two or more cycloaliphatic molecules in the molecule include: selected from the group consisting of double-presence epoxy resin, month::=tip, biphenyl fluorene oxide resin, and triphenyl sulfonate ring At least one of the bifunctional or trifunctional epoxy resin oxime resins in the oxygen tree group may be contained alone or in combination of two or more. Preferably, the oxime resin has a softening point of 4 (rc or more, i: liquid: 曰 = blame epoxy resin solubility in liquid crystal, low expansion, and the replenishment of ^ w is difficult. The moisture resistance of the sealing member obtained by hardening the liquid crystal sizing agent is improved. Further, 201242986, the above-mentioned lyoreoxy resin preferably has a weight average molecular weight of 1 〇 _, preferably 〜5 。. The towel preferably has the above weight average. The molecular weight of the scale is decanted. Epoxy tree (4) Weight average - measured in the same manner as described above. Examples of the aromatic epoxy resin include: aroma represented by a double A, a sb Alkanediols, and diols obtained by modifying ethylene glycol, propylene glycol, and glycerol with such aryls = aromatic polyglycidol obtained by reaction with surface gas alcohols And 曱 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ A glycidyl ether compound or the like. ^ Among the above aromatic epoxy resins, a nonylphenol novolak type ring is preferred. Resin 'mold phenol novolak type epoxy resin, bisphenol A type epoxy resin, double type epoxy resin, three stupid epoxy resin, triphenyl sulfonate ring, resin 'trisphenol type epoxy Resin, dicyclopentadiene type epoxy resin, oxime ether type epoxy resin, biphenyl type epoxy resin. These aromatic epoxy tree candies may contain only one type or two or more types. The amount of the epoxy resin having two or more decyloxy groups in the molecule is preferably set to 丨 part by mass to 3 〇 parts by mass, more preferably set to 3 parts by mass to 20 parts by mass per 100 parts by mass of the liquid crystal sealing agent. (2) Hardener Additive Hardener is a secondary polythiol hardener with a softening point of 5 (TC~90〇C polyphenol hardening point of 23 C or less, and a bright point of 201242986 60°) Two or more selected from the group consisting of a primary polyamine curing agent having a C to 180 ° C. The specific combination of the curing agent includes the following four types: the above polyhydric phenol curing agent and the above secondary polythiol curing agent; Phenolic curing agent and the above-mentioned primary polyamine curing agent; the above secondary polythiol hardener and The first-stage polyamine curing agent; the above polyhydric phenol curing agent, the above-mentioned secondary polythiol curing agent, and the above-mentioned primary polyamine curing agent. In the liquid crystal sealing agent, it is also possible to avoid the effects and objects of the present invention. The curing agent other than the curing agent is contained. The secondary polythiol curing agent is liquid at room temperature, and the plurality of hardening agents are soluble in other components contained in the liquid crystal sealing agent. When the polyhydric phenol curing agent is combined with the above-mentioned secondary polythiol curing agent, the liquid crystal sealing agent does not contain a powder hardening agent, and the amount of the powder component can be greatly reduced. Further, the curing agents are easily dissolved homogeneously. In the epoxy or the fat, the sealing member obtained by curing the liquid crystal sealing agent exhibits high adhesive strength. As described above, the polyhydric phenol curing agent can be dissolved in other components contained in the liquid crystal sealing agent. Therefore, when the above polyhydric phenol curing agent is combined with the above-mentioned primary polyamine curing agent, the amount of the powder component in the liquid crystal sealing agent can be reduced as compared with the case where only the primary polyamine curing agent is added. In addition, the above-mentioned secondary polythiol hardener is also liquid at room temperature, so the combination of the above-mentioned primary multi-sulfur fresh hardener with the above-mentioned primary polyamine hardener is added to the case where only the above-mentioned primary polyamine hardener is added. Compared with 'can reduce the amount of powder components. 12 201242986 In the case where the above-mentioned primary polyamine curing agent, the above secondary polythiol curing agent, and the above primary polyamine curing agent are combined, the amount of the powder component in the liquid crystal sealing agent can be reduced for the above reasons. The amount of all the hardeners in the liquid crystal sealing agent is from 4 parts by mass to 30 parts by mass, more preferably from 5 parts by mass to 20 parts by mass, per 100 parts by mass of the liquid crystal sealing agent. If the total amount of the hardener exceeds the upper limit, there is a possibility that the viscosity stability is lowered. On the other hand, when the total amount of the curing agent is less than the lower limit, the curing of the resin may be insufficient, and the uncured component may be eluted in the liquid crystal or the like, indicating deterioration in quality or adhesive strength. Hereinafter, each curing agent will be described. (Polyphenol Curing Agent) The polyhydric phenol curing agent used in the present invention is a compound having two or more aromatic mercapto groups in one molecule, and has a softening point of 〜, preferably 60 ° C to 8 (TC. When the softening point is in this range, it softens when the liquid crystal sealing agent is thermally cured, and it can contribute to (1) (fluorenyl) acrylic acid-modified epoxy resin or (1-2) having two or more epoxy groups in the molecule. On the other hand, if the softening point is lower than the lower limit, the viscosity stability of the liquid crystal sealing agent may be affected. Further, when the upper limit is exceeded, the above resin may not be sufficiently hardened. Examples of the phenol curing agent include a phenol novolak resin or a phenol aralkyl resin, etc. The phenol novolak resin may be a condensate obtained by condensing phenol or indophenol with formalin.秘曰,曰 refers to the condensate of hope or expectation with p-xylene glycol in the presence of acid catalyst or an organic catalyst. The hardener can also be the above 13 201242986i • - - one - 1 condensate purified articles It may also be a city (4) secret varnish resin or a phenol aryl-based resin, etc. These hardeners may be contained alone or in combination of two or more. In the case where the excess contains a plurality of hardening agents, there may be a liquid crystal sealant. The adhesive strength of the cured product is insufficient. Further, if the ratio of the plurality of hardeners in the hardener is too large, the photocurability of the liquid crystal sealant may be hindered. Therefore, it is difficult to determine the amount of the hardener according to the liquid crystal seal. The adhesive strength of the cured product of the agent and the photocuring property of the liquid crystal sealing agent are set. (Secondary polythiol hardener) The polythiol hardener is a secondary thiol group having two or more secondary thiol groups in one molecule. The compound has a melting point of 231 or less. Examples of the above-mentioned secondary polythiol compound include an ester thiol compound obtained by esterification reaction of a mercaptocarboxylic acid having a secondary mercapto group with a polyhydric alcohol, that is, a mercaptoester. ; an aliphatic polythiol; an aromatic polythiol; a thiol-modified reactive eucalyptus, etc. The secondary polythiol compound may be contained alone or in combination of two or more.The second-order polythiol hardener is suitably a sulfhydryl ester obtained by esterification of a mercaptocarboxyl group having a secondary mercapto group with a fulcic alcohol. In the example of a mercaptocarboxylic acid having a secondary sparing group Containing 2-mercaptopropionic acid, 3-thiobutyric acid, 2-mercaptobutyric acid, etc. Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, 14-butanol, 1,6-hexanediol, glycerin, Trihydroxydecylpropane, di-trihydroxydecylpropanoid, quaternary tetraol, dipentaerythritol, sorbitol, etc. Specific examples of the secret class include pentaerythritol tetrakis(3-mercaptobutyrate), etc. 14 201242986 If the secondary polythiol hardener is excessively contained, the storage stability of the liquid crystal sealing agent may be insufficient. Therefore, the amount of the secondary polythiol hardener is preferably adjusted according to the viscosity stability of the liquid crystal sealing agent. (Primary polyamine hardener) The primary polyamine hardener is a compound having two or more primary amine groups (-NH2) in the molecule, and has a melting point of 6 (rc~18 (rc, preferably 7〇〇c~). 140 C. The hydrazinyl group is also included in the monthly female base. The primary polyamine hardener is solid when stored in a liquid crystal encapsulant, usually in the form of a powder. Examples of the primary polyamine hardener include organic acid di-quinone compounds, amine/urea adducts, dicyanodiamides, imidazole derivatives, aromatic amines, epoxy modified polyamines, and polyaminoureas. These primary polyamine hardeners may contain only one type and may contain two or more types. Examples of the organic acid diterpene compound include diammonium adipate (refining point. 180C), 1,3-bis(decylcarboethyl)_5. isopropylethyl carbazide (melting point 12〇C) 7,11_18 carbon two women], 18_ two carbon ploughing (melting point 16 〇{>c) and so on. Examples of the amine/urea adduct include a curing agent or the like which is commercially available as the Fujicure FXR series. When the above-mentioned primary polyamine curing agent is contained in the right excess, the liquid crystal sealing agent may have an increased viscosity and a decrease in coating stability. The formulation 1 of the primary polyamine hardener is preferably set in accordance with the curing rate of the liquid crystal sealing agent. When the first-stage polyamine hardener is in the form of a powder, the number thereof is preferably from G.1 μm to 5 μm, more preferably G 5 μm to 3 μm. By setting the enthalpy to the upper limit or less, the coating stability of the liquid crystal sealing agent is improved, and it is possible to use 15 201242986 --- Γ ': liquid sealing member. In addition, if it is set to the lower limit or more, =; Γ: during storage, the inhibitable-grade polyamine hardened two-milk average particle size can be determined by a dry particle size distribution meter, and the latter agent is used to make (1) (methyl) Acrylic acid modified epoxy resin, base) (10) acid s intended to be light hard / containing photoinitiator, which can be hardened by light hardening when manufacturing a liquid lique panel (4) Row Sealing_ Temporary hardening, the working light initiator can be a known article. Examples of the photoinitiator include a benzophenone compound, a phosphine oxide compound, a titanocene compound, a (four) systemic content, a benzoin compound, an acetophenone compound, and a benzophenone compound. a compound, an α-fluorenyl-based compound, a benzamidine-based compound, a benzene-based compound, an azo compound, a diphenyl sulfide-based compound, an organic dye-based compound, an iron-phthalocyanine-based compound, a benzoin ether a compound, an oxime compound, etc. Examples of the basic lanthanide compound include: 2,2-dimethoxy-1 2 diphenylethane-l-_ (IRGACURE 651), etc. a ketal; an a-aminoalkyl benzophenone such as 2-mercapto-2-morphinyl (4-thiononylphenyl)propane ketone ketone (nRGACURE 907 ); iota-hydroxy-cyclohexyl-phenyl - α-hydroxyalkyl benzophenone such as ketone (IRGACURE 184), etc. Examples of the fluorenyl phosphine oxide-based compound include 2,4,6-trimethyl benzomethyl hydrazino-diphenyl phosphine oxide. The titanium compound contains bis(η5_2,4-cyclopentadienyl)-bis(2,6-difluoro-3_(1^1-decyl-1-yl)-phenyl)titanium or the like. Example of 旨g-specific compound 201242986, child Contains 1.2-octyl-1-[4-(this thio)-2-(0-benzamide)] (IRGACURE OXE 01), etc. Light start with respect to 100 parts by mass of liquid crystal sealant The blending amount of the agent is preferably 0.01 parts by mass to 5 parts by mass, more preferably 0.1 parts by mass to 3 parts by mass. By setting the lower limit value or more, (1) (fluorenyl) acrylic acid modified ring gas The curability of the resin or the (4) (fluorenyl) acrylate-based monomer and/or oligomer described later is improved, and the liquid crystal sealing agent is stabilized at the time of application by setting it to the upper limit or less. (4) (Mercapto) Acrylic Acid Acetate Monomer and/or Oligomer The liquid crystal sealing agent of the present invention may optionally contain a (fluorenyl) acrylate monomer and/or oligomer. When the liquid crystal sealing agent contains a (fluorenyl) acrylate monomer and/or an oligomer, the liquid crystal sealing agent is light-cured, and the workability in the production of the liquid crystal panel is improved. (Mercapto) acrylate monomer and/or The type of the oligomer is not particularly limited as long as the object and effect of the present invention are not impaired. Examples of the (fluorenyl) acrylic monomer and/or oligomer include (Methyl) acrylic acid vinegar monomer Niu Shui u Yi, internal diol, Ge Yi Yi Ge's second internal acid and / or dimethyl propyl amide; tris (tetra) ethyl) Cyanuric acid _-acrylic acid and / or dimethyl _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ A succinic acid 1; a methacrylic acid diacrylate acrylate and/or two 201242986, a methacrylate obtained by adding 1 mole of double A to 2 moles of Wei Yi Qiang propylene propylene; _ Lubei r aurantia acid and/or dimethacrylate duck or trimethyl acrylate vinegar purchased by methyl two-burning addition of 3 moles or more = ethane or 1 oxonium; For =: Α 士士: propylene oxide or propylene oxide above the molar content of propylene and / or dimethyl propyl _ _; three (2 _,, and / or trimethyl Propylene _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Or an oligomer thereof; dipentaerythritol = polyacrylic acid S and/or polymethyl propylene tris((10) decyloxyethyl) heterotrimer Acid S is intended to be modified by tris(propylene oxyethyl) isotrimer diester; ester modified tris(methacryloxyethyl) iso-cyanate The second season; the polyacrylic acid ester of tetrahydric alcohol and/or polymethacrylic acid, the polyacrylic acid g of the modified diquaternary alcohol, or the polymethyl propylene phthalate, hydroxypivalic acid neopentyl Alcohol diacrylate and/or bismuth dimethacrylate, caprolactone modified hydroxypivalic acid neopentyl glycol diacrylate and/or dimethacrylate; epoxy ethene modified acid acrylate and / or dimercapto acrylate; ethylene oxide modified alkylated phosphoric acid acrylate and / or dimethyl propylene oxime ester; neopentyl glycol, trimethylolpropane, pentaerythritol oligomeric acrylic acid 3 and / Or oligomeric mercapto acrylate I. The amount of the (meth) acrylate monomer and/or oligomer is preferably set to 1 part by mass to 50 parts by mass with respect to 100 parts by mass of the liquid crystal sealing agent. More preferably, it is set to 5 parts by mass to 20 mass%. Share. (5) Thermoplastic polymer fine particles In the liquid crystal sealing agent of the present invention, if necessary, a thermoplastic polymer having a softening point temperature of 耽 12 (r, preferably 7 叱 to 刚·c) determined by the ring and ball test of 201242986 is contained. Further, the thermoplastic polymer microparticles having a number average particle diameter of α 〇 5 μπι 5 μιη, and preferably 0.1 μηη to 3 μηη may be contained. The sealant contains _ polymer microparticles, which can be moderated and sealed. By setting the number average particle diameter to the upper limit or less, it is possible to prevent the coating stability from being lowered by the thermoplastic polymer fine particles when forming the sealing member having a small line width. The method of measuring the particle diameter is the same as the method described above. Examples of the thermoplastic polymer microparticles include: suspending & combining a resin containing an epoxy group and a double bond with a monomer capable of radical polymerization. The obtained fine particles. In the example of the resin containing an epoxy group and a double bond group, a resin obtained by reacting a double-preferred F-type epoxy resin with methyl acrylic acid in the presence of a tertiary amine can be carried out. Examples of the monomer-polymerized monomer include butyl butyl acrylate, glycidyl methacrylate, and divinyl benzene. = 1 part by mass of the thermoplastic polymer microparticles is preferably 1 part by mass based on the liquid crystal sealing agent. 5 parts by mass to 40 parts by mass, more preferably 7 parts by mass to 30 parts by mass. By setting it as such a range, the thermoplastic polymer fine particles can alleviate the shrinkage stress at the time of heat curing of the liquid crystal sealing agent, and can have a target line width. (6) Filler The liquid crystal sealing agent of the present invention may further contain a filler. The filler may be used to suppress the viscosity of the liquid crystal sealing agent, the strength of the member obtained by curing the liquid crystal sealing agent, and the line. Expandability, etc. The filler is not particularly limited, and examples thereof include calcium carbonate, magnesium carbonate, 201242986, barium sulfate, sulfuric acid town, (four) Ming, Wei wrong, iron oxide, oxidized chin, alumina, zinc oxide, Inorganic fillers such as cerium oxide, potassium titanate, kaolin, talc, glass beads, ymite activated clay, clay, nitriding, nitrogen, etc., preferably cerium oxide, talc. * Shape of filler In particular, it may be any of a fixed shape or a fixed shape such as a spherical shape, a plate shape, or a needle shape. The filling is preferably an average of less than 1.5 μmη, and preferably a surface occupation ratio of 5 With ~ buckle m / g. The average primary particle size of the filler can be used to record the laser diffraction of the melon. In addition, the specific surface _ can be Xiangguai like two. Bhuert (Brunauei· Emmett Teller, BET) method to measure U00 parts by mass relative to the liquid crystal sealing, filling amount of the filler (four) ^ parts by mass to 50 parts by mass, more preferably 1 () parts by mass to 3 parts by mass; = exceeding the upper limit' In this case, the amount of the component in the liquid crystal sealing agent may be increased, and the coating stability may be lowered. 』 (7) The hardening catalyst of the oxy-resin is hardened, the liquid crystal is sealed, and the epoxy resin may be contained in the liquid crystal. ΐ: The hardening catalyst containing epoxy resin is sealed, and the hardening property of the sealing member obtained by hardening the shell and the aging agent becomes good, and the bonding strength of the sealing member is also improved. As long as the curing catalyst of the epoxy resin does not impair the limitations of the present invention and its strength, for example, the mass fraction of the liquid crystal is relatively better than that of the 20 201242986, which is preferably O'l quality. More preferably, it is Q 5 parts by mass to 3 parts by mass. (8) Other Additives In the liquid crystal sealing agent of the present invention, if necessary, it may further contain a thermal radical polymerization initiator, a Wei coupling fresh coupling agent, an ion trapping agent, an ion exchanger, a leveling agent, a pigment, a dye, and a plastic. Additives such as chemicals and defoamers. Further, in order to adjust the gap of the liquid crystal panel, a spacer or the like may be disposed. The liquid crystal sealing agent of the present invention contains (1) a (meth)acrylic modified epoxy resin, (2) a hardener, and (1) a photoinitiator, and thus can be preferably used in a liquid crystal dropping method for photohardening and thermosetting. Liquid crystal sealant used. The liquid crystal sealing agent for liquid crystal dropping method preferably further contains (1_2) an epoxy resin having two or more epoxy groups in the molecule, and (4) a (meth)acrylic acid vinegar monomer and/or oligomer. More preferably, it further contains (5) thermoplastic polymer microparticles and (6) a filler. 25 of the liquid crystal sealing agent of the present invention obtained by an E-type viscosity meter. The viscosity under the condition of 匸, 2 5 卬m is preferably 3〇 pa.s~4〇〇 pa, s, more preferably 5〇.

Pa.s~350 Pa.s. The liquid crystal sealing agent having a viscosity within the above range is excellent in coating property. (9) Method for producing liquid crystal sealing agent The liquid crystal sealing agent of the present invention is (1) a (meth)acrylic acid-modified epoxy resin containing an epoxy group and a (meth)acrylic group in the molecule, and (2) hardening. The agent, (3) a photoinitiator, and other components as needed are uniformly mixed and produced. The method of uniformly mixing is not particularly limited, and for example, it is preferably sufficiently kneaded using a three-parent mixer. Further, at this time, it is preferable to sufficiently defoam so that the liquid crystal sealing film 21 201242986 does not contain air bubbles. 2. Method of Manufacturing Liquid Crystal Display Panel The liquid crystal display panel of the present invention includes a display substrate, a pair of opposing earth plates inserted into a frame-shaped sealing member between the display substrate and the opposite substrate, and a filling substrate. A liquid crystal layer in a work chamber surrounded by a sealing member with the opposite substrate. The cured product of the liquid crystal sealing agent of the present invention can be made into a sealing member. The display substrate and the opposite substrate are both transparent substrates. The material of the transparent substrate is particularly limited, and examples thereof include glass, polycarbonate, polyethylene terephthalate, poly, wind, and polymethyl methacrylate (Methacrylate, pMMA). plastic. A thin matrix, a thin film transistor (TFT), a color light-emitting sheet, a black matrix, or the like may be disposed on the surface of the display substrate or the counter substrate. Further, the surface of the display substrate or the counter substrate is formed with an alignment, and a known organic alignment agent or inorganic alignment agent is contained in the alignment film. Method for manufacturing a liquid crystal display panel by using a liquid crystal dropping method package 3 · The sealing of the first agent is difficult; (4) The mechanical device is issued in a state in which the sealing is difficult to be hardened, and the pattern is surrounded by the above pattern. a region, or a liquid crystal added to the region of the other substrate that is surrounded by the seal pattern; and weight =); 2 step 'make the substrate and the other substrate to form a seal pattern 22 201242986t a4) 4 steps to harden the seal pattern. The state in which the seal pattern in the step a2) is not hardened refers to the state in which the hardening reaction of the liquid crystal post-sealant proceeds to the point before the gelation point. Therefore, in the step a2), in order to suppress the dissolution of the liquid crystal sealant in the liquid crystal, The seal pattern may be lightly irradiated or heated to be semi-hardened. One of the substrates and the other of the substrates are respectively a display substrate or a counter substrate. The liquid crystal sealing agent of the present invention has a small amount of powder in the curing agent, so that the sealing pattern can be thinned. The sealing pattern of the liquid crystal sealing agent of the present invention may have a cross-sectional area of about 15 μm 2 to 3 μ μm 2 . In the step a4), only hardening by heating may be performed, and it is preferred to perform hardening (temporary hardening) by light irradiation, followed by hardening by heat (formal hardening). The liquid crystal sealing agent is instantly hardened by temporary hardening by light irradiation, whereby the dissolution of each component in the liquid crystal can be suppressed. The photohardening time also depends on the composition of the liquid crystal encapsulant, for example, about 1 〇 t. The light irradiation energy may be an energy which can harden the (1) (meth)acrylic acid modified epoxy resin or the (4) (fluorenyl) acrylate monomer and/or oligomer. The light is preferably ultraviolet light. The heat hardening temperature also depends on the composition of the liquid crystal sealant, for example, Hot, and the heat hardening time is about 2 hours. Here, in the case where the liquid crystal display panel is manufactured by the liquid crystal dropping method, the step a3 is often carried out under reduced pressure, and the step a4) is carried out after being opened to atmospheric pressure. Specifically, after the two substrates are superposed in the step a3), the liquid crystal display panel is returned to atmospheric pressure. At this time, the area surrounded by the two substrates and the liquid crystal sealing agent was sealed, and the pressure-reduced state was maintained 23 201242986 4 1 . Therefore, in the region surrounded by the liquid crystal sealing agent, the force acts on the two substrates in the direction in which the substrates approach each other. On the other hand, since the outside of the frame of the liquid crystal sealing agent is opened to atmospheric pressure, the force does not act on the two substrates in the direction in which the substrates approach each other. Therefore, there is a problem that the substrate warps and the gap widens from the center portion of the liquid crystal display panel toward the outside of the liquid crystal sealing agent. If the gap is uneven in the liquid crystal display panel, the display reliability is lowered. In order to solve such a problem, a method of further arranging another frame (auxiliary seal) on the outer side of the frame (main seal) of the liquid crystal sealing agent has been conventionally used (for example, refer to Japanese Laid-Open Patent Publication No. 2002-328382). According to this method, the area outside the frame of the main seal, i.e., the main seal and the auxiliary seal, also becomes a depressurized state. Thereby, on the outer side of the main seal, the force acts on the two substrates in the direction in which the substrates approach each other, and the warpage of the substrate can be suppressed. Therefore, according to the method ', the gap in the liquid crystal display panel can be made uniform. Moreover, in order to improve the manufacturing efficiency of the liquid crystal display panel, it is desirable that the auxiliary seal is not formed. Therefore, as a method of making the two sheets of the gap uniform without forming an auxiliary seal, for example, the flexibility of the liquid crystal sealing agent is considered. After the liquid crystal is filled, when the liquid crystal display panel is opened to atmospheric pressure, the liquid crystal (four) ship is deformed with the movement of the substrate of the main (four) (the substrate is close to the I direction), and the emission suppression substrate is not required to be formed. Auxiliary seal. On the other hand, in the case of the liquid crystal sealing agent, the liquid crystal sealant has a large amount of powdery liquid crystals, and the liquid crystal sealing agent is hard. Further, the liquid crystal sealing agent of the present invention has a small amount of the powder component 24 20124298, and the liquid crystal sealing agent has high flexibility. Therefore, the liquid crystal display panel can be manufactured without forming the seal pattern necessary for sealing the liquid crystal without forming the auxiliary seal pattern. Further, the liquid crystal sealing agent of the present invention can be used not only for the above-described method for producing a liquid crystal surface panel by a liquid crystal dropping method but also for a method for producing a liquid crystal display panel by a liquid crystal injection method. A method of manufacturing a liquid crystal display panel using a liquid crystal injection method includes: M) a first step of forming a sealing pattern of the liquid crystal sealing agent of the present invention on a substrate; b2) a second step of sealing one substrate from another substrate [b3] In the third step, the sealing pattern is thermally cured to obtain a liquid crystal injecting unit having an injection port for injecting liquid crystal; b4) In the fourth step, liquid crystal is injected into the liquid crystal injecting unit via the injection port. And b5) Step 5, sealing the injection port. In the steps M to b3), the liquid crystal injection unit is prepared. First, prepare two transparent substrates (for example, glass plates). Then, a sealing pattern is formed on one of the substrates using a liquid crystal sealing agent. After the other substrate is superposed on the surface on which the substrate is formed, the sealing pattern may be cured. In this case, it is necessary to provide a filling port for injecting liquid crystal into a part of the liquid crystal injecting unit, and the injection port may be provided with a part of the opening when the sealing pattern is drawn. Further, after the seal pattern is formed, the pattern of the desired portion may be removed to provide an injection port. , 25 2012429861 b3) The thermal hardening conditions in the step also depend on the liquid formation 'for example 150. (: 2 hours to 5 hours or so. ^, and b4) steps are performed by the following known method, that is, the liquid crystal injection unit of the liquid crystal injection unit obtained in the step - b3) The injection port draws in the liquid crystal. b 5 Step 2 The liquid crystal sealing agent can also be sealed to the injection chamber of the liquid crystal injection unit to be hardened. The coating property of the liquid crystal sealing agent of the present invention is good, and the sealing member can be formed finely. In addition, the bonding strength is also good, and the viscosity stability is also excellent. By using the liquid crystal sealing agent of the present invention, it is possible to form only a sealing pattern necessary for sealing a liquid crystal without forming an auxiliary sealing pattern, and to obtain a liquid crystal display panel excellent in gap stability between substrates. Soil example [Synthesis Example 1] Synthesis of methacrylic acid modified bisphenol F type epoxy resin (7〇% partial thiol acrylate) 160 g of liquid bisphenol F type epoxy resin (Ep〇t〇ht 〇YDF-8170C, manufactured by Dongdu Chemical Co., Ltd., epoxy equivalent l6〇g/eq), 0.1 g of p-methoxyphenol as a polymerization inhibitor, g2 g of triethanolamine as a catalyst, and 70.0 g The methacrylic acid was added to the flask, and the mixture was allowed to react for 5 hours while stirring at 90 ° C under dry air. The obtained compound was washed twice with ultrapure water to obtain a methacrylic acid modified bisphenol F type epoxy resin. 26 201242986^ Here, the amount of the epoxy group contained in the bisphenol F-type epoxy resin which is a raw material is 1 mole. The number of mercaptoacrylic groups contained in the mercaptoacrylic acid to be reacted is 〇.7〇莫耳. Therefore, the obtained mercaptoacrylic acid modified bisphenol F type epoxy resin is a 70% partial mercapto acrylate. [Example 1] 5 parts by mass of a fluorenyl acrylate-modified bisphenol F-type epoxy resin (7 〇〇 / 0 part thiol acrylate) obtained in Synthesis Example 1 and a polyphenol were hardened using a two-roll mixer Agent A (manufactured by Mitsui Chemicals Co., Ltd.: Milex 3L, softening point 71 C) 4 parts by mass, secondary polythiol hardener B (manufactured by Showa Denko ΡΕ·1), 8 parts by mass, primary polyamine hardener D (adeka) Manufactured by the company: EH-5057, melting point 80. 4 parts by mass, photo-radical polymerization initiator as photoinitiator (manufactured by Ciba_Gage: IrgaCUre651) 1 part by mass, hardening catalyst (four Manufactured by Guohuacheng Co., Ltd.: 2MAOK) 2 parts by mass, manufactured by Thermoplastic Polymer Microparticles Co., Ltd.: F351) 20 parts by mass, filler (filler) si〇2 1 〇 parts by mass, Shi Xi Shao coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd. : KBM-403) 1 part by mass of the resin composition was sufficiently mixed to obtain a uniform liquid, and a liquid crystal sealing agent was obtained. The viscosity (initial viscosity) was measured by the method described later, and as a result, it was 240 Pa.s. [Example 2] A liquid crystal sealing agent was obtained in the same manner as in Example 1 except that the polyhydric phenol curing agent A was 8 parts by mass, the primary polyamine curing agent D was 8 parts by mass, and the secondary polythiol curing agent was 〇 by mass. Further, the viscosity (initial viscosity) was measured by the method described later, and as a result, it was 320 Pa.s. 27 201242986

» Λ I

[Example 3] A liquid crystal sealing agent was obtained in the same manner as in Example 1 except that the polyhydric phenol curing agent was 8 parts by mass, the secondary polythiol hardener B was 8 parts by mass, and the primary polyamine curing agent was yt by mass. Further, the viscosity (initial viscosity) was measured by the method described later, and as a result, it was 250 Pa.s. [Example 4] A liquid crystal sealing agent was obtained in the same manner as in Example 1 except that the secondary polythiol curing agent B was 8 parts by mass and the primary polyamine curing agent D was 8 parts by mass. Further, the viscosity (initial viscosity) was measured by the method described later, and as a result, it was 260 Pa.s. [Example 5] The amount of the thioglycol-modified double-type F-type epoxy resin (70% partial methyl acrylate) obtained in Synthesis Example 1 was 4 parts by mass, and the amount of the polyphenol phenol hardener A was 7 parts by mass of the secondary polythiol curing agent B is 14 parts by mass, the amount of the primary polyamine curing agent d is 7 parts by mass, the amount of the thermoplastic polymer fine particles is 19 parts by mass, and the amount of the filler is 9 mass. A liquid crystal sealing agent was obtained in the same manner as in Example 1 except for the wound. Further, the viscosity (initial viscosity) was measured by the method described below, and as a result, it was 21 〇 pa, s. [Example 6] ^ The amount of the methacrylic acid-modified bisphenol F-type epoxy resin (70% partial methacrylate) obtained in Synthesis Example 1 was 56 parts by mass, and more = the amount of hardening = jA* If the amount of the second-order polythiol hardened 3: 3 parts by mass of the '--type polyamine hardener D is 】 by mass, the amount of the thermoplastic polymer is 23 f, and the mass of the filler is 12 quality ' 28 201242986l j. In addition to the amount, and the example 1 IS] 丨 secret liquid crystal secret. Further, the viscosity (initial viscosity) was measured by the method described later as a result of 3 GGPa·8. [Example 7] In addition to using a multi-component hardener B (manufactured by DIC Corporation, TD2131, softening point 8G〇C), 4 parts by mass was used instead of the poly-chemical agent A' and the amount of the second-order polythiol hardener B was 8 parts by mass. A liquid crystal sealing agent was obtained in the same manner as in Example 1 except that the amount of the primary polyamine curing agent D was 4 parts by mass. In addition, the result of measuring the viscosity (initial viscosity) by the method described later is 250 Pa*s 〇 [Example 8] In addition to the use of polyphenol hardener c (Mitsubishi Chemical Co., Ltd. 170, softening point 90Ϊ:) 4 parts by mass instead of plural A liquid crystal sealing agent was obtained in the same manner as in Example 1 except that the amount of the secondary polythiol curing agent B was 8 parts by mass and the amount of the primary polyamine curing agent d was 4 parts by mass. Further, the viscosity (initial viscosity) was measured by the method described later, and as a result, it was 255 Pa.s. [Example 9] The amount of the hardener A was 4 parts by mass, the amount of the secondary polythiol hardener B was 8 parts by mass, and a polyamine hardener a (manufactured by Hydrazine Hydrazine: ADH, melting point i80) was used. 〇c) A liquid crystal sealing agent was obtained in the same manner as in Example 1 except that 4 parts by mass and a polyamine curing agent D4 parts by mass were used as the primary polyamine curing agent. Further, the viscosity (initial viscosity) was measured by the method described later, and as a result, it was 270 Pa.s. [Example 10] 29 201242986t The amount of the phenol curing agent A was 4 parts by mass, the amount of the secondary polythiol curing agent B was 8 parts by mass, and the polyamine curing agent B (Fuji Chemical Industrial Co., Ltd.: Fujicure FXR-1020) was used. In the same manner as in Example 1, a liquid crystal sealing agent was obtained in the same manner as in Example 1 except that 4 parts by mass of the Fe-based curing agent D and 4 parts by mass were used as the primary polyamine curing agent. Further, the viscosity (initial viscosity) was measured by the method described later, and as a result, it was 260 Pa*s. [Example 11] The amount of the phenolic hardener A was 4 parts by mass, the amount of the secondary polythiol hardener B was 8 parts by mass, and a polyamine hardener c (Ajin〇m〇t〇) was used.

Made by Fine-Techno: νχ) Η, dazzle 12 〇. 〇) 4 parts by mass of a liquid crystal sealing agent was obtained in the same manner as in the example hydrazine as a primary polyamine curing agent. Further, the viscosity (initial viscosity) was measured by the method described later, and as a result, it was 250 Pa·s. [Comparative Example 1] A liquid crystal sealing agent was obtained in the same manner as in Example 1 except that the phenol curing agent A as the curing agent was 16 parts by mass, the secondary polythiol curing agent, and the primary polyamine curing agent were 5% by mass. Further, the viscosity (initial viscosity) was measured by the method described later, and as a result, it was 350 Pa*s. [Comparative Example 2] A liquid crystal sealing agent was obtained in the same manner as in Example 1 except that the secondary polythiol curing agent B as a curing agent was 16 parts by mass, and the polyhydric phenol curing agent and the primary polyamine curing agent were in the form of a mass fraction. . Further, the viscosity (initial viscosity) was measured by the method described later, and as a result, it was 21 〇 pa*s. [Comparative Example 3] 30 201242986, except that the primary polyamine curing agent D as a curing agent was 16 mass damage, the polyphenol curing agent, and the secondary polythiol curing agent were 〇 mass parts, the same as in Example 1. A liquid crystal sealing agent was obtained. Further, the viscosity (initial viscosity) was measured by the method described later, and as a result, it was 370 Pa.s. [Comparative Example 4] The amount of the mercaptoacrylic acid-modified bisphenol F-type epoxy resin (70% partial methyl acrylate) obtained in the synthesis example was % by mass, and the difference was jA. 8 parts by mass, the amount of the secondary polythiol hardener B is 16 masses = parts, the amount of the polyamine hardener D is 8 parts by mass, the amount of the filler is = parts by weight, and the amount of the thermoplastic polymer fine particles is 8. A liquid crystal sealing agent was obtained in the same manner as in Example 1 except for the mass portion. In addition, the viscosity (initial viscosity) was measured by the method described later, and the result was 28 〇Pa, s. [Comparative Example 5] The amount of the methacrylic acid-modified double-type F-type cyclic emulsion resin (70% partial methyl acrylate) obtained in Synthesis Example 1 was % by mass, and the amount of phenol was used. The amount of G. 5 parts by mass, the amount of the secondary polythiol curing agent B, the amount of the polyamine curing agent D is G 5 f parts, the amount of plastic outer particles is 23 parts by mass, and the amount of the filler is 12 parts by mass of the liquid crystal sealing agent was obtained in the same manner as in Example 1. Further, the viscosity (initial viscosity) was measured by the method described later, and as a result, it was 27 〇Pa, s. [Comparative Example 6] A liquid crystal sealing agent was obtained in the same manner as in Example 1 except that 8 parts by mass of a polyvalent thiol curing agent (manufactured by Seiko Chemical Co., Ltd.: hard trimethyl hydrazinyl mercaptopropionic acid) was used as the polythiol hydrazine. Further, Lee 31 201242986 measured the viscosity (initial viscosity) by the method described later and found that it was 260 Pa, s. [Comparative Example 7] A liquid crystal sealing agent was obtained in the same manner as in Example 1 except that a phenol curing agent D (manufactured by DIC Corporation, TD2090, softening point 100 C) was used as the polyvalent hardener. Further, the viscosity (initial viscosity) was measured by the method described later, and as a result, it was 270 Pa, s. [Comparative Example 8] 10 parts by mass of (meth) acrylate monomer and/or oligomer containing epoxy resin (manufactured by Nippon Kayaku Co., Ltd.: EOCN-1020-75) was used. (Manufactured by Osaka Organic Chemical Industry Co., Ltd.: Biscoat #300) 53 parts by mass, a primary polythiol hardener A5 parts by mass, a primary polyamine compound (manufactured by Ajinomoto Fine-Techno Co., Ltd.: Amicure VDH) 5 parts by mass, photoradical Polymerization initiator (manufactured by Ciba Specialty Chemicals Co., Ltd., Irgacure 184) 2 parts by mass, thermoplastic polymer microparticles (manufactured by Ganz Co., Ltd.: F351) 12 parts by mass, SiO 2 (filler) 12 parts by mass, Shi Xiyuan coupling agent (Xin Yue) Manufactured by Ju Shi Xi Oxygen Co., Ltd.: KBM_403) 1 part by mass of the curable resin composition is thoroughly mixed to form a uniform liquid, and a liquid crystal sealing agent is obtained. Further, the viscosity (initial viscosity) was measured by the method described later, and as a result, it was 250 Pa*s. [Evaluation] Viscosity stability, seal coatability, adhesion strength, display state, high-temperature and high-humidity reliability, and gap precision were measured for Examples 1 to 11 and Comparative Examples 1 to 8. Each measurement method is as follows. The results of these measurements are shown in Tables 1 to 3. 32

201242986 x I 1) Viscosity stability The weight of the liquid 曰宓la nightly sealant in the dispensing syringe was 10 g, and the results were obtained in the example and the comparative example. After the liquid crystal sealant of the cake 9 of your field c, carry out the defoaming post-release, type 8 viscometer at room temperature (25. 〇, 25 rpm

The initial viscosity was determined by the conditions. The viscosity was measured again under the same conditions following @ 5 P. The rate of increase of the _ degree relative to the initial viscosity after one week of storage was determined. The evaluation of the viscosity after storage with respect to the initial viscosity was ◎ (very excellent). The phase, the two η ^ borrowed from the following: hangs down, and exceeded u times and was 12 times to evaluate as 〇 (excellent); more than 1.2 and rabbit τ < Μ士, σ is 1.5 times or less, and is evaluated as Δ (slightly worse); when it is more than 1.5 times, it is evaluated as X (poor). 2) Seal coating property The liquid crystal sealing agent 2 〇 g obtained in the examples and the comparative examples was filled under vacuum into a syringe. Then, after lg was spit out from a syringe equipped with a needle tip having a diameter of 0.35, the next day was placed under 23t:. Then, the syringe was placed in a dispenser (manufactured by Hitachi Plant Technol〇gies Co., Ltd.) to form 5 3 3 5 mm χ 4 〇 on a glass substrate for a liquid crystal display panel of 360 mm x 470 mm (manufactured by Sakamoto Electric Glass Co., Ltd.). Mm seal pattern. At this time, the discharge pressure was set to 0.3 MPa, the cross-sectional area was set to 3000 μm, and the coating speed was set to i 〇〇 mm/s. The shape of the obtained seal pattern was evaluated as follows. 'The frame mold with no seal notch and seal drawing at all is 5 :: ◎ (often excellent) No seal notch is produced at all, and the frame mold for sealing wire drawing is 48~49 33 201242986 pieces: 〇 (excellent) No seal at all The frame mold of the notch and the sealed wire drawing is less than 48: X (poor) 3) Display state and high temperature and high humidity reliability test The liquid crystal sealant utilization distributor obtained in the above examples and comparative examples (Shot Master. Musashi -Engineering) Manufactured a square seal of 35 mm><40 mm on a 40 mm><45 mm glass substrate ("RT-DM88-PIN" manufactured by EHC) in which a transparent electrode and an alignment film were formed in advance. Pattern (cross-sectional area 3500 μιη2) (main seal). Then, a square seal pattern (a square seal pattern of 38 mm x 43 mm) was formed on the outer periphery thereof. Then, a liquid crystal material (MLC-119000-000: manufactured by Merck) equivalent to the amount of the panel content after the bonding was accurately dropped into the frame of the main seal by means of a dispenser. Then, the glass substrate paired therewith was bonded under reduced pressure, and then the atmosphere was opened and bonded. Next, the two glass substrates to be bonded were held in a light-shielded box for 3 minutes, and then irradiated with ultraviolet rays of 2 〇〇〇 mJ/cm 2 and further heated at 1 ° C for 1 hour. The obtained liquid crystal display panel was stored in a temperature bath at a temperature of 7 ° C and 95% RH for several hours. The chromatic aberration caused by the liquid crystal around the seal portion before and after storage was observed. The color is judged to be excellent when it is completely undetermined); it is evaluated when the color difference is hardly confirmed. (Excellent); when the color difference is confirmed, it is evaluated as x (differential) when the color difference is recognized. Further, the liquid crystal display panel taken out after being stored in the tank with a voltage of 5 V is applied by a DC power supply device. According to the liquid crystal sealing agent: 34 201242986 =; == Initial: No function normally, and the liquid crystal display is mixed. Normally, the display characteristic 'will be less than the vicinity of the edge of the sealing edge (it is evaluated as ◎ (excellent) when U mm U, and is evaluated as good in the seal. (good), when the sealing g5 endures the abnormality of the liquid crystal display function, the south is When the ten-edge is more than 0.1 mm and less than 0.3, the abnormality of the two-crystal display function is evaluated as Δ (slightly worse), and the price is X (1 "poor". If the abnormality of the display function is confirmed at the 茁 3 3 The adhesion strength is the same as in the above 3) 'The sample of the liquid crystal display panel which was stored in the & warming tank, and the rib extension test was made (manufactured by Imese), and the tensile strength was measured at a tensile speed of 2. The adhesion was evaluated as follows. The bonding strength was 20 MPa or more: ◎ (excellent) The bonding strength was 15 MPa or more and less than 2 G MPa : (excellent) 15 MPa : Δ The bonding strength was less than 7 MPa : χ ( Poor) 5) Clearance accuracy for examples and comparative examples The obtained liquid crystal sealing agent was formed on a 40 mm><45 mm glass substrate (manufactured by EHC, RT-DM88-PIN) in which a transparent electrode and an alignment film were formed in advance using a dispenser (Shot Master: manufactured by Musashi Hi-Tech). 35 mm><40 mm square sealing pattern (cross-sectional area 3000 μm 2) (main seal). Thereafter, the outer peripheral seal pattern is not formed. The line width of the sealant after bonding the paired substrates is measured. The clearance accuracy is checked according to the value. When the seal line width is less than 1 mm, it is evaluated as 〇35 201242986 -----rl (excellent) when it is 1 mm or more, it is evaluated as χ (poor). 36 201242986 JUfNal inch [11 example 〇 \ 1 1 1 1 00 inch 1 1 inch fN 〇 - 〇〇〇 ◎ ◎ 〇 00 1 1 inch 1 1 00 1 I 1 inch CN 〇*·« 〇〇〇 ◎ ◎ 〇 1 1 1 1 1 00 1 1 1 inch (N 〇〇〇 ◎ ◎ ◎ 〇v〇l〇1 1 1 1 m 1 1 1 (N (N ◎ ◎ ◎ ◎ ◎ 〇o 卜 1 1 1 1 1 1 1 卜 CN 〇 \ ON 〇〇 ◎ ◎ ◎ 〇 1 1 1 1 1 〇〇 1 1 1 00 CN 〇〇〇 ◎ ◎ ◎ 〇 00 1 1 1 1 00 1 1 1 1 (N 〇 ◎ ◎ 〇 ◎ ◎ 〇CN 00 1 1 1 1 1 1 1 1 00 «Ν 〇〇〇 ◎ ◎ ◎ 〇 inch 1 1 1 1 00 1 1 1 inch »—Η CN 〇〇〇◎ ◎ ◎ 〇 /-~N ύ t ^ 5 ^ !φ备VV· Mj ^ rr ^ 5f <°Si B-phenol hardener A (softening point 71 °C) Anticipating agent B (softening point 80 °c) Phenol hardener C (softening point 90 °c) phenol hardener D (softening point 100 °c) thiol hardener A (grade polythiol) thiol hardener B (secondary polythiol) amine hardener A (melting point 180 °c) Amine hardener B (melting point 125 ° c) Amine hardener C (melting point 120 ° c) Amine hardener D (melting point 80 ° C) Irgacure 651 2MAOK F351 Si02 KBM-403 Viscosity stability seal coating adhesion Strength display state high temperature and high humidity reliability gap precision phenolic hardener thiol-based hardening amine hardener photoinitiator hardening catalyst thermoplastic polymer microparticle filler coupling agent composition evaluation

Li 5 201242986

Ja(N£inch[&lt;N&lt;] Bu&lt;1 1 inch 1 00 1 1 1 inch CN 〇◎ 〇X &lt;] &lt;3 〇 inch 1 1 1 00 1 1 1 1 (N 〇X 〇&lt ; &lt;1 &lt;1 &lt; 〇to 00 ν-ί Ο 1 1 1 1 (N 1 1 1 ο (N m CN (N ◎ ◎ XXX 0 Comparative example inch 〇〇CO οο 1 1 1 1 Ο 1 1 1 οο &lt;;N oo 00 &lt;〇&lt;&lt;&lt;&gt; X ΓΟ I 1 1 1 1 1 1 1 1 ν〇(N 〇&lt; X ◎ ◎ ◎ X (Ν I 1 1 1 1 1 1 1 I CN 〇 < ◎ &lt;&lt;&lt;&lt; lt1 1 1 1 1 1 1 1 1 (N 〇◎ 〇X &lt;&lt; 〇λ: inch 1 1 1 1 00 1 1 inch 1 CN 〇&lt; 〇〇◎ ◎ 〇 〇 inch 1 1 1 1 00 1 inch 1 inch &lt;N 〇0 Ο 〇〇〇0 /—N flavor I ft π anger 4j Β-phenol hardener A (softening point 71 ° C) Hope hardener B (softening point 80°c) Anti-hardener C (softening point 90°c) Phenol hardener D (softening point 100°c) Thiol hardener A (grade polythiol) Thiol hardener B (secondary polythiol) Amine hardener A (melting point 180 ° c) Amine hardener B (melting point 125 ° c) Amine hardener C (melting point 120 ° c) Amine hardener D (melting point 80 ° C) Irgacure 651 2MA0K F351 Si〇2 KBM-403 Viscosity stability seal coating adhesive strength display state high temperature and high humidity reliability gap precision phenolic hardener thiol-based hardening amine hardener photoinitiator hardening catalyst thermoplastic polymer microparticle filler Evaluation of coupler composition °°e 201242986 J-aCNrnz-l inch bucket e&lt;] Comparative example 8 ο 1 1 1 &lt;IT) 1 1 1 1 (N 1 (N «•Η &lt;〇&lt;&lt; 〇〇 EOCN-1020-75 Biscoat #300 Tantalum Hardener A Hope Hardener B Hope Hardener C Hope Hardener D Thiol Curing Agent A Thiol Curing Agent B Amine Hardener A Amine Hardener B Amine Hardener C Amine Hardener D Irgacure 651 1 F351 Si02 ΚΒΜ-403 Viscosity stability seal coating adhesive strength display state high temperature and high humidity reliability gap precision epoxy resin (meth)acrylic acid vinegar monomer and / or oligophenolic hardener thiol system Hardener amine curing agent photopolymerization initiator hardening catalyst thermoplastic particle filler coupling agent composition evaluation

201242986a X According to Tables 1 and 2, it is known that a secondary polythiol hardener selected from a polyphenol curable agent having a softening point of 5 (^c to 90 ° C, a melting point of 23 or less, and a bright point) are used. In the case of two or more kinds of hardeners in a group consisting of 60 ° C to 18 (TC primary polyamine hardener), viscosity stability, seal coatability, adhesion strength, display state, high temperature and high humidity Both reliability and gap precision are excellent (Examples 1 to 1 1 ). On the other hand, when only a polyphenol hardener having a softening point of 50 t: to 90 ° C (Comparative Example 1) is used, the bonding strength is low. The display state and the high-temperature and high-humidity reliability were slightly inferior to those of Examples 1 to 11. In addition, when only the second-order polythiol hardener having a bright spot of 23 C or less (Comparative Example 2) was used, the viscosity stability, The bonding strength, the display state, and the high-temperature and high-humidity reliability were all inferior to those of Examples 1 to 11. Further, when only the melting point was 60. (: 180 ° C grade polyamine curing agent (Comparative Example 3), Low viscosity stability, poor sealability and gap accuracy. The free softening point is selected to be 5 〇. 多元~90 °C multi-component hardener, secondary polythiol hardener with a melting point below 23 ° C, and primary polyamine hardening with a melting point of 60 C~180 ° C In the case of the hardener of the rain or more in the group of the agent, when the amount is less than 4 parts by mass relative to 1 part by mass of the liquid crystal sealing agent (Comparative Example 5), the bonding strength and the opening are improved. In the case of the case where the amount of the hardener exceeds 3 〇 by mass (Comparative Example 4) with respect to 10 parts by mass of the liquid crystal sealant, viscosity stability and adhesion strength are obtained. The display state, the high temperature and high humidity reliability are lowered, and the gap precision is poor. Further, when the -stage polythiol hardener is used instead of the second-order polythiol 201242986 hardener (Comparative Example 6 and Comparative Example 8), the viscosity is stable. The adhesion is lowered, the bonding strength, the display state, and the high-temperature and high-humidity reliability are also lowered. In addition, when the softening point of the phenol curing agent exceeds 90 ° C (Comparative Example 7), the bonding strength is lowered, and the display state and high temperature are high. Wet reliability also declined. [Industry UTILITY] Since the liquid crystal sealing agent of the present invention has a small amount of a powder component derived from a curing agent, when a liquid crystal sealing agent is applied to form a fine sealing member, coating stability can be improved. It is also excellent in strength or viscosity stability, so that a liquid crystal panel excellent in display reliability can be provided. Therefore, the liquid crystal sealing agent of the present invention is suitable for manufacturing a liquid crystal display panel. [Simplified illustration] jttfi 〇#, 》, [main component symbol Description] Benefit. 41

Claims (1)

201242986 VII. Patent application scope: A liquid crystal sealant 'containing (丨) molecules containing epoxy groups and (meth)acrylic groups (fluorenyl) acrylic modified epoxy resins, (2) hardeners and (3) a photoinitiator, and the component (2) is selected from the group consisting of a polyhydric phenol curing agent having a softening point of 5 〇 ° c to 9 (c), a secondary polythiol curing agent having a melting point of 23 t or less, and a melting point of 60 C. Two or more kinds of the hardening agent in the group consisting of the first-stage polyamine curing agent in the range of ～180° C., and the above-mentioned component is contained in an amount of 4 parts by mass to 3 parts by mass based on 1 part by mass of the liquid crystal sealing agent ( 2. The liquid crystal sealing agent according to the above aspect of the invention, wherein the liquid crystal sealing agent contains 5 parts by mass to 5% by mass of the two components (1) and 〇〇1 parts by mass to 5 parts by mass of the liquid crystal sealing agent. The liquid crystal sealing agent according to the above paragraph, wherein the liquid crystal sealing agent (10) parts by mass further contains 1 part by mass of the (meth) acrylate of the 〇5 里 pulp. Monomer and / or oligomer. 4. As stated in the scope of patents The liquid crystal ί=2 or more epoxy groups of epoxy resin, the above ring == free phenol type epoxy resin, biphenyl type epoxy tree = fat and triphenyl epoxide group = 2 a functional or trifunctional epoxy resin. The liquid crystal _ according to the ring term, contains a thermoplastic polycondensate of the thief ~not, and has a number average particle diameter. The liquid crystal sealing agent according to claim 1, wherein the liquid crystal sealing agent according to the above-mentioned liquid crystal sealing agent contains an amount of parts of not more than 5 parts by mass relative to 100 parts by mass of the liquid crystal sealing agent. 7. The liquid crystal sealing agent according to item [i] of the invention, wherein the hardening catalyst of the epoxy resin containing Q] parts by mass to 5 parts by mass relative to the above liquid crystal sealing agent HK) parts by mass 8. The liquid crystal sealing agent according to claim 2, which is used for the manufacture of a liquid crystal display panel using a liquid crystal dropping method. 9. A method of manufacturing a liquid crystal display panel comprising the steps of: preparing for display Substrate and its opposite pair Applying a liquid crystal sealing fine film according to claim 1 on a substrate; in a state where the sealing pattern is not hardened, in a sealing pattern region of the substrate or in pair with the substrate Adding liquid crystal to the other substrate; superimposing the one substrate on the other substrate; and thermally curing the sealing pattern after curing. ^1〇. Liquid crystal display according to claim 9 In the method of manufacturing a panel, the step of forming the seal pattern is a step of forming the seal pattern by using the liquid crystal sealant without forming an auxiliary pattern. U. A liquid crystal display panel comprising: a display substrate and a pair of the display substrate a facing substrate, 43 201242986, a frame-shaped sealing member interposed between the display substrate and the opposite substrate, and a liquid crystal layer in a space surrounded by the sealing member and filled between the display substrate and the opposite substrate And the sealing member is a cured product of the liquid crystal sealing agent according to claim 1 of the patent application. 201242986 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the component symbols of this representative figure: None. 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: jttk 〇Μ,, 3 201242986 " For the Chinese manual No. 101106121, there is no slash correction. This revision period: June 22, 2011. Invention patent Manual 1 (The format and order of this manual are not to be changed at all, please do not fill in the ※ part) ※Application number: ※Application date: ※卩匚卩匚 Classification: 1. Invention name: (Chinese/English), liquid crystal sealant A method of manufacturing a liquid crystal display panel using the same, and a liquid crystal display panel 0 LIQUID CRYSTAL SEALING AGENT, FABRICATING METHOD OF LIQUID CRYSTAL DISPLAY PANEL USING THE SAME AND LIQUID CRYSTAL DISPLAY PANEL 2. Abstract: The object of the present invention is to provide a stable storage A liquid crystal sealing agent which is excellent in sealing property and can form a sealing member having a narrow line width. The liquid crystal sealing agent of the present invention contains a (meth)acrylic modified epoxy resin containing an epoxy group and a (meth)acrylic group in the molecule. , (2) a hardener, and (3) a photoinitiator, and the above component (2) is selected from the group consisting of The polyphenol hardener having a melting point of 5 (TC~9〇°c, a secondary polythiol hardener having a melting point of 23 ° C or less, and a primary polyamine hardener having a melting point of 60 ° C to 180 ° C) Two or more kinds of hardeners in the group of the components are contained, and 4 parts by mass to 30 parts by mass of the above component (2) is contained with respect to 10 parts by mass of the liquid crystal sealing agent. III. Abstract: The object of This invention is to provide a liquid crystal 201242986 for the Chinese manual No. 106121 without a slash correction. This revision date: 1 δ δ 片 22 丨 、, invention description: [Technical field of invention] The present invention is related to A liquid crystal sealing agent, a liquid crystal display panel manufacturing method using the same, and a liquid crystal display panel. [Prior Art] In recent years, image display of various electronic devices typified by mobile phones or personal computers (pers 〇 Iial computers) A liquid crystal display panel is widely used for a panel. The liquid crystal display panel has the following structure. A liquid crystal material is sandwiched between two transparent substrates having electrodes on the surface (hereinafter referred to as liquid crystal). One of the manufacturing methods of the liquid crystal display panel which is expected to improve the productivity by the liquid crystal sealing agent is a liquid crystal dropping method. The liquid crystal dropping method is the following method: (1) coating on a transparent substrate A liquid crystal sealing agent forms a frame; (2) a minute liquid crystal is dropped in the frame; (3) two substrates are superposed; and (4) a liquid crystal sealing blade is hardened to produce a panel. In this method, a liquid crystal sealing agent which is cured by light and heat is usually used. For example, in the step (3), the liquid crystal sealing agent is temporarily hardened by irradiating light such as ultraviolet rays, and then post-cured by heating in the step (4). As the liquid crystal sealing agent, a liquid crystal sealing agent containing a resin component having both ultraviolet curability and thermosetting property has been proposed (see, for example, Patent Document I, Patent Document 2). In the liquid crystal sealing sword containing the above resin component, a photoinitiator for ultraviolet curing and a curing agent for thermosetting are usually added together with the above resin component. From the viewpoint of workability, the liquid crystal sealing agent is desirably set to a 201242986 "Revised date: June 22, 2011, No. 101106Π1 Chinese manual without a sizing correction of this liquid type. However, in liquid When the resin component and the curing agent are contained, the components are reacted during storage. Therefore, it is proposed to mix a powdery curing agent in a one-liquid type liquid crystal sealing agent. The powdery hardener and the resin are composed. The reaction is carried out in the form of a solid solution, that is, the reaction between the resin composition and the curing agent during storage can be suppressed, and the storage stability becomes good. Patent Document 1: Japanese Laid-Open Patent Publication No. 2001-133794 (Patent Document 2) discloses a liquid crystal sealing agent which requires storage stability. On the other hand, in recent years, a sealing member thin line in a liquid crystal panel is desired. Chemical. From the viewpoint of thinning the sealing member, it is preferred that the liquid crystal sealing agent does not contain a large amount of powder component. When a powder component is contained in a large amount, the line width at the time of coating is affected by the particle diameter of the powder. Further, when the powder component is contained, the viscosity is liable to rise, and it is difficult to melt the liquid crystal sealing film into a linear shape. Therefore, it is difficult to form a sealing member having a thin line width. SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the invention is to provide a liquid crystal sealing agent which can form a sealing member with a fine line width and which is excellent in robustness. As described above, in order to thin the sealing member, it is important to reduce the amount of the powder component in the liquid sealant. On the other hand, when the curing agent of the liquid crystal sealing agent is reduced, the hardenability of the resin component is lowered. In addition, it is also considered to replace the powdery hardener with a hardener with a bright point or a low softening point, but &amp; 201242986 is the Chinese manual No. 106121 without a slash correction. Amendment date: 1〇1年吲22 Π Storage stability is easily reduced. The present inventors focused on the combination of the components of the hardener. The inventors have found that at least two of the first-stage polyamine hardeners from the solid state, the polyphenol curable agent having a softening point of a predetermined range, and the second-order polythiol which is liquid at room temperature are selected. When the compounds are combined, the storage stability becomes good. Further, it has been found that the amount of the powder component can be reduced, so that the coating stability becomes good. The present invention is based on such findings. A first invention of the present invention relates to a liquid crystal sealing agent. [1] A liquid crystal sealing agent comprising (1) a (meth)acrylic modified epoxy resin containing an epoxy group and a (meth)acrylic group in the molecule, (2) a hardener, and (3) a photoinitiator And the component (2) is a polyhydric phenol hardening agent selected from a softening point of 50 ° C to 90 ° C, a secondary polythiol curing agent having a melting point of 23 〇 c or less, and a melting point of 6 (rc 〜 18 ( Two or more kinds of curing agents in the group consisting of the primary polyamine curing agent of rc, and containing 4 parts by mass to 30 parts by mass of the above component (2) with respect to 100 parts by mass of the liquid crystal sealing agent. [2] In the liquid crystal sealing agent of the above-mentioned liquid crystal sealing agent, 5 parts by mass to 95 parts by mass of the above component (1) and 0.01 part by mass to 5 parts by mass of the above component (3) are contained with respect to 100 parts by mass of the liquid crystal sealing agent. (3) The liquid crystal sealing agent as contained in [1] or [2], wherein the (meth) acrylate monomer is further contained in an amount of from 1 part by mass to 5% by mass based on 100 parts by mass of the liquid crystal sealing agent. / or oligomer. ' [4] The liquid crystal seals as described in any one of [1] to [3] have more than 2 molecules in the molecule. Epoxy resin on the epoxy group, the above epoxy resin 201242986. Revision date: June 22, 2011 is the 101101121 Chinese manual without a slash correction 丨 selected from the double-type epoxy resin, biphenyl At least one type of bifunctional or trifunctional epoxy resin in the group consisting of epoxy resin, biphenyl bond type epoxy resin and diphenol type epoxy resin. [5] as in [1] to [4] The liquid crystal sealing agent according to any one of the invention, which has a softening gambling degree of thief 〜12() by a global method, (3) a plastic polymer, and a number average particle diameter of 〇〇5 μm to 5 μm埶 Plastic polymer microparticles. [6] The liquid crystal sealing agent according to any one of [1] to [5], wherein the filler is contained in an amount of i parts by mass to 5% by mass based on the amount of the liquid crystal sealing agent. [7] The liquid crystal sealing agent according to any one of [1] to [6], wherein the curing agent containing 1 part by mass to 5 parts by mass of the epoxy resin is contained in an amount of the mass of the liquid crystal sealing agent. . [8] The liquid crystal sealing film according to any one of [1] to [n], which is used for the production of a liquid crystal display panel by a liquid crystal dropping method. The second invention of the present invention relates to the manufacture of a liquid crystal display panel. [9] A method of manufacturing a liquid crystal display panel includes the steps of: preparing a display substrate and forming a counter-optical wire thereon, and using the same on the silk plate a liquid crystal sealing agent according to one of the above-mentioned liquid crystal sealants is formed into a seal pattern; in a state in which the upper four seal patterns are not cured, liquid crystal H is added to the other substrate on the substrate in the seal pattern region of the substrate, and the other The substrate is superposed; and the sealing pattern is photocured and then thermally cured. 201242986 Revision period: 101 years 6丨j 22"| For the 101101121 Chinese manual without marking [10] If [9] § has been installed in the liquid crystal display panel, the above steps to form the "ί ® case The step of forming the above-described sealing pattern by using the liquid crystal sealing agent* to form a dummy pattern. The third invention of the present invention relates to a liquid crystal display panel. [11] A liquid crystal display panel comprising a display substrate and The pair of facing substrates H of the display substrate, the frame-shaped (four) member between the upper substrate and the opposite substrate, and the space surrounded by the sealing member filled between the opposite substrate of the display substrate disk Liquid crystal = and the above-mentioned sealing member is a cured product of the liquid crystal sealing agent described in (1) to (A). [Effect of the Invention] According to the present invention, it is possible to provide a storage stability and an excellent bonding strength. Liquid-sealing sealant of liquid-type sealant. 1. Liquid crystal sealant The liquid crystal sealant of the present invention contains (1) intramolecular inclusion (with 曱=Γ湖(meth)acrylic acid modified epoxy resin, (7) Hard 2! 乂 and (3) Photoinitiator. Liquid crystal sealant, if necessary, may also be used! Epoxy resin having two or more epoxy groups in the molecule, (d1:2) = monomer and / or oligomers, (5) thermoplastic polymer particles (A = filler and (7) epoxy resin hardening catalyst, etc. Q6) (1) (fluorenyl) acrylic modified epoxy resin (fluorenyl) acrylic acid modified As long as the epoxy resin is modified by the epoxy resin epoxy resin, the acid base can be used to make the epoxy 201242986 _ , 1 is the 101106121 Chinese manual without a slash correction. Period: On June 22, 101, a (mercapto)acrylic modified epoxy resin obtained by reacting a fat with a (mercapto)-acid in the presence of a diligent age. 环氧树脂 The epoxy resin to be used as a raw material is only intramolecular. The bifunctional or higher epoxy resin having two or more types of epoxy earth may be, for example, bisphenol A ^, double-preferred F type, 2,2,-di-dipropyl fluorene type A, and gasification. Double-dragon-type bismuth-type epoxy resin; benzene-preferred acid varnish type, hop-on-the-spot type, joint stupid varnish type and three _ secret lacquer type secrets, moon paint·oxy resin Biphenyl type epoxy resin; naphthalene type epoxy resin, etc. The amount of functional groups of the epoxy resin of the material is limited, and the polyfunctional epoxy resin of the second material is converted into a dilute acid by a (meth)acrylic acid. Among the cross-linked dense 2-functional epoxy resins of the modified epoxy resin, 'excellently double-type and double-presence 裒=裒 oxy-resin. Double-epoxy epoxy resin and biphenyl _ etc. = Compared with 'lower crystallinity, more excellent coating stability. 曰F type (4) (4) Α type Wei resin or · It's epoxy resin, it is better to use (A; Upgraded. (Caf _ = the content rate is too low (4) (4) Acid-modified epoxy = 201242986 Revision date: 丨01年6爿22 |_:| is No. 106121 Chinese manual without sizing correction (meth)acrylic acid modification The weight average molecular weight of the epoxy resin may be from about 300 to about 500. The weight average molecular weight of the (meth)acrylic acid modified epoxy resin is determined by Gel Permeation Chromatography (GPC). The ethyl acrylate acid-modified epoxy resin has an epoxy group and a (meth)acrylic group in the molecule, and therefore the liquid crystal sealing agent containing the (meth)acrylic modified epoxy resin has both photohardenability and thermosetting. Sex. The amount of the (meth)acrylic acid-modified epoxy resin to be added is preferably from 5 parts by mass to 95 parts by mass, more preferably from 10 parts by mass to 60 parts by mass, based on 100 parts by mass of the liquid crystal sealing agent. When the amount is less than the lower limit, there is a possibility that the sealing member has a small component and the liquid crystal (four) property is insufficient. Further, when the amount is more than the upper limit, the amount of other components may be relatively small, and the chemical properties may be insufficient. (1-2) Epoxy resin having two or more epoxy groups in the molecule The liquid crystal sealing agent of the present invention may contain an epoxy resin having an epoxy group as needed in the liquid crystal sealing agent. * In the example of having two or more of 3 in the sub-group, it is selected from the group consisting of bisphenol-type cyclic oxime resin, yam, and bisphenol: The at least one bifunctional or trifunctional = oxime resin may be contained alone or in combination of two or more. The above-mentioned % oxygen resin preferably has a softening point of at least the above, and the solubility and diffusibility of the epoxy resin in the liquid crystal are low, and the moisture resistance of the sealing member obtained is improved. It is called hard 10 201242986Li Revision date: June 22, π is the 101101121 Chinese manual without scribe correction The epoxy resin preferably has a weight average molecular weight of ~1〇_' preferably 500~_. Among them, an aromatic epoxy resin having the above weight average molecular weight is preferred. The weight average molecular weight of the epoxy resin was measured in the same manner as described above. Examples of the aromatic epoxy resin include: aromatic diols represented by biguanide A, double age S, sulphide F, double spleen AD, and the like, and ethylene glycol represented by the aromatic diols , propylene glycol, hydrazine: a secret varnish resin derived from the reaction of an aromatic poly-monohydric succinol or a formazan obtained by the reaction with the alcohol of the table J; the surface condensed by the 3 base (four) or its silk material The benzene surface, and epichlorohydrin = the secret varnish fresh water shrinkage compound; the xylene test resin glycidyl ether compound. It is recommended that the material of the family of epoxy tree is better for the secretive paint type epoxy epoxy resin, the age-old secret varnish type epoxy resin, the double test epoxy resin, the double test oxygen 2 read grease, the triphenyl A variety of epoxy resin, triphenyl acetonitrile type, milk day, three fine epoxy resin, dicyclopentadiene type epoxy resin, a _ type epoxy resin, biphenyl type epoxy (four) containing - And 4=::-Fangxiang epoxy tree, 100 parts by mass of the crystal sealant, and the amount of the epoxy resin having two or more clear = soil in the molecule is preferably set to the mass part - such as The Berry injury is more preferably set to 3 parts by mass to 20 parts by mass. (2) The sclerosing agent is a primary polyhydric thiol hardener having a softening point of 5 吖 to 9 为, which is 3 C or less, and a melting point of 201242986, which is a Chinese syllabus (2). : Two or more groups selected from the group consisting of 6 π 60 π 60 C to 180 C primary polyamine hardeners. The specific combination of the curing agent includes the following four types: the above polyhydric phenol hardening d and the above-mentioned first-order polysulfide hardener, the above-mentioned multiple hardening agent and the above-mentioned primary polyamine hardener; the above-mentioned secondary polythiol hardener and the above-mentioned first-order plural An amine curing agent, the polyhydric phenol curing agent, the second-order polythiol curing agent, and the first-stage polyamine curing agent. In the liquid crystal sealing agent, a curing agent other than the curing agent may be contained within a range that does not impair the effects and objects of the present invention. The secondary polythiol curing agent is liquid at room temperature, and the polyhydric phenol curing agent is soluble in other components contained in the liquid crystal sealing agent. Therefore, when the above-mentioned polyhydric phenol curing agent and the above-mentioned secondary polythiol curing agent group =, the liquid crystal sealing agent does not contain a powder hardening agent, and the amount of the body component can be greatly reduced. Further, since these hardeners are easily dissolved homogeneously in the epoxy resin, the sealing member obtained by curing the liquid crystal sealing agent exhibits high adhesive strength. As described above, the above polyhydric phenol curing agent can be dissolved in other components contained in the liquid crystal sealing agent. Therefore, when the above-mentioned multi-component polybasic hardener is combined with the above-mentioned multi-component hardener disk, the amount of the powder component in the liquid crystal sealing agent can be reduced as compared with the case where only the first-stage polyamine is added; Further, since the above-mentioned primary polythiol hardener is also liquid at room temperature, if the above-mentioned secondary polythiol hardener is combined with the above, it is better than adding only the above-mentioned polyamine hardener. It can reduce the amount of powder components. 12 201242986^ For the Chinese manual No. 101106121, there is no slash correction. This revision date: June 22, 2001 F1 When the above polyhydric phenol hardener, the above two-stage polythiol hardener, and the above-mentioned primary polyamine hardener are combined, For the above reasons, the amount of the powder component in the liquid crystal sealing agent can be reduced. The amount of all the hardeners in the liquid crystal sealing agent is from 4 parts by mass to 30 parts by mass, more preferably from 5 parts by mass to 20 parts by mass, per part by mass of the liquid crystal sealing agent. If the total amount of the hardener exceeds the upper limit, there is a possibility that the viscosity stability is lowered. On the other hand, when the total amount of the curing agent is less than the lower limit, the curing of the resin may be insufficient, and the uncured component may be eluted in the liquid crystal or the like, indicating deterioration in quality or adhesive strength. Hereinafter, each curing agent will be described. (Multiple-purpose hardener) The multi-component hardener used in the present invention is a compound having two or more aromatic hydroxyl groups in one molecule, and has a softening point of 5 〇 π 9 9 π, preferably 6 (TC 〜 80 ° C. If the softening point is in this range, then the thermal curing of the liquid crystal encapsulant can help (1) (fluorenyl) propylene modified epoxy resin or (1-2) has 2 molecules On the other hand, if the softening point is lower than the lower limit, the viscosity stability of the liquid crystal sealing agent may be affected. Further, when the upper limit is exceeded, the above resin may not be obtained. The phenol novolak resin or the phenol aralkyl resin may be a condensate of phenol or cresol and formalin. The phenol aralkyl resin refers to a condensate obtained by condensing benzene 对 对 二甲 二甲 二醇 diol in the presence of a catalyst or an organic catalyst. The hardener may also be the above-mentioned 13 201242986 as the 106121 Chinese manual without line correction The simmering period: 1 6 1 6 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 In the case where the polyphenol hardener is excessively contained, the adhesive strength of the cured product of the liquid crystal sealing agent may be insufficient. Further, if the proportion of the polyphenol curable agent in the hardener is too large, There is a possibility that the photocurability of the liquid crystal sealing agent may be hindered. Therefore, the amount of the multi-component curing agent is preferably set according to the bonding strength of the cured product of the liquid crystal sealing agent and the photocuring property of the liquid crystal sealing agent. The polythiol curing agent is a compound having two or more secondary thiol groups in one molecule and having a melting point of 23 ° C or lower. Examples of the above secondary polythiol compound include: An ester-based thiol compound obtained by esterification reaction of a mercaptocarboxylic acid having a secondary mercapto group with a polyhydric alcohol, that is, a mercaptoester; an aliphatic polythiol; an aromatic polythiol; a mercaptan-modified reactive antimony oil Etc. The polythiol compound may be contained alone or in combination of two or more. The secondary polythiol hardener is suitably obtained by esterification of a mercaptocarboxylic acid having a secondary mercapto group with a polyhydric alcohol. Examples of the mercaptocarboxylic acid having a secondary mercapto group include 2-mercaptopropionic acid, 3-mercaptobutyric acid, 2-mercaptobutyric acid, etc. Examples of the polyhydric alcohol include ethylene glycol and propylene glycol. 1,4-butanediol, 1,6-hexanediol, glycerin, trihydroxydecylpropane, di-trihydroxydecylpropane, pentaerythritol, dipentaerythritol, sorbitol, etc. Specific examples of Weiyl esters It contains pentaerythritol tetrakis(3-mercaptobutyrate), etc. 14 201242986ti Revision period: June 21, 2011 is No. 101106121 Chinese manual no underline ^; ^# # excess containing-grade polythiol In the case of a hardener, there is a possibility that the storage stability of the liquid crystal sealing agent becomes insufficient. Therefore, the adjustment of the secondary polysulfide __ is preferably set according to the viscosity stability of the liquid crystal sealing agent. (First-Oriented Polyamine Curing Agent) The primary polyamine curing agent is a compound having two or more -amino groups (-NH2) in the molecule, and has a melting point of 6 ° C to 18 ° C, preferably 7 Å. 〇 ~ 140 ° C. The primary amine group also contains a hydrazinylgr〇up. The first grade 多元 polyamine hardener is solid when stored in a liquid crystal sealant, usually in the form of a powder. Examples of the primary polyamine hardener include an organic acid diterpene compound, an amine/urea adduct, a gas diamine, a β-million derivative, an aromatic amine, an oxygen-modified polyamine, and a polyamine group. Urea. These primary polyamine hardeners may be contained alone or in combination of two or more. Examples of the organic acid diterpene compound include diammonium adipate (melting point 180 ° C), 1,3-bis(decylcarboethyl)_5-isopropylhydantoin (melting point) 120 ° C ), 7,11-octadecadiene_, 18-dicarbenium (melting point 16 (rc), etc. Examples of the amine/urea adduct include a curing agent commercially available as the Fujicture FXR series. When the first-stage polyamine curing agent is excessively contained, the viscosity of the liquid crystal sealing agent may increase, and the coating stability may be lowered. The amount of the primary polyamine curing agent is preferably set according to the curing rate of the liquid crystal sealing agent. When the polyamine curing agent is in the form of a powder, the number average particle diameter thereof is preferably 0.1 μηη to 5 μηη', more preferably 〇·5 μιη to 3 μηι. By setting the upper limit value or less, the liquid crystal sealing agent The coating stability becomes good, and it can be used in the Chinese manual of No. 106 201242986 without a slash correction. This correction date: 101 years 6 丨] 22 丨 1 fine line width to form a sealing member. In addition, + is in liquid crystal sealing agent When it is stored, it can be set to the lower limit or more, and the oxygen resin reacts. The amount average particle size can be determined by the M4 branching agent and the ring (1) light agent MUM. The photoinitiator is used to make (1) (I I or (4) (meth) acrylate acid epoxy resin described later. The initiator of the reaction, if the liquid crystal is dense, the light hard Id contains the photoinitiator, the temporary hardening of the sealant can be performed by photohardening in the production of the board, and the agent can be used as an agent. It is a known article. Examples of the photoinitiator include a green ketone oxime compound, a ruthenium oxide compound, a dimethine compound, a vinegar oxime content, a benzoin compound, an acetophenone compound, and a diphenyl group. a ketone compound, a sultone compound, an α-sulfenyl compound, a benzoquinone + decanoic acid δ-based compound, a benzoic acid compound, an azo compound, a benzene sulfur (tetra) compound, or an organic pigment system a compound, an iron-phthalocyanine compound, a benzoin ether compound, an agerene compound, etc. Examples of the alkylphenone compound include: 2,2-dimethoxy-1,2-diphenylethene- Benzene oxime dimethyl ketal such as 1-ketone (IRGACURE651); 2-mercapto-2-morpholinyl (4-thiolphenyl) propyl Examples of α-aminoalkyl ketones such as α-aminoalkyl ketones such as _ i ketone (IRGACURE 9〇7); hydroxy-cyclohexyl-phenyl-ketone UKGACURE 184), etc. Examples of fluorenyl phosphine oxide compounds Containing 2,4,6-trimethylphenylnonyl-diphenyl-phosphine oxide, etc. The ferrocene-based compound contains bis(η5-2,4-cyclopentadien-1-yl)_ double (2,6-Difluoro-3-(lH-.pyrrole-fluorenyl)-phenyl)titanium, etc. Example 16 of an oxime ester compound 201242986. Date of revision: June 21, 2011 is the 101106121 The Chinese manual has no drawing line 11 and contains 1.2-octadiene-1-[4-(phenylthio)-2-(0-benzylidene fluorenyl)] (IRGACURE OXE 01 ). 〇 The amount of the photoinitiator to be added is preferably from 0.01 part by mass to 5 parts by mass, more preferably from 0.1 part by mass to 3 parts by mass, per part by mass of the liquid crystal sealing agent. By setting it to the lower limit or more, the curing property of the (1) (fluorenyl) acrylate-modified epoxy resin or the (4) (fluorenyl) acrylate monomer and/or oligomer described later becomes good. In addition, by setting it to the upper limit or less, the stability at the time of application of a liquid crystal sealing agent becomes favorable. (4) (Meth) acrylate monomer and/or oligomer The liquid crystal sealing agent of the present invention may further contain a (meth) acrylate monomer and/or an oligomer. When the liquid crystal sealing agent contains a (fluorenyl) acrylate monomer and/or a material, the liquid crystal sealing agent is light-cured, and the workability at the time of production of the liquid crystal panel is improved. There are no special restrictions on the purpose and effect of Yuming's 7-wire (4) surface material damage and this &quot; (Examples of the Lr oligomer include the following (meth)propene monodipropylene glycol and/or -methyl ketone, propylene glycol, etc., 4 mol or more of diacrylic acid; Dipropylene Ethylene Ethylene Light (4) Fine Lay It (4) A Addition 2 More W-Alcohol Diacrylate and/or II 17 201242986 is the first 〇ιι〇6ΐ2 二醇Chinese manual without slash correction This revision period: June 22, Η 甲基 methacrylate; 3 烧 几 几 _ _ 环氧 环氧 环氧 环氧 环氧 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或More than 4 moles of acid ester and / or dimethacrylate or trimethyl, acrylate or tripropylene oxime addition of more than 4 moles of epoxy; for 1 mole of double acrylic vinegar and / or two A diol polycyanate triacrylate and/or dimethyl decyl ethyl) bis-trimethyl sulphate is obtained as ===, three = and / or trimethyl propyl hydride, Or oligomers thereof; i: = poly = and / or polymethyl acrylate vinegar; three (pro- s = t hexane vinegar modified three (acrylic oxyethyl) diced cyanide; Internal _ modified three (methyl olefinic Ethoxyethyl) dicene 4 cyanate vinegar: 2, dipentaerythritol polypropylene _ and 7 or polymethyl propyl i acid g 曰, ... s 曰 modified pentaerythritol polyacrylic acid vinegar and / or polymethyl Acetic acid S曰 'secretic acid new red alcohol two coffee and / or dimethyl ketone vinegar '2: 岐 _ _ ketic acid neopentyl glycol two __ and / or dimethyl 1 diluted, vinegar; Epoxy epoxide modified amic acid acrylic acid vinegar and / or dimethyl propylene % oxyethylene modified alkylated phosphoric acid acrylate and / or dimethacrylate; neopentyl glycol, Trimethylolpropane, oligoacrylate of pentaerythritol, and/or oligomeric methacrylate, etc. Compared with 100 parts by mass of the liquid crystal sealing agent, the amount of (meth) acrylate monomer and/or oligomer is more It is preferably set to 1 part by mass to 50 parts by mass, more preferably set to 5 parts by mass to 20 parts by mass. (5) Thermoplastic polymer microparticles The liquid crystal sealing agent of the present invention contains, as needed, a method determined by the ring and ball method. 201242986 _ LX is the first wish slogan Chinese _ book no face correction this correction coffee ring month 22 softening point temperature is 50 ° C ~ 120. 〇 preferably 7 〇 ° c ~ 1 〇〇〇 c a plastic polymer, and may also contain thermoplastic polymer microparticles having a number average particle diameter of 〇〇5 μηι 5 μπ;, preferably 0.1 μη!~3 μηη, by containing thermoplastic polymer microparticles in a liquid crystal sealing agent. It is possible to alleviate the shrinkage stress generated in the cured product of the liquid crystal sealing agent. Further, by setting the number average particle diameter to the upper limit or less, it is possible to prevent the thermoplastic polymer particles from being caused when forming the sealing member having a fine line width. The coating stability is lowered. The method of measuring the number average particle diameter 〇 is the same as the method described above. Examples of the thermoplastic polymer microparticles include: a resin containing an epoxy group and a double bond group, and a radical polymerization capable of The fine particles obtained by suspension polymerization of the monomers. Examples of the resin containing an epoxy group and a double bond group include a resin obtained by reacting a bisphenol F type epoxy resin with methacrylic acid in the presence of a tertiary amine. Examples of the monomer which can be freely bonded include butyl butyl acrylate, glycidyl methacrylate, and divinyl benzene. The blending amount of the thermoplastic polymer fine particles is preferably 5 parts by mass to 4 parts by mass, more preferably 7 parts by mass to φ30 of the mass of the liquid crystal sealing agent, from ☆, 里切. By setting it as such a range, the thermoplastic polymer fine particles can alleviate the shrinkage stress at the time of heat curing of the liquid crystal sealing agent, and the sealing member can be formed with a target line width. The filler may also further contain a filler in the liquid crystal sealing agent. By filling 1 - the viscosity of the liquid crystal sealing agent can be suppressed, and the liquid crystal sealing agent can be hardened to obtain the strength of the member, the linear expansion property, and the like. The filler is not particularly limited, and examples thereof include calcium carbonate and magnesium carbonate. 19 20124298^ Revision date: 101 years 6 22 [I is the first instruction of the Chinese translation No. 106121 No underline correction of the sulfuric acid pin, magnesium sulfate, Shi Xi _ Lu, qt chemical (alumina), zinc oxide, dioxocene talc, glass beads, sericite, active collar ^, industrial clay, aluminum telluride, nitriding core nuclear machine filling. It is preferably dioxane or talc. The shape of the filler to be used is not particularly limited, and any of the two-plate shape and the needle-shaped private filling table of a fixed shape or an indefinite shape is preferably an average-time 2 Γ埴 right HI, and preferably a specific surface area thereof. It is 55m2/g~20g. The true charge_average-secondary particle size can be measured by the laser diffraction method of Jisna (5). In addition, the surface area of the feng σ ^ ^ 可 表面积 表面积 表面积 表面积 表面积 表面积 表面积 表面积 表面积 表面积 表面积 表面积 表面积 表面积 表面积 表面积 表面积 表面积 表面积 表面积 表面积 表面积 表面积 表面积 表面积 表面积 表面积 表面积 表面积 表面积 表面积 表面积 表面积 表面积 表面积 表面积 表面积 表面积 表面积 表面积 表面积 表面积 表面积 表面积 表面积 表面积 表面积 表面积 表面积 表面积 表面积 表面积, better Α 1 Λ 曰, car ^ u better for 1G quality reading ~ 3G parts by mass. The amount of the powder component in the liquid crystal sealing agent may increase, resulting in a decrease in coating stability. (7) Epoxy resin hardening catalyst Hardening month, liquid enthalpy into the sealing process 'Optional epoxy resin may also be included. When the liquid crystal sealing agent contains a curing catalyst for an epoxy resin, the sealing property of the sealing member obtained by curing the liquid crystal sealing agent is improved, and the bonding strength of the sealing member is also improved. The curing catalyst for the epoxy resin is not controlled as long as it does not impair the purpose and effect of the present invention, such as an amine, an amine, an adduct thereof, and the like. Compared with the liquid crystal sealant, the blending amount of the hardening catalyst is 20 201242986. The revised period: 1〇1 June 22nd is the 101106121 Chinese manual without scribe correction. The best is 0.1 heavy injury~5 quality The wound is more preferably 0.5 parts by mass to 3 parts by mass. (8) Other Additives The liquid crystal sealing agent of the present invention may further contain a coupling agent such as a ruthenium radical polymerization initiator or a zea stagnation coupling agent, an ion trapping agent, an ion exchanger, a leveling agent, and the like. Additives such as pigments, dyes, plasticizers, defoamers. Further, in order to adjust the gap of the liquid crystal panel, a spacer or the like may be disposed. The liquid crystal sealing agent of the present invention contains (1) (meth)acrylic acid modified epoxy tree ruthenium, (2) a hardener, and (3) a photoinitiator, and thus can be preferably used for mostly photohardening and heat. A liquid crystal sealing agent for a hardened liquid crystal dropping method. The liquid crystal sealing agent for liquid crystal dropping method preferably further contains (1_2) an epoxy resin having two or more epoxy groups in the molecule, and (4) a (meth)acrylic acid vinegar monomer and/or oligomer. More preferably, it contains # (5) thermoplastic polymer microparticles and (6) a filler. The viscosity of the liquid crystal sealing agent of the present invention at 25 ± 25 rpm obtained by an E-type viscometer is preferably 3 〇 Pa.s to 4 〇〇 p ^ s, more preferably 刈 Pa.s 〜 35GPW viscosity of the liquid crystal sizing agent in the above range is stable (9) Method for producing liquid crystal sealing agent The liquid crystal sealing agent of the present invention is a (1) molecularly modified propyl group-containing (meth)propionic acid. Epoxy tree, (2) hard ^3 (3) photoinitiator and other components as needed are uniformly mixed and the material = square: and: not limited, for example, it is preferred to use a three-parent mixer to fill the knife . Further, at this time, it is preferable to sufficiently defoam the liquid crystal sealing agent. 21 201242986 Revision date: June 22, 2011 is No. 106121 Chinese manual No scribe correction No bubble. 2. Method of Manufacturing Liquid Crystal Display Panel The liquid crystal display panel of the present invention includes a display substrate, a counter substrate paired therewith, a frame-shaped sealing member interposed between the display substrate and the counter substrate, and a display substrate and a pair A liquid crystal layer in a space between the substrates surrounded by the sealing member. The cured product of the liquid crystal sealing agent of the present invention can be made into a sealing member. The display substrate and the opposite substrate are both transparent substrates. The material of the transparent substrate is not particularly limited, and examples thereof include glass, polycarbonate, polyethylene terephthalate, polyethersulfone, and p〇lymethyl Methacrylate (PMMA). A matrix-shaped thin film transistor (TFT), a color filter, a black matrix, or the like may be disposed on the surface of the display substrate or the counter substrate. An alignment film is further formed on the surface of the display substrate or the opposite substrate. The alignment film contains a known organic alignment agent or inorganic alignment agent. The manufacturing method of the liquid crystal display panel by the liquid crystal dropping method includes: a) the first step of forming a sealing pattern of the liquid crystal sealing agent of the present invention on one substrate; a2) the second step, in a state where the sealing pattern is not hardened Adding liquid crystal to a region surrounded by the seal pattern of the f-plate or another substrate opposite to the region surrounded by the seal pattern; a3) The third step of separating one substrate from the other substrate The seal pattern is overlapped; and 22 201242986^ is the 10th 1106121 Chinese saying that the duck viscera correction date: June 22, 2011 a4) The fourth step is to harden the seal pattern. The state in which the seal pattern in the step a2) is not cured refers to a state before the hardening reaction of the liquid crystal sealant proceeds to the gel point. Therefore, in the step a2), in order to suppress the dissolution of the liquid crystal sealing agent in the liquid crystal, the sealing pattern may be light-irradiated or heated to be semi-hardened. One of the substrates and the other of the substrates are respectively a display substrate or a counter substrate. Since the liquid crystal sealing agent of the present invention has a small amount of powder in the curing agent, it is possible to achieve thinning of the street seal pattern. The sealing pattern of the liquid crystal sealing agent of the present invention may have a cross-sectional area of about 15 μm 2 to 3 μm 2 . In the step a4), only hardening by heating may be performed, and after hardening (temporary hardening) by light irradiation, it is preferable to perform hardening by heating (formal hardening). The liquid crystal sealing agent is instantly cured by temporary hardening by light irradiation, whereby the respective components can be suppressed from being dissolved in the liquid crystal. The photohardening time also depends on the composition of the liquid crystal sealant, for example, about 10 children. The light irradiation energy may be energy of a degree of hardening which can be cured by (1) (fluorenyl)acrylic acid modification Q $ocene oxide resin or (4) (meth) acrylate monomer and/or oligomer. The light is preferably ultraviolet light. The heat hardening temperature also depends on the composition of the liquid crystal sealant, for example, 120 〇c, and the heat hardening time is about 2 hours. Here, in the case where the liquid crystal display panel is manufactured by the liquid crystal dropping method, in many cases, the step a3) is performed under reduced pressure, and the step of &amp; 4) is performed after being opened to atmospheric pressure. Specifically, after the two substrates are superposed in the step a3), the liquid crystal display panel is returned to atmospheric pressure. At this time, the area surrounded by the two substrates and the liquid crystal sealing agent is sealed and kept under reduced pressure. 23 201242986 i L is the 101106121 Chinese manual without a slash correction. Revision date: 丨01年6 f] 22丨| Therefore, in the region surrounded by the liquid crystal sealing agent, the force acts on the two substrates in the direction in which the substrates approach each other. On the other hand, since the outside of the frame of the liquid crystal sealing agent is opened to atmospheric pressure, the force does not act on the two substrates in the direction in which the substrates approach each other. Therefore, there is a problem that the substrate warps and the gap widens from the center portion of the liquid crystal display panel toward the outside of the liquid crystal sealing agent. If unevenness occurs in the gap in the liquid crystal display panel, display reliability is lowered. 0 In order to solve such a problem, a method of additionally providing another frame (auxiliary seal) on the outer side of the frame (main seal) of the liquid crystal sealing agent is conventionally used (for example, Reference is made to Japanese Patent Laid-Open Publication No. 2002-328382. According to this method, the area between the main seal and the main seal and the auxiliary seal is also reduced. Thereby, on the outer side of the main seal, the force acts on the two substrates in the direction in which the substrates approach each other, and the warpage of the substrate can be suppressed. Therefore, according to this method, the gap in the liquid crystal display panel can be made uniform. Further, in order to improve the manufacturing efficiency of the liquid crystal display panel, it is desirable to form an auxiliary package. Therefore, as a method of making a two-piece base = gap = uniform without forming an auxiliary seal, for example, when the liquid crystal display panel is opened to atmospheric pressure, the liquid crystal display panel is opened to atmospheric pressure, for example, when the liquid crystal display panel is opened to atmospheric pressure. The movement of the substrate on the inside of the seal (toward the warpage of the substrate toward each other: it and the liquid crystal sealant can be deformed) can suppress the substrate inscription without forming an auxiliary seal. The amount of the liquid crystal sealant of the previous body is 'liquid crystal The sealing agent is large; the component 'the liquid crystal sealing agent is hard, and it is difficult to carry out the above-mentioned variation. The content of the powder component of the liquid crystal sealing agent of the present invention is 24 201242986 _ L1 is No. 01106121 This correction period: 6 1 6 June 22 ,, the liquid crystal sealant has high flexibility. Therefore, the seal pattern necessary for sealing the liquid crystal can be formed without forming the auxiliary seal pattern, and the liquid crystal display panel 0 can be manufactured. The liquid crystal sealing agent of the invention can be used not only for the above-described method for manufacturing a liquid crystal display panel using a liquid crystal dropping method, but also for a liquid crystal display panel using a liquid crystal injection method. The manufacturing method of the liquid crystal display panel using the liquid crystal injection method includes: O bl) the first step of forming a sealing pattern of the liquid crystal sealing agent of the present invention on one substrate; b2) the second step, one substrate and another a substrate is overlapped by a sealing pattern; b3) in the third step, the sealing pattern is thermally hardened to obtain a liquid crystal injecting unit having an injection port for injecting the liquid crystal; b4) Step 4: Injecting liquid crystal into the liquid crystal through the injection port In the injection unit; and 3 b5) the fifth step, the injection port is sealed. In the step bl) to the step b3), a liquid crystal injection unit is prepared. First, prepare two transparent substrates (for example, glass plates). Then, a sealing pattern is formed using a liquid crystal sealing agent on one of the substrates. After the other substrate is superposed on the surface on which the sealing pattern of the substrate is formed, the sealing pattern may be cured. In this case, it is necessary to provide an injection port for injecting liquid crystal into a part of the liquid crystal injecting unit. The injection port may be provided in the portion where the sealing pattern is drawn. Alternatively, after the seal pattern is formed, the seal pattern of the desired portion is removed to provide an injection port. 25 201242986 For the Chinese manual No. 106121, there is no slash correction. The revised period: 101 years 6 丨 22 22 Η (6) The thermal hardening conditions of the step towel also depend on the formation, for example, 2 hours to 5 hours at 150 C. In the group M) step of sealing d, the liquid crystal injection unit obtained in the step - b3) is subjected to the following steps: (4) internal state is straight L) state 'inhalation of liquid crystal from the injection port of the liquid crystal injection unit 2. The liquid crystal sealing agent of the present invention is excellent in the coating property of the liquid crystal sealing agent of the present invention, and the coating property of the liquid crystal sealing agent of the present invention is good, and the strength is also good, and the strength is also good, and further, the storage is performed. According to the liquid crystal sealing agent of the present invention, it is possible to form only a liquid crystal display panel having excellent gap stability between the seals (4) necessary for sealing the liquid crystal without forming the auxiliary read pattern. Example of soil plate [Synthesis Example 1] Synthesis of thioglycol-modified bisphenol F-type epoxy resin (7〇% partial methylpropionate) 160 g of liquid bisphenol f-type epoxy resin (Epotohto) YDF-8170C, manufactured by Dongdu Chemical Co., Ltd., epoxy equivalent 16 〇g/eq), 0.1 g of p-methoxyphenol as polymerization inhibitor, 0 2 g of ethanolamine as a catalyst, and methacrylic acid added by g The flask was placed in a dry air and refluxed at 90 ° C for 5 hours. The obtained compound was washed 2 times with ultrapure water to obtain a thioglycol-modified bisphenol F-type epoxy resin. 26 201242986Α The first copy of the duck in the slogan is 细 丨 丨 6 6 6 6 6 6 6 6 此处 此处 此处 此处 此处 此处 此处 此处 此处 此处 此处 此处 此处 此处 此处 此处 此处 此处 此处 此处 此处 此处 此处 此处 此处 此处 此处 此处 此处 此处 此处 此处The amount of the methyl acrylate group contained in the methacrylic acid to be reacted was 0.70 mol. Therefore, the obtained mercaptoacrylic acid modified bisphenol F type epoxy resin is a 70% partial methacrylate. [Example 1] A methacrylic acid-modified bisphenol F-type epoxy resin (7 % by weight partial methacrylate) obtained in Synthesis Example 0 was used, using a two-roll mixer, 0 parts by mass, a polyphenol hardener Α ( Manufactured by Mitsui Chemicals Co., Ltd.: MileX3L·, softening point 71 C) 4 parts by mass, secondary polythiol hardener B (manufactured by Showa Denko ΡΕ-1) 8 parts by mass, primary polyamine hardener D (manufactured by adeka company: EH-5057, melting point 8 (rc) 4 parts by mass, photoradical polymerization initiator as photoinitiator (manufactured by Ciba_Gage Co., Ltd.: Irgacure 651) 1 part by mass, hardening catalyst (four countries) Manufactured by Chemical Co., Ltd.: 2MAOK) 2 parts by mass, thermoplastic polymer microparticles (manufactured by Ganz: F351) 20 parts by mass, filler (filler), Si〇2, 1 part by mass, simmering coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd.: The resin composition of the mass fraction was sufficiently mixed to obtain a uniform liquid, and a liquid crystal sealing agent was obtained. The viscosity (initial viscosity) was measured by the method described later, and as a result, it was 240 Pa*s ° [Example 2] In addition to the polyphenol curing agent Eight is 8 parts by mass, one A liquid crystal sealing agent was obtained in the same manner as in Example 1 except that the polyvalent amine curing agent D was 8 parts by mass, and the second-order polythiol curing agent was a mass fraction of ruthenium. The viscosity (initial viscosity) was measured by the method described later as a result of 320 Pa. *s. 27 201242986 l For the Chinese manual No. 101106121, there is no slash correction. This revision date is: June 22, Η [Example 3] In addition to making the polyphenol phenol hardener into 8 parts by mass, the secondary polythiol hardener A liquid crystal sealing agent was obtained in the same manner as in Example 1 except that B was 8 parts by mass and the primary polyamine curing agent was in the form of a mass fraction. The viscosity (initial viscosity) was measured by the method described later as a result of 250 Pa.s. A liquid crystal sealing agent was obtained in the same manner as in Example 1 except that the secondary polythiol curing agent B was 8 parts by mass and the primary polyamine curing agent D was 8 parts by mass. The viscosity (initial viscosity) was measured by the method described later. The result was 260 Pa*s. [Example 5] The amount of the mercaptoacrylic acid-modified bisphenol F-type epoxy resin (70% partial mercapto acrylate) obtained in Synthesis Example 1 was 40 parts by mass, polyphenol hard The amount of the agent A is 7 parts by mass, the amount of the secondary polythiol hardener B is 14 parts by mass, the amount of the primary polyamine hardener D is 7 parts by mass, and the amount of the thermoplastic polymer fine particles is 19 parts by mass, and the filler A liquid crystal sealing agent was obtained in the same manner as in Example 1 except that the amount was 9 parts by mass. Further, the viscosity (initial viscosity) was measured by a later method and found to be 21 Å Pa.s. [Example 6] The amount of the thiol-acrylic acid modified double-aged F plastic ring-air resin (70% partial methacrylate) obtained is 56 parts by mass, the amount of the polyphenol curing agent A is 1 part by mass, and the second-order polythiol hardener B The amount is 3 parts by mass, the amount of the primary polyamine curing agent D is 1 part by mass, the amount of the thermoplastic polymer fine particles is 23 parts by mass, and the mass of the filler is 12 quality. 28 201242986^ Revision date: June 21, 2011 The Japanese manual No. 1_01106121 has no underline correction of the crystal sealant. In addition, the utilization result is 300 Pa*s. In the same manner as in Example 1, the viscosity (initial viscosity) was measured in the same manner as in Example 1. [Example 7] In addition to the use of a multi-component hardener B fDTr VIII 4 β company: TD2m, softening point 80 ° c) 4 mass In place of the multi-round wheel, the sulphuric acid hardener A, and the amount of the second-grade polysaccharide sulphur hardener B is 8 mass parts, θ ^ v , t berry s knife-level polyamine hardener D ΓΛ田里广 &quot; The same liquid crystal sealant was obtained. In addition, the degree of enthalpy (initial toxicity, knot % Pa*s was measured by the method described later. [Example 8] ^ Using a multi-purpose hardener c (manufactured by Mitsubishi Chemical Corporation: 17〇, 匕 point % C ) 4 parts by mass Instead of multi-pure hardener a, and the amount of secondary polythiol hardener B is 8 皙蔷 in hail ^ ^ Λ shell 罝, first-class polyamine hardener D = n ί injury' and Example 1 In the same manner, the liquid crystal sealing agent was obtained. In addition, the dot (initial viscosity) was measured by the method described later, and the result was 255 Pa*s. [Example 9] The amount of the hardener A was 4 parts by mass, and the secondary polysulfide was used. Alcohol hardening (4) B is 8 parts by mass of bismuth, and polyamine hardener A (manufactured by Japan Hydrazine Co., Ltd.: ADH, melting point 18 (Γ(:) 4 parts by mass and polyamine hardener D4 parts by mass) is used as the -type polyamine hardener. In the same manner as in Example 1, except for the case of Example 1, the viscosity (initial viscosity) was measured by the method described later, and the result was 27 〇Pa.s. [Example 10] 29 201242986 is the first specification of No. 1) Painted dirty correction date of revision: 1〇ι年6丨]22 y except that the amount of phenolic hardener A is 4 The amount of the second-component polythiol hardener B is 8 parts by mass, and the polyamine curing agent B (Fuji Cure Industrial Co., Ltd.: Fujicure FXR-1020, melting point 125 ° C) is used in an amount of 4 parts by mass and the polyamine hardener D4 is used. A liquid crystal sealing agent was obtained in the same manner as in Example 1 except that the first-stage polyamine curing agent was used. The viscosity (initial viscosity) was measured by the method described later, and it was 260 Pa, s. [Example 11] In addition to the phenol curing agent A The amount is 4 parts by mass, the amount of the secondary polythiol hardener B is 8 parts by mass, and 4 parts by mass of the polyamine curing agent C (manufactured by Ajinomoto Fine-Techno Co., Ltd., VDH, melting point: 120 〇C) is used as the primary plural. A liquid crystal sealing agent was obtained in the same manner as in Example 1 except for the amine curing agent. The viscosity (initial viscosity) was measured by the method described later, and it was 250 Pa*s. [Comparative Example 1] In addition to the phenol curing agent A as a curing agent A liquid crystal sealing agent was obtained in the same manner as in Example 1 except that the mass fraction was 16 parts by mass, the secondary polythiol curing agent, and the primary polyamine curing agent were used. The viscosity (initial viscosity) was measured by the method described later. The result was 350 Pa*s. [Comparative Example 2] In addition to the fact that the secondary polythiol hardener B as a curing agent was 16 masses, the polyhydric phenol hardener, and the primary polyamine hardener were 〇 mass parts, The liquid crystal sealing agent was obtained in the same manner as in Example 1. The viscosity (initial viscosity) was measured by the method described later, and it was 210 Pa*s. [Comparative Example 3] 30 201242986, Revision date: June 22, 2011 Γ〇1106121 Chinese manual No sizing correction This is the same as Example 1 except that the primary polyamine curing agent D as the curing agent is 16 parts by mass, the polyhydric phenol curing agent and the secondary polythiol curing agent are 〇 mass parts. A liquid crystal sealing agent was obtained. Further, the viscosity (initial viscosity) was measured by the method described later, and as a result, it was 37 〇Pa.s. [Comparative Example 4] The amount of the mercapto-acrylic acid-modified double-hop F-type epoxy resin (70% partial methacrylate) obtained in Synthesis Example 1 was 38 parts by mass, and the amount of the phenol curing agent A was 8 parts by mass. The amount of the polythiol curing agent B is 16 parts by mass, the amount of the polybasic curing agent D is 8 parts by mass, the amount of the filler is 18 mils, and the amount of the thermoplastic t ary granule is $ parts by mass, and examples 1 A liquid crystal sealing agent was obtained similarly. Further, the viscosity (initial viscosity) was measured by the method described later, and the result was 280 pa*s. [Comparative Example 5] The amount of the methyl acetoacetate-modified bis-oxygen resin (70% partial methyl acrylate) obtained in Synthesis Example 1 was % by mass, and the amount of the catalyzing agent A was The amount of 0.5 parts by mass, the amount of the secondary polythiol hardener b is 2 parts by mass, and the amount of the polyamine curing agent D is Q.5. The amount of the fine particles is 23f parts, and the amount of the filler is outside the amount ' A liquid crystal sealing agent was obtained in the same manner as in Example 1. In addition, the viscosity (initial viscosity) was measured by the method, and the result was 27 〇Paq. &lt;Comparative Example 6], 4 to a less cardiac sterol hardening agent (manufactured by Sigma Chemical Co., Ltd.: TMMP (trimethane thiol propionate h mass parts as poly-alcohol curing agent, obtained in the same manner as in Example 1) Liquid crystal sealing agent ^ ^ 31 201242986 is the Chinese manual of No. 106121 No underline correction This correction date: 101 years 6&gt;j 22 测定 The viscosity (initial viscosity) was measured by the method described later, and the result was 260 Pa*s. 7] A liquid crystal sealing agent was obtained in the same manner as in Example 1 except that a phenolic curing agent D (manufactured by DIC Corporation: TD2090, softening point: 100 ° C) was used as the polyhydric phenol curing agent. The viscosity (initial viscosity) was measured by the method described later. The result was 270 Pa*s. [Comparative Example 8] Using a three-roll mixer, epoxy resin (manufactured by Nippon Kayaku Co., Ltd.: EOCN-1020-75) 10 parts by mass, (mercapto) acrylate single Body and/or oligomer (manufactured by Osaka Organic Chemical Industry Co., Ltd.: Biscoat #300) 53 parts by mass, primary polythiol hardener a 5 parts by mass, primary polyamine compound (Amicore Fine-Techno: Amicure VDH) 5 Parts by mass, Photoradical polymerization initiator (Irgacure 184) 2 parts by mass, thermoplastic polymer microparticles (manufactured by Ganz: F351) 12 parts by mass, Si〇2 (filler) 12 parts by mass, 矽院偶Mixture (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM-403) 1 part by mass of the curable resin composition was sufficiently mixed to obtain a uniform liquid, and a liquid crystal sealing agent was obtained. Further, the viscosity (initial viscosity) was measured by the method described later, and the result was 250 Pa*s [Evaluation] Viscosity stability, seal coatability, adhesion strength, display state, high temperature and high humidity reliability, and gap precision were measured for Examples 1 to 11 and Comparative Examples 1 to 8. The method is as follows. The results of the measurements are shown in Tables 1 to 3. 32 201242986 Stomach No. 1^) No. 1106121 Chinese specification without a line &quot; Correction period: June 22, 101 1) Viscosity stability The method of 'liquid crystal sealant in the main shot ☆ is 1G g. The liquid crystal sealant of the example and the comparative example is selected to be degassed after the liquid crystal sealant of 1010.+.φ9 pieces. The initial viscosity was measured for the f2g using the E_degree meter. Then: recognize. ), 2.5 - Ο Ο in the environment for 1 week, then - owe 2 7 ° σ; 23 c, 50% RH, the point after i week is increased relative to __ ^ The rising price of the initial _ degree is ◎ (very excellent); when it is more than 丨丨 and ., when it is seven or less, it is 〇; when it is more than U times and is less than i/time, the difference is); when it is more than 1.5 times, it is evaluated as X ( difference). Sealing coatability for A (slightly 2) The liquid crystal sealant 2 〇 g obtained in the examples and the comparative examples was filled in/main morphing state. Then, 1 g was discharged from the ^2 undershooter equipped with a caliber 〇 35, and then left at 23 ° C for 1 day. Then, the injector of the ^ is placed on the distributor (Hitachi Plant Technologies, Inc., in the injection, at 360 mm&gt;&lt; 470 mm for the display panel of the liquid crystal display panel and manufactured by the company). 35 mmx40 mtn board (曰 pattern. At this time, the discharge pressure is set to 0_3 MPa, the cut seal is 3000 μm, and the coating speed is set to 100 mm/s. The shape of the household seal pattern is as follows Evaluation: The frame mold that is not produced at all and has no sealing gap and seal drawing is 5〇. Often excellent) *@( ^ There is no sealing notch at all, and the frame mold for sealing drawing is 48~49 33 201242986 —5脳(2) Chinese Reward No Strike Correction Revision Date: 丨01年6 n 22丨 〇:〇(Excellent) No seal notch is produced at all, and the frame mold for seal drawing is less than 48.x (poor) * 3 Display state and high-temperature high-humidity reliability test The liquid crystal sealant obtained by the above examples and comparative examples was produced by a dispenser (Shot Master, manufactured by Musashi-Engineering), in which a transparent electrode and an alignment film were formed in advance. 4 A triangular seal pattern (cross-sectional area 3500 μιη2) (main seal) was formed on a 0 mmx45 mm glass substrate (made by EHC, RT_DM88_PIN). Then, a square seal pattern (a square seal pattern of 38 mrnx 43 mm) was formed on the outer periphery thereof. Then, a liquid crystal material (MLC-119000-000: manufactured by Merck) equivalent to the amount of the panel content after the bonding was accurately dropped into the frame of the main seal by means of a dispenser. Then, the glass substrate paired therewith was bonded under reduced pressure, and then the atmosphere was opened and bonded. Next, the two glass substrates to be bonded were held in a light-shielded box for 3 minutes, and then irradiated with ultraviolet rays of 2000 mJ/cm 2 and further heated at 10 ° C for 1 hour. The obtained liquid crystal display panel was stored in a thermostatic chamber at 70 ° C and 95% RH for 500 hours. The chromatic aberration caused by the liquid crystal around the sealing portion before and after storage was visually observed. When the color difference was not confirmed at all, it was evaluated as ◎ (non-苇k), and it was evaluated as 0 (excellent) when almost no chromatic aberration was tolerated; Δ was evaluated when chromatic aberration was confirmed; and X (poor) was evaluated when chromatic aberration was clearly confirmed. Further, the liquid crystal display panel taken out in the constant temperature bath and stored after being applied with a voltage of 5 V by a DC power supply device was driven. According to the liquid crystal sealant attached 34 201242986 _ Li Correction period: 1〇1 June 22R is No. 1106121 Chinese manual without scribe line correction The current liquid crystal display function is functioning normally at the beginning of self-driving to evaluate the liquid crystal display The display characteristics of the panel. The display characteristics were evaluated as ◎ (excellent) when the liquid crystal display function was normally performed up to the sealing margin, and was evaluated as 〇 (good) when the abnormality of the liquid crystal display function was confirmed at a position near the sealing margin of 1 mm. When the abnormality of the liquid crystal display function was confirmed to be Δ (slightly worse) when the sealing margin was more than ο"mm and less than 〇3 mm, the abnormality of the display function was confirmed to be x (poor) when the sealing margin exceeded 0.3 mm. . '° 4) Bonding strength In the above 3), the tensile test apparatus (manufactured by Intesco) was used for the sample of the liquid crystal display panel stored in the thermostatic chamber, and the plane tensile strength was measured at a tensile speed of 2 m/min. . The adhesion was evaluated as follows. Bonding strength is 20 MPa or more: ◎ (excellent) Bonding strength is 15 MPa or more and less than 20 MPa : 〇 (excellent) Bonding strength is 7 MPa or more and less than 15 MPa : △ (slightly poor) Bonding strength is less than 7 MPa : X (poor) 5) Clearance accuracy For the liquid crystal sealant obtained in the examples and the comparative examples, a dispenser (Shot Master, Musashi 2) was used to form a 40 mm &lt; 45 mm preformed with a transparent electrode and an alignment film. A triangular seal pattern of 35 mm x 40 mm (cross-sectional area 3000 μm 2) was formed on a glass substrate (manufactured by EHC, RT-DM88-PIN) (main seal). Thereafter, the seal pattern of the outer periphery is not formed. The line width of the sealant after bonding the paired substrates was measured, and the gap precision was confirmed based on the value. When the seal line width is less than 1 mm, it is evaluated as 〇35 201242986 Revision date: 101 years 6 Η 22 Η It is No. 106106 Chinese manual without line correction (excellent), when it is 1 mm or more, it is evaluated as X (difference 36 201242986 cm Εί 9 聍Ξι:a&gt;s nr 讲 囚 · · · · · · · · · · · · · · 1 1 inch T ' ^ (N 〇〇〇〇 ◎ ◎ 〇 00 1 1 inch 1 1 00 1 1 1 inch rN 〇〇〇〇 ◎ ◎ 〇 1 inch 1 1 00 1 1 1 inch (N 〇〇〇 ◎ ◎ ◎ 〇 VO ί—Η 1 1 1 1 1 1 1 &lt;N (N —_ Η ◎ ◎ 〇 ◎ ◎ 〇〇 1 1 1 1 1 inch 1 1 1 卜 CN On 〇 〇〇 ◎ ◎ ◎ 〇 Inch 1 1 1 1 1 00 1 1 1 00 fN 〇〇〇◎ ◎ ◎ 〇cn 〇〇1 1 1 1 〇〇t 1 1 1 CN 〇◎ ◎ 〇◎ ◎ 〇fN 00 1 1 1 1 1 1 1 1 00 (N 〇〇〇 ◎ ◎ ◎ 〇 inch 1 1 1 1 00 1 1 1 inch (N 〇〇〇 ◎ ◎ ◎ 〇-S? cold r *f ί ^ · TM φ Γ &quot; ^ac 5| B- Hardener A ( Chemical point 71 °C) Hardener B (softening point 80 °c) Hope hardener C (softening point 90 °c) Phenol hardener D (softening point 100 °c) Thiol hardener A (grade polythiol) Thiol hardener B (secondary polythiol) amine hardener A (melting point 180 ° c) amine hardener B (melting point 125 ° c) amine hardener C (melting point 120 ° c) amine hardener D (melting point 80 °c ) 1 Irgacure 651 1 2MAOK F351 Si02 ΚΒΜ-403 Viscosity stability seal coating adhesive strength indication state high temperature and high humidity reliability gap precision tantalum hardener thiol hardening m 1 amine hardener photoinitiator Hardening catalyst: evaluation of composition of thermoplastic polymer microparticle filler coupling agent 201242986 I UUi 9 ii :smHT _ 柃ΗΓ 槲5a· _Era,^«#-^t(N19 0 1I0l^ii£l mdrNIal inch [&lt;NS 卜1 1 1 inch 1 〇〇f 1 1 inch (N 〇◎ 〇X &lt;3 &lt;1 inch 1 1 1 00 1 1 1 1 inch (N 〇X 〇&lt;] 〇in 00 ir&gt; *Λ 1 1 1 1 (N 1 1 1 m 〇r Η (N (N ◎ ◎ ◎ XXX 你 你 寸 oo m 〇〇» 1 1 1 1 » 1 00 Η (N 〇〇00 1—^ &lt;〇&lt; ] &lt;&lt;1 X m 1 1 1 t 1 1 1 1 1 CN 〇X ◎ ◎ ◎ X (N 1 1 1 1 1 1 » 1 1 (N 〇 &lt;] ◎ &lt;&lt;] 〇1 1 1 1 1 1 1 1 1 1&quot;&quot;Η fN 〇◎ 〇X &lt;] 〇&gt;1'« inch 1 1 1 1 〇〇1 1 inch painting r &lt; (N 〇1 1 &lt;1 〇〇◎ ◎ 〇 〇1 1 i 1 〇〇t inch 1 inch (N 化合物 compound obtained in Synthesis Example 1 (methacrylic acid modified bisphenol epoxy resin) phenol hardener A (softening point 71 ° c) Phenol hardener B (softening point 80 ° C) Phenol hardener C (softening point 90 ° C) Phenol hardener D (softening point 100 ° C) Thiol hardener A (grade polythiol) alcohol hardening Agent B (Secondary polythiol) Amine hardener A (melting point 180 ° C) Amine hardener B (melting point 125 ° C) Amine hardener C (melting point 120 ° C) Amine hardener D (melting point 80 ° C) Irgacure 651 2MA0K F351 ^1 $ KBM-403 Viscosity stability seal coating adhesive strength indication state high temperature and high humidity reliability gap accuracy: thiol hardening of the hardener; amine hardener 1 light initiator 1 hardening Medium 1 thermoplastic polymer microparticles Filler coupling agent composition evaluation 201242986 Hsi 9ltrlGl :δ&gt;Β3Ι _ pieces w_ 鹱観 _ Kj Helmet «旮黟ItNI 9 0 II Ο I 濉 vein c-arNIal inch [£&lt;] Comparative Example 8 〇m 1 1 1 1 irj 1 1 1 in 1 CN 1 CN rsj &lt;〇&lt;&lt;&gt; 〇〇EOCN-1020-75 Biscoat #300 硬硬剂 A 盼硬剂剂 B 硬硬剂 c 1 硬硬剂D thiol hardener A thiol hardener B amine Hardener A Amine hardener B Amine hardener C Amine hardener D Irgacure 651 1 F351 Si〇2 KBM-403 Viscosity stability seal coating adhesive strength indication state high temperature and high humidity reliability gap precision epoxy resin (methyl Acrylate monomer and/or oligomer sclerosing agent thiol-based hardener amine-based hardener photopolymerization initiator hardening catalyst thermoplastic particle: filler coupling composition evaluation 6 £ 201242986 is the first 隐 隐 隐__正本赃·如询η [丨 According to Table 1 and Table 2, it is known to use a secondary polythiol selected from a multi-component hardener having a softening point of 5 (rc~90〇C, and a sleek point of 231 or less). The hardener and the melting point are in the group consisting of 6 (rc~18 (rc-class polyamine hardener) In the case of the above-mentioned hardeners, viscosity stability, seal coatability, adhesion strength, display state, high temperature and high humidity reliability, and gap precision are excellent (Examples 1 to 11). In the case of the multi-pure hardener of the machine-thief (Comparative Example 1), the 'bonding strength is low, and the display state and the high-temperature and high-humidity reliability are slightly inferior to those of the examples 1 to n. In addition, only the melting point is used. In the case of the second-order polythiol hardener of 23 C (Comparative Example 2), the viscosity stability, the adhesion strength, the display state, and the high-temperature and high-humidity reliability were all inferior to those of Examples 1 to 11. Further, only In the case of a primary polyamine curing agent having a melting point of 6 (rc to 18 〇t: (Comparative Example 3), the viscosity stability is low, and the seal coatability and the gap precision are lowered. Further, even if the use is selected from a softening point of 5 〇.〇~9〇t: a polyphenol hardener, a secondary polythiol hardener having a melting point of 23 ° C or less, and a primary polyamine hardener having a melting point of 60 C to 180 C. Two or more hardeners, as opposed to When the amount of the crystal sealant is less than 4 parts by mass (Comparative Example 5), the adhesive strength, the display state, and the high temperature and humidity reliability are lowered. On the other hand, the quality is relative to the liquid crystal sealant. In the case where the amount of the above-mentioned curing agent exceeds 3 parts by mass (Comparative Example 4), the viscosity stability, the adhesion strength, the display state, the high-temperature and high-humidity reliability are lowered, and the gap precision is poor. Furthermore, the use of a primary polythiol hardener instead of a secondary polythiol 40 201242986. For the "01106121 Chinese manual without a slash correction of this revision date: 101 years of the month 22 曰 hardener (Comparative Example 6 and comparison In the case of Example 8), the viscosity stability was lowered, and the adhesion strength, the display state, and the high-temperature and high-humidity reliability were also lowered. In addition, when the softening point of the phenol curing agent exceeded 90 ° C (Comparative Example 7), the bonding strength was observed. In the liquid crystal sealing agent of the present invention, since the powder component derived from the curing agent is small, the liquid crystal sealing agent is applied to form a fine seal. In the case of the member, the coating stability is also good at 0. Further, since the adhesive strength and the viscosity stability are excellent, a liquid crystal panel excellent in display reliability can be provided. Therefore, the liquid crystal sealing agent of the present invention is suitable for producing a liquid crystal display. Panel. [Simple diagram description] None. [Main component symbol description] None. 41 201242986" For the Chinese manual No. 101106121, there is no slash correction. This revision period: June 22, 2011. Invention patent specification one (The format and order of this manual are not subject to change, please do not fill in the ※ part) ※Application Case No.: ※Application date: ※卩匚卩匚Classification: 1. Invention name: (Chinese/English), liquid crystal sealing agent, manufacturing method of liquid crystal display panel using the same, and liquid crystal display panel 0 LIQUID CRYSTAL SEALING AGENT, FABRICATING METHOD OF LIQUID CRYSTAL DISPLAY PANEL USING THE SAME AND LIQUID CRYSTAL DISPLAY PANEL 2. SUMMARY OF THE INVENTION An object of the present invention is to provide a liquid crystal sealing agent which has good storage stability and can form a sealing member having a fine line width. a (meth)acrylic modified epoxy resin containing an epoxy group and a (meth)acrylic group in the molecule, (2) a hardener, and (3) a photoinitiator, and the above component (2) is selected a polyphenol hardener having a free softening point of 5 (TC to 9 〇 °c, a secondary polythiol hardener having a melting point of 23 ° C or less, and Two or more kinds of hardeners in a group consisting of a primary polyamine hardener having a melting point of 60 ° C to 18 ° C and containing 4 parts by mass to 30 parts by mass relative to 10 parts by mass of the liquid crystal sealing agent The above component (2). III. English Abstract: The object of this invention is to provide a liquid crystal 201242986 is the Chinese manual of No. 106121 without a slash correction. Amendment date: June 22, η sealing The liquid crystal sealing agent includes: (1) a (meth)acrylic modified epoxy resin having an epoxy group and a (meth)acrylic group in a molecular, (2) a curing agent and (3) a photo initiator, the component (2) is two or more curing agents selected from a group consisting of a poly phenol curing agent with a soften point of 50 to 90°C, a secondary Polythiol curing agent with a melting point of 23 °C or less, and a primary polyamine with a melting point of 60 to 180 ° C. The content of the Component (2) is 4 to 30 part by mass based on 100 parts by mass of the liquid crystal sealing agent. 201242986 is No. 106121 Chinese _ book _ 镰 正本 lilEB»〇liF6/]22 VII, apply for patent garden: A liquid crystal sealing agent comprising (1) a (meth)acrylic modified epoxy resin containing an epoxy group and a (meth)acrylic group in the molecule, (2) and (3) a photoinitiator, and The component (2) is selected from the group consisting of a softening point of 5 to 7 to 9 Å. a polyhydric phenolic hardener of hydrazine, a secondary polyhydric thiol hardener having a melting point of 23 t or less, and two or more hardeners of a group consisting of a primary polyamine hardener having a melting amount of 60 C to 180 C, and The component (2) is contained in an amount of 4 parts by mass to 30 parts by mass based on 1 part by mass of the liquid crystal sealing agent. 2. The liquid crystal sealing agent according to the above aspect of the invention, wherein the phase of the liquid crystal sealing agent is 100 parts by mass, and the above component (1) and the read mass portion to 5 parts by mass of the above-mentioned component (1) and the mass of the mass are contained in the above-mentioned liquid crystal sealing agent. The liquid crystal sealing agent according to the invention of claim 1, wherein the liquid crystal sealing agent is 100 parts by mass or more, and further contains 1 part by mass of the (meth) acrylate. Monomer and / or oligomer.八4. The patent of the towel 4, &amp; the liquid crystal sealant of the above item i, further contains an epoxy resin having two or more epoxy groups, the above epoxy resin = free double (tetra) epoxy resin, joint At least one scoop bifunctional or trifunctional epoxy resin in a group consisting of a benzene type epoxy resin, a biphenyl sulphur type epoxy resin, and a triphenyl sulphur type epoxy resin. The liquid crystal sealing agent described in the first aspect of the invention is the softening point temperature determined by the ball-and-ball method, which is muscle ~ (10). The thermoplastic poly 42 of 2012 c. 201242986li ^ is the 101st leg of the 21st Chinese manual without a slash correction. The 〆 〆 . . . . . . . . . . . 101 101 101 101 101 101 101 101 101 101 101 101 101 101 101 101 101 101 101 101 101 101 101 101 101 Thermoplastic polymer microparticles. 6. The liquid crystal sealing agent according to the above aspect of the invention, wherein the liquid crystal sealing agent contains 100 parts by mass of the filler, and contains 1 mass of the filler to the mass. 7. The liquid helium sealant according to the first item of the patent application, wherein the hardening catalyst containing 0.1 part by mass of the epoxy resin is contained in an amount of 0.1 part by mass relative to the liquid crystal sealant. . 8. The liquid crystal sealing agent according to claim 1, which is used for the production of a liquid crystal display panel using a liquid crystal dropping method. A method of manufacturing a liquid crystal display panel, comprising the steps of: preparing a display substrate and a pair of opposite substrates, and forming a sealing pattern on a substrate using the liquid crystal sealing agent according to claim 1; In a state where the sealing pattern is not cured, liquid crystal is dropped on the sealing 图案 pattern region of the substrate or another substrate paired with the substrate; the one substrate is overlapped with the other substrate; and the sealing pattern is performed After photohardening, thermal hardening is performed. The method of manufacturing a liquid crystal display panel according to claim 9, wherein the step of forming the seal pattern is a step of forming only the seal pattern by using the liquid crystal sealant without forming an auxiliary pattern. 11. A liquid crystal display panel comprising: a display substrate, an opposite substrate paired with the display substrate, 43 201242986 Revision date: 6/U2 "I is No. 106121 Chinese manual without drawing! Correcting a frame-shaped sealing member inserted between the display substrate and the opposite substrate, and a liquid crystal layer in a space surrounded by the upper sealing member filled between the display substrate and the opposite substrate, and The second sealing member of the agent is the liquid crystal sealing device described in the first paragraph of the patent application. 201242986. For the Chinese manual No. 101106121, there is no slash correction. The date of revision: June 22, 2011 Η 4. Designated representative map: (1) The representative representative of this case is: No. (2) The symbol of the symbol of this representative figure is simple: jfe 〇5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: ❹ No.