TW201132667A - Liquid crystal sealing agent, method for fabricating liquid crystal display panel using the same and liquid crystal display panel - Google Patents

Abstract

The purpose of the invention is to provide a liquid crystal sealing agent, wherein the display characteristics would not change even under conditions of high temperature and high humidity, showing excellent reliability. The liquid crystal sealing agent of the invention comprises a (meth)acrylate modified epoxy resin, curing agent, and photopolymerization initiator by the reaction of epoxy resin with two or more epoxy groups and (meth)acrylic acid. The (meth)acrylate modified epoxy resin contains a hydroxyl group produced by the above-mentioned reaction of epoxy resin with two or more epoxy groups and (meth)acrylic acid. The ratio of the equivalence of (meth)acryloyl group/ the equivalence of epoxy group of the (meth)acrylate modified epoxy resin exceeds 9, and the hydrogen bonding functional group value containing the hydroxyl group is 3x10<SP>-3</SP> mol/g to 5x10<SP>-3</SP> mol/g.

Description

201132667 VI. Description of the Invention: This application claims priority based on Japanese Patent Application No. 2010-072893 filed on March 26, 2010. The contents described in the specification and drawings of the application are all incorporated in the specification of the present application. [Technical Field] The present invention relates to a liquid crystal sealing agent, a method of manufacturing a liquid crystal display panel using the same, and a liquid crystal display panel. [Prior Art] In recent years, liquid crystal display panels have been widely used as image display panels of various electronic devices typified by mobile phones or personal computers. The liquid crystal display panel is an image display panel having a structure in which a liquid crystal material (hereinafter simply referred to as "liquid crystal") is formed between two transparent substrates having electrodes provided on the surface thereof, and the periphery thereof is sealed by a liquid crystal sealing agent. Although the liquid crystal sealing agent is used in a very small amount, it is in direct contact with the liquid crystal, and thus has a large influence on the reliability of the liquid crystal display panel. Therefore, in order to achieve high image quality of the liquid crystal display panel, highly desirable and diverse characteristics of the liquid crystal sealing agent have been achieved. Previously, liquid crystal display panels have been mainly manufactured by liquid crystal injection. The liquid crystal injection method is generally a method of forming a frame by applying a liquid crystal sealing agent on a ruthenium transparent substrate, and (2) drying the liquid crystal sealing agent by prebaking the substrate, and bonding the other substrate; (3) The two substrates are heated and pressure-bonded to connect the substrates to each other, thereby forming a frame (cell) of the liquid crystal sealing agent between the substrates; (4) after injecting an appropriate amount of liquid crystal into the empty cells, 4 201132667 is sealed The liquid crystal injection port 'by this manufactures a liquid crystal display panel. On the other hand, recently, as a method of manufacturing a liquid crystal display panel which is expected to have improved productivity, a liquid crystal dropping method is being studied. The liquid crystal dropping method is a method of (1) coating a liquid crystal sealing agent on a transparent substrate to form a frame for filling a liquid crystal; (2) dropping a minute liquid crystal in the above frame; (3) keeping the liquid crystal sealing agent unhardened In the state, the two substrates are superposed under high vacuum; (4) the liquid crystal sealing agent is cured to produce a panel. In the liquid crystal dropping method, a liquid and a thermosetting liquid crystal sealing agent are used, and in the step (3), the liquid crystal sealing agent is temporarily hardened by irradiation with light such as ultraviolet rays, and then post-hardened by heating. Regarding the liquid crystal sealing agent for liquid crystal dropping method, for example, the use of liquid % oxygen contact (special dispersion) has been proposed. However, this Wei Na has a solubility in a liquid crystal at normal temperature, and is a factor that degrades the display characteristics of a liquid crystal display panel.

Patent document 2); containing propyl fumarate modified glutamate and urethane urethane crystal sealant (for example, Patent Document 3), etc. [Prior Art Document] [Patent Document] Benzene acid varnish (novolac) epoxy [Killow Document 1] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. 〇〇6 124698 bulletin 201132667

I ^ ^ Λ L The resins described in Patent Document 2 and Patent Document 3 are all low in solubility in liquid crystal at room temperature. However, since the resin is easily dissolved in the liquid crystal under high temperature and high humidity conditions, the display characteristics of the liquid crystal display panel may be degraded. In particular, in the liquid crystal dropping method, since the uncured liquid crystal sealing agent is in contact with the liquid crystal, the components of the liquid crystal sealing agent are easily dissolved in the liquid crystal, and the display characteristics of the liquid crystal display panel are liable to be lowered. In view of the above, it is an object of the present invention to provide a liquid crystal sealing agent which is excellent in display reliability even when the display characteristics are not changed under conditions of high temperature and high humidity. As described above, in order to prevent the display characteristics of the liquid crystal display panel from deteriorating, it is important to suppress the dissolution of the liquid crystal sealing agent in the liquid crystal. The dissolution of the resin in the liquid crystal can be suppressed to some extent by using a crystalline resin. However, in particular, the resin is easily dissolved at a temperature, and therefore it may be dissolved in the liquid crystal. Further, since the conventional liquid crystal sealing agent which is inhibited from being dissolved in the liquid crystal is likely to have a high viscosity, it has a problem of poor coatability and workability. On the other hand, the inventors of the present invention have focused on a method of reacting a part of an epoxy group of an epoxy resin with (mercapto)acrylic acid, and introducing a hydroxyl group having a low compatibility with a liquid crystal. This inhibits the dissolution of the resin in the liquid crystal. Further, it has been found that the solubility of the resin in the liquid crystal is not only greatly affected by the absolute number of hydroxyl groups contained in the resin, but also by the ratio (equilibrium) of the number of hydroxyl groups to the number of unreacted epoxy groups. That is, it was found that 'by increasing the ratio of the number of hydroxyl groups to the number of unreacted epoxy groups, specifically, the range of the hydrogen bonding functional group is within a certain range, and (methyl) 6 201132667 -----Γ1Ι The equivalent of the olefin group / the equivalent of the epoxy group is a certain value or more, and can be inhibited from being dissolved in the liquid crystal. The present invention is based on such findings. The first invention of the present invention relates to a liquid crystal sealing agent. [1] Liquid crystal sealant 'comprises (meth)acrylic modified epoxy resin, thermosetting agent, and photopolymerization obtained by reacting an epoxy resin containing two or more epoxy groups in the molecule with (mercapto)acrylic acid Starting agent 'the above (fluorenyl) = dilute acid-modified epoxy resin containing a hydroxyl group formed by the reaction of the above-mentioned (mercapto)acrylic acid epoxy resin having two or more % oxygen groups in the molecule a hydrogen bond functional group, and the equivalent of the (/) acryl group of the above (fluorenyl) acrylate-modified epoxy resin has an equivalent weight of more than 9, and the above hydrogen bond functional group value is 3 x 3 · 3 mol /g~5xl〇-3 m〇l/g. [2] The liquid crystal sealing agent according to [1], wherein the epoxy resin having 1 to 2 or more epoxy groups in the molecule is selected from the group consisting of biphenyl type epoxy tree ruthenium naphthalene type epoxy resin And a difunctional epoxy resin in a group consisting of double-type epoxy resins. The liquid crystal encapsulant according to [2], wherein the difunctional % oxygen resin is a double-type A type epoxy resin or a double-fluorene type F epoxy resin. [4] The liquid crystal sealing package according to any one of [1] to [3] wherein the softening point is further contained in an amount of from 1 to 20 parts by weight based on 100 parts by weight of the liquid crystal sealing agent. It is a solid epoxy resin of 40 ° C or more and 150 ° or less. The liquid crystal sealing pair according to any one of the above-mentioned items, wherein the photopolymerization initiator is selected from the group consisting of a benzophenone compound and a phosphatide phosphine compound. At least one compound of the group consisting of a titanocene compound and a compound of the group 201132667. [6] The liquid crystal sealing agent according to any one of [1], wherein the thermal hardener has a melting point of 5 Å. 〇 Above 25〇〇»c below. [7] The liquid crystal sealing agent according to any one of [1] to [6], which is selected from the group consisting of an organic acid diterpenoid compound, an imidazole compound, a dicyandiamide compound, and the like. At least one of the groups consisting of amine compounds. [8] The liquid crystal sealing agent according to any one of [1] to [7], wherein the liquid crystal sealing agent 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 a method of manufacturing a liquid crystal display panel using a liquid crystal sealing agent, and the like. [9] A method of manufacturing a liquid crystal display panel, comprising the steps of: forming a seal pattern by using a liquid crystal sealant according to any one of items [1] to [8] on a substrate; In a state where the pattern is not hardened, liquid crystal is dropped on the other of the substrate in the region of the sealing pattern of the one substrate or on the other substrate paired with the one substrate; the one substrate is overlapped with the other substrate; and the sealing pattern is caused to be performed. After photohardening, thermal hardening is performed. [10] A liquid crystal display panel comprising a display substrate, a counter substrate paired with the display substrate, a frame-shaped sealing member interposed between the display substrate and the opposite substrate, and a display substrate and the opposite direction A liquid crystal layer in a space surrounded by the above-mentioned sealing member between the substrates, and the sealing member is a cured product of the liquid crystal sealing agent according to any one of the items [1] to [8]. [Effect of the Invention] According to the present invention, it is possible to provide a liquid crystal sealing which is excellent in display reliability so that the above and other objects, features and advantages of the present invention can be more clearly understood. The drawings are described in detail below. [Embodiment] I liquid crystal sealing agent The liquid crystal sealing agent of the present invention contains (A-1) (meth)acrylic modified epoxy resin, (B) thermal curing agent, and (C) photopolymerization initiator, as needed Further, it may further contain (A-2) a solid epoxy resin, (D) an acrylic resin, and (E) a filler. (A) Epoxy Resin (A-1) (Meth) Acrylic Modified Epoxy Resin ^ The inventive (meth)acrylic modified epoxy resin is preferably obtained by using a ring-resin with a (meth)acrylic acid. For example, a (meth)acrylic modified epoxy resin obtained by a reaction in the presence of a basic catalyst. It is known that the epoxy resin to be a raw material has two or more rings in the molecule, and a difunctional or higher epoxy resin in the earth. 2, 2, 2.: diallyl double A type, double expectant type AD And hydrogenation double ^ = sizing #, oxygen resin; benzene riding paint type, a secret varnish type, fat type t triphenyl _ varnish type varnish type epoxy tree 笪 two t sorrel resin, naphthalene ring Oxygen resin, etc. For the tri- or tetra-functional ^ &amp; epoxy resin (meth) acrylic acid modified (曱201132667 drop, so 夂 is better; the density is high, the adhesion strength is easy to lower the fat and oxime is better Epoxy resin, naphthalene type ring tree is double bis-type, excellent Hi touch (4) (4) oxy resin secret, epoxy resin with coated body 2 raw material can be one type, or two or more kinds of 钽 "method Preferably, the epoxy resin is obtained by a molecular vapor evaporation method, and the reaction between the epoxy resin obtained by adding t and the methyl group and the (meth)acrylic acid is preferably in a quantity (four) of the county. It is better to tear it in a ί μ style. The equivalent of the (meth) (tetra) acid-modified epoxy resin terpene fluorenyl group is a (meth)acrylic acid-modified epoxy resin of Γι Weight average molecular weight: the amount of epoxy in the epoxy resin modified by "冋 methyl) acrylate, the weight of the epoxy resin contained in the sulfonic acid modified epoxy resin Formal representation of MW). That is, the equivalent of (methyl) dilute/epoxy group 201132667 is the same as the average number of (meth)(tetra)fluorenyl groups/the average number of epoxy groups. The ratio of the number of hydroxyl groups (produced by the reaction) to the number of unreacted county bases of the (meth)acrylic acid-modified epoxy resin having an equivalent of (meth)acrylonitrile group and an equivalent weight of the epoxy group of less than 9. Small, or the ratio of the reactant (% oxygen-containing resin containing a radical) to the unreacted material (the epoxy resin containing no secret) is small, and it is difficult to obtain an effect of suppressing dissolution in the liquid crystal material. The above case will be specifically described by taking an epoxy resin as a raw material as a difunctional epoxy resin. When a difunctional epoxy resin reacts with (meth)acrylic acid, both of the epoxy groups are unreacted. Residual unreacted material, 2) one (meth)acrylic acid modified part of (meth)acrylic acid, and 3) 2 epoxy groups all modified by (meth)acrylic acid ( Three kinds of methyl) acrylates. In addition, when the difunctional epoxy resin and the (meth)acrylic acid are reacted such that the number of (fluorenyl) acrylonitrile groups/the number of epoxy groups is 丨, it is confirmed that cesium is significantly dissolved in the liquid crystal. The ratio of the formation of unreacted materials remains at about 25 mol%. On the other hand, when the number of (meth)acrylic fluorenyl groups/the number of epoxy groups exceeds 9, the ratio of 1) unreacted materials which are apparently dissolved in the liquid crystal can be reduced to 2 m. When 〇1% or less, the dissolution in the liquid crystal can be remarkably suppressed. In particular, the (fluorenyl) acrylic modified epoxy resin used in the present invention preferably has a relatively soft skeleton and has low crystallinity. The sealant containing such a (meth)acrylic modified epoxy resin tends to be relatively low in degree and easily dissolved in the liquid crystal. By making the ratio of the equivalent of the (meth)acrylonitrile group / the equivalent of the epoxy group more than 9', even such a low-viscosity (mercapto) propylene

S 11 201132667_r Acid-modified epoxy resin is also difficult to dissolve in liquid crystal. The weight average molecular weight of the (meth)acrylic modified epoxy resin may be about 310 to 500. The weight average molecular weight Mw of the (meth)-glycolic acid-modified epoxy resin can be, for example, by gel permeation chromatography (Gd)

Permeation Chromatography, GPC). On the other hand, when the ratio of the equivalent of the (meth) acrylonitrile group to the equivalent of the epoxy group exceeds 9 ❿, the hydroxyl group formed by the addition reaction of (meth) propylene gamma may increase. Therefore, the moisture resistance of the cured product is lowered. Therefore, it is preferable to set the upper limit of the ratio of the equivalent of the (meth) acrylonitrile group to the equivalent of the epoxy group to such an extent that the moisture resistance is not greatly impaired. Alternatively, by using (A-2) a solid epoxy resin having a softening point of 40 C to 150 ° C as described later, or using a high-temperature hot hardener as the (B) heat hardener, it is also possible to maintain _ . Further, the (meth)propionate-modified epoxy resin having a ratio of the equivalent of the (meth)acrylinyl group to the equivalent of the epoxy group of less than 9 has a small content ratio of the (fluorenyl)acrylonitrile group. Therefore, the liquid crystal sealing unit is less likely to be temporarily hardened by light, and it is difficult to suppress elution of the liquid crystal cell. The (meth)acrylic modified epoxy resin has a hydroxyl group and an amine group. Hydrogen such as an acid ester bond, an acid amine group, or a silk is functional, and examples of such an exemplary functional group include at least an epoxy group formed by an epoxy group and a hydroxyl group formed by (meth)acrylic acid. a hydroxyl group, an amino formic acid, a recording domain, or the like contained in a (fluorenyl)acrylic acid or epoxy resin which is a (fluorenyl) acrylic modified epoxy resin mooncake. A resin having a hydrogen bonding functional group and The hydrophobic liquid crystal material has low compatibility, so it is inhibited from being dissolved in the liquid crystal material. The hydrogen bond functional value of the (fluorenyl) acrylic modified epoxy resin is preferably 3 x l 〇 -3 mol / g. ~5xl〇-3 m〇l/g, more preferably 3 5xl〇-3 咖%~ 4_5xl〇_3 m〇l/g. When the hydrogen bond functional group value is less than 3χΐ〇3 m〇l/g, the number of hydrogen bond functional groups contained in one molecule of the (fluorenyl)acrylic acid modified epoxy resin is small, so that it is difficult to obtain inhibition. When the effect of dissolution in the liquid crystal exceeds 5 χ 10·3 mol/g ', the moisture resistance of the cured product of the (meth)acrylic acid-modified epoxy resin is liable to lower. Hydrogen bond of the (meth)acrylic acid-modified epoxy resin The functional group value (two 〇i/g) is based on "1 molecule of (meth)acrylic acid modified epoxy resin, hydrogen bond functional group number" / "(meth) propylene riding modified epoxy resin The weight average is expressed in the form of Sub® (Mw). For example, a (meth)-acid-modified epoxidation domain functional group having only a radical obtained by reacting (meth)acrylic acid with an epoxy resin as a nitrogen-bonding functional group can be used by The molar number of the (indenyl)acrylic acid of the reaction was determined by dividing the weight average molecular weight (Mw) of the (meth)acrylic acid-modified % oxygen resin. -Methyl) (4) The hydrogen bond functional group value of the acid-modified epoxy resin can be adjusted, for example, by the reaction of the (meth)acrylic acid which is a complementary epoxy resin, which is a raw material (sub-base) The amount of the hydrazone functional group which the acid or the epoxy resin has is controlled. The base value of the acid-modified epoxy resin is preferably 3 by 3 _ to 5 χ 10 mol/g, and the weight of the liquid crystal sealing agent is just as the weight of the epoxy resin to be reacted with the (meth)acrylic acid. Parts, (methyl) propyl acid conversion ring

S 13 201132667 The content of the oxygen resin is difficult to be 1 G by weight to 7 parts by weight to 50 parts by weight. It is better to have 20 weights of such a '(meth)acrylic acid modified epoxy tree f and = acrylic acid base, so it can have both photocurable fat and also inhibit the liquid crystal by the base number relative to the epoxy group __ Ί Dissolved in. The singularity (Α-2) solid epoxy resin of the present invention (4) The need for (4) % 1 low dispersion The liquid crystal panel obtained has good display characteristics and can improve the moisture resistance of the cured product. Deficit f 诵 this!:! Epoxy resin can be an aromatic epoxy resin with a weight average molecular weight of 50 () ~ = L 曰 ~ 5000. The weight average molecular weight of the solid oxime can be measured in the same manner as described above. Rolling ς ^1 species / fragrant epoxy 旨 赖 包括 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 Aromatic polyglycidol obtained from the reaction with Table = ir ydrin: a mouthful, a multi-age bribe represented by a varnish resin derived from phenol or cresol and formaldehyde, polyalkenyl or a copolymer thereof The secret varnish type polyglycidyl test compound obtained by the reaction, the glycidyl ether compound of the benzene dimethylphenol resin, and the like. Among the above aromatic epoxy resins, the indophenol novolac type epoxy 201132667, the benzene-clear varnish-type epoxy resin, the double-aged A-type epoxy resin, and the bisphenol-r-three-type epoxy resin are preferred. , triphenyl (10); two epoxy resin, dicyclopentadiene epoxy resin, === rhyme, biphenyl epoxy resin. Further, these may be preferred; =; =: /, the amount of two, two υ 里 里, more preferably 3 parts by weight ~ 10 Cao 詈: too much tamping content, sometimes the viscosity of the liquid crystal sealant (4) When the content of the epoxy resin (four) is too small, the moisture resistance of the cured product of the liquid crystal sealing agent may be insufficient. (A-1) (methyl) propyl benzoate modified epoxy resin with (

Acid-modified epoxy resin / solid-state ring G property view = two =: =: the wettability of the hardened material is higher than the upper right 篁 则 则 则 则 则 则 筚 筚 筚 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶When the ratio is too small, the content of the solid epoxy resin is large, so the viscosity is sometimes changed to two, and the coatability is lowered. (Β) The thermosetting agent is a thermosetting agent which is not mixed in an epoxy resin, and is not in a state of being usually accompanied by a resin (at room temperature, under visible light, etc.); Hardener hardened by epoxy resin. The liquid crystal sealing agent containing ruthenium and ketone is excellent in storage stability and excellent in thermosetting property. The thermal curing agent used in the invention may be a known thermal curing agent, liquid crystal sealing _ viscosity stability, and moisture resistance. The point of view and 201132667 ·*» ·&quot;··»··························································· It is preferably a thermosetting agent of not more than 100 Å or less, and further preferably a melting point of 15 CTC or more and 20 (a thermal curing agent of TC or less. Preferred examples of such a thermosetting agent include an organic acid diterpenoid compound and an imidazole system. a compound, a dicyandiamide compound, a polyamine compound, etc. Examples of the organic acid diterpenoid compound include diammonium adipate (melting point of 181 〇C) and 1,3-double (fluorenyl group). Carbon ethyl)·5_isopropylethyl carbazide (melting point 120 ° C), 7,11-octadecadiene-1,18-dicarbenium (melting point 160 ° C), twelve Bismuth alkanoic acid (melting point ι9 〇ΐ) and azelaic acid 肼 炼 (refining point is 189 ° C), etc. Examples of the oxime compound include 2,4-diamino -6-[2 |-B Imidazolyl-(anthracene ethyl carbaryl (melting point: 215 ° C ~ 225 C) and 2-phenylimidazole (melting point i37 ° C ~ 147 eC), etc. Examples of dicyandiamide compounds include dicyandiamide Diamine (melting point: 209 C), etc. The polyamine compound is a thermal latent curing agent having a polymer structure obtained by reacting an amine with an epoxide (ep〇xy ), and specific examples thereof include ADEKA (manufacturing) Adeka Hardener EH4339S (softening point is 120 ° C ~ 130 ° C), and Adeka Hardener EH4357S (softening point is 73 ° C ~ 83 ΐ) manufactured by ADEKA Co., etc. These thermal hardeners can be used alone' The amount of the thermosetting agent to be added is preferably adjusted so that the amount of active hydrogen equivalent is from 0.8 equivalent to 1.2 equivalents per equivalent of the amount of the ring. The liquid crystal sealant containing a heat hardening agent can form a so-called one-liquid hardening resin. Composition: The one-liquid curable resin composition does not need to be mixed with a hardener in use, and is excellent in properties. 201132667 (c) Photopolymerization initiator Photopolymerization initiator is used to make (A-) ( (meth)acrylic acid modified epoxy resin or (D) described later When the liquid crystal sealing agent contains a photopolymerization initiator, when the liquid crystal sealing agent contains a photopolymerization initiator, the sealing agent can be temporarily cured by photocuring, and the working procedure becomes easy. A known photopolymerization initiator can be used, and examples thereof include an alkylphenone-based compound, a fluorenylphosphine oxide-based compound, a titanocene-based compound, an oxime ester-based compound, a benzoin-based compound, and an acetophenone-based compound. a benzophenone compound, a thioxanthone compound, an α-mercapto oxime compound, a phenylglyoxylate compound, a benzoin compound, an azo compound, or a diphenyl sulfide A compound, an organic dye-based compound, an iron-phthalocyanine-based compound, a benzoin ether-based compound, an anthraquinone-based compound, or the like. Examples of the ketone-based ketone-based compound include: 2 2-dimethoxy-12-diphenylethene-1-(IRGACURE651) and the like; Α-aminoalkyl benzoquinone such as lysine (4_thiodecylphenyl) propyl sulfonate (nRGACURE 907); α_ county silk benzene such as 丨-hydroxy-cyclohexyl-phenyl-ketone (IRGACURE 184) Ketones, etc. Examples of the fluorenyl oxide-based compound include 2,4,6-trimethyl benzhydryl-diphenylphosphine oxide and the like. The titanocene-based compound includes bis(10)·2,4·cyclodecadiene small group) bis (2,6-dioxa-3-(lH-t each small group)-stupyl) titanium or the like. Examples of the compound include I.2-octanedione-1-[4-(phenothionyl)_2_(IRGACURE 0XE 01), etc. The photopolymerization starting group content is relative to

S 17 201132667 The total amount of the epoxy resin, (A-2) solid epoxy resin, (b) thermal curing agent, and (d) acrylic resin described later (hereinafter also referred to as "resin unit") is 1 part by weight. It is 0.3 parts by weight to 5.0 parts by weight. When the content is set to 0.3 parts by weight or more, the curability of the liquid crystal sealing agent by light irradiation becomes good. By setting it to 5.0 parts by weight or less, the stability at the time of coating the substrate is improved. (D) Acrylic resin The liquid crystal sealing agent of the present invention may contain an acrylic resin as needed. Examples of the acrylic resin include bismuth diacrylate or dimethyl acrylate acid such as polyethylene glycol, propylene glycol, and polypropylene glycol; and di acrylate vinegar and/or dimethyl acrylate. Propylene ketone ketone; bisphenol oxime; molybdenum and/or dioxin; Di-acrylic acid/monomethacrylate of diol obtained from ethene propylene oxide; == 4 methacrylate of triol of trimethylolpropane 1 ===== bisphenol A 1笪 and t 铉^ on the upper part of the oxygen or epoxy propylene riding two _=== _ and / or three 3: three (2_ thioethyl) iso-cyanide _ tripropylene or Triterpene _ acid vinegar; trimethyl ketone triacetate and / or trimethyl 4::, ti oligomer; pentaerythritol three rounds of vinegar and / _ "oxygen cycline r: poly, wake up;素内•质三(_氧(基=基

IX IX201132667 vinegar modified tris(methacryloxyethyl) isomeric cyanurate; alkyl modified dipentaerythritol polyacrylate and / or polymethacrylate; caprolactone modified dipentaerythritol Polyacrylate and/or polymethacrylate; hydroxypivalic acid neopentyl glycol diacrylate and/or dimethacrylate; caprolactone modified hydroxypivalic acid neopentyl glycol diacrylate and / Or dimethacrylate vinegar; ethylene oxide modified phosphoric acid acrylate and / or dimethacrylate; epoxy Ethylene modified carboxylic acid acrylate and / or dimethyl acrylate; Ethylene glycol, trimethylolpropane, pentaerythritol oligoacrylate and/or oligomeric methacrylate. The content of the acrylic resin is also dependent on the degree of photocurability required, and is preferably 5 parts by weight to 4% by weight, more preferably 10 parts by weight, based on 1 part by weight of the liquid crystal sealing agent. Share. (E) Filler The liquid crystal sealing agent of the present invention may further contain a filler. The viscosity of the liquid crystal sealing agent, the strength of the cured product, and the control of the linear expansion property can be controlled by adding a filler. The filler is not particularly limited, and examples thereof include calcium carbonate, magnesium carbonate, barium sulfate, sulfuric acid, (four)!s, Wei wrong, iron oxide, oxidized chin, alumina, zinc oxide, cerium oxide, titanium. Potassium acid, kaolin, talc, glass beads, sericite activated clay, bentonite (becain, nitrided inorganic filler, preferably dioxide 7, talc. The shape of the filler is not particularly limited, may be spherical, The shape of the plate is irregular or irregular. The filler preferably has a diameter of less than h5哗, and preferably has a specific primary particle diameter of the surface area oW/g=201132667 mV. The measurement of the specific surface area can be measured by the BET method described in the guar z8 gamma. The filling amount of the t filler is relative to (4)) (methyl) propylene glycol acid modified epoxy tree. It is known that (Α·2) solid, Wei oxygen resin, (B) thermal curing agent, and (8) propylene glycol-based resin (hereinafter also referred to as "resin unit") (10) parts by weight, preferably 1 part by weight - 50 parts by weight, more preferably 1 part by weight to 3 parts by weight. (F) Thermoplastic Resin Particles The liquid crystal sealing agent of the present invention may optionally contain an epoxy resin-modified thermoplastic resin particle (also referred to as "epoxy modified particle"). The thermoplastic resin particles are obtained by suspension polymerization of a resin containing an epoxy group and a double bond with a monomer capable of undergoing radical aggregation. The thermoplastic resin particles are preferably added in the case of a liquid crystal sealing agent for liquid crystal injection. The reason for this is that the shrinkage stress generated in the cured product due to heating can be alleviated. Examples of the resin containing 'epoxy group and double bond' include a resin which reacts bisphenol F type epoxy resin with methacrylic acid in the presence of a tertiary amine. Examples of the radical polymerizable monomer include butyl acrylate, glycidyl methacrylate, and divinylbenzene. Since the gap of the liquid crystal cell is 5 or less from the melon below, the average particle size of the thermoplastic resin particles is usually 〇. 5 μιη to 5 μηι, preferably 〇〇7 μιη to 3 The range of μιη. ‘, the thermoplastic resin particles are preferably 1 part by weight to 30 parts by weight based on 1 part by weight of the resin unit. Earthworm (G) Other Additives 20 201132667 • i The liquid crystal sealing agent of the present invention may further contain a coupling agent such as an intrusion agent, a Wei coupling agent, an ion trapping agent, an ion “J agent, a pigment, a dye, and a plastic” as needed. Additives such as chemicals and defoamers. In addition, in order to adjust the liquid-to-day surface clearance of the liquid, it is also possible to use Wei spacers (ah (seven), etc..) The liquid crystal sealing agent of Moonlight contains (4)) (meth)acrylic acid to change the oxygen "Monthday, (Β) thermal hardener and (c) photopolymerization initiator, so can be better than in most cases, using light hardening and thermosetting liquid crystal dripping j liquid crystal dense. Liquid crystal for liquid crystal dropping method Preferably, the sealant is further composed of (A-2) solid epoxy resin and (D) propylene glycol resin, and more preferably (E) filler. The liquid crystal sealing agent of the present invention uses an E-type viscometer. The viscosity under the conditions of 25 ΐ and 25 咖 is preferably 30 Pa · s to 350 Pa s. The liquid crystal sealing agent having a viscosity within the above range is excellent in applicability. 2. Manufacturing method of liquid crystal display panel A liquid crystal display panel according to the invention includes a display substrate, a counter substrate which is =, and a display substrate a frame-shaped seal member that enters between the display substrate and the opposite substrate, and a liquid crystal layer in a space surrounded by the sealing member that is filled between the display substrate and the opposite substrate. The cured product of the liquid crystal sealing agent of the present invention can be obtained. The sealing substrate and the opposite substrate are transparent substrates. The transparent substrate may be made of glass or polycarbonate, polyethylene terephthalate, polyether sulfone and polymethyl acetoacetate (Polymethyl). METacrylate, PMMA), etc. On the surface of the display substrate or the opposite substrate, a matrix of thin thin film 201132667t (Thin Film Transistor, TFT), col〇r filter, black matrix (black) 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, etc. Such a liquid crystal display panel can be produced by using the liquid crystal sealing agent of the present invention. Among the methods for producing the display panel, there are a liquid crystal dropping method and a liquid crystal injection method. The method for manufacturing a liquid crystal display panel using the liquid crystal dropping method includes the following Step: a) the first step, forming a sealing pattern of the liquid crystal sealing agent of the present invention on one substrate; a2) the second step 'in a region surrounded by the sealing pattern of the substrate in a state where the sealing pattern is not hardened, or The liquid crystal is dropped in the region of the other substrate facing the region surrounded by the seal pattern; a3) in the third step, one substrate and the other substrate are overlapped via a seal pattern; and a4) the fourth step is to harden the seal pattern. The state in which the seal pattern in the step is not hardened refers to a state in which the hardening reaction of the liquid sealant has not proceeded to the gelation point. Therefore, in order to suppress the dissolution of the liquid crystal sealant in the liquid crystal, it is also possible to The dense g pattern is semi-hardened by light irradiation or heating. One substrate and the other g plate are respectively a display substrate or a facing substrate. In the step of 枓), only hardening by heating may be performed, and it is preferred to perform curing (temporary hardening) by illuminating light, and then heat-treating the stone 22 201132667 (formally hardened). This is because the liquid crystal sealing agent is instantly cured by temporary hardening by light irradiation, whereby dissolution in the liquid crystal can be suppressed. The photohardening time also depends on the composition of the liquid crystal sealing agent, for example, about 10 minutes. The light irradiation energy may be an energy that can be cured (AD (meth)acrylic acid modified epoxy resin or (D) acrylic resin, etc. The light is preferably ultraviolet light. The heat curing temperature also depends on the liquid crystal sealing agent. The composition is, for example, 12 (TC, the heat hardening time is about 2 hours. In the liquid crystal dropping method, the contact time of the uncured liquid crystal sealing agent with the liquid crystal is relatively long, so liquid crystal contamination is likely to occur. In contrast, the present invention Since the solubility of the crystal sealing agent in the liquid crystal is low, the liquid crystal display panel obtained by the liquid crystal dropping method using the liquid crystal sealing agent of the present invention has excellent display reliability. The method for manufacturing a liquid crystal display panel using the liquid crystal injection method includes Step: bl) the first step, forming a sealing pattern of the liquid crystal sealing agent of the present invention on the substrate; b2) the second step of "making the substrate and the other substrate via the sealing pattern b3" The yeast is thermally hardened to inject the liquid crystal injection cell into the liquid crystal injection port; useful: 4); Γ step, the liquid crystal is injected into the liquid crystal injection b5 through the injection port) 5th step 'Note The inlet is sealed. M) ~ b3) step shot, prepare the liquid crystal injection cell. First, the standard

23 S 201132667 Prepare 2 transparent substrates (such as glass plates). Then, a sealing pattern is formed by 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 is formed on the substrate, 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 injection cell, but the injection port may be provided with a part of the opening when the seal pattern is drawn. Alternatively, after the seal pattern is formed, the seal of the desired portion may be removed to provide an injection port. The thermal hardening conditions of the 'b3) step also depend on the liquid crystal sealant, for example 150. (:, 2 hours to 5 hours or so. The step b4) is a vacuum in which the inside of the liquid crystal injecting cell obtained by the steps Μ) to (8) is vacuumed, and the liquid crystal is sucked from the injection port of the liquid crystal injecting cell. The silk can be carried out. B5) The step towel may be sealed with a liquid crystal (10) agent until the population of the liquid crystal injecting cells is hardened. Door phase = main entrance, ί hardened liquid crystal sealing agent in contact with liquid crystal t Even liquid crystal sealing agent for liquid crystal injection cell uses liquid crystal injection agent of the present invention to use liquid crystal injection method LCD panel. 『After being abducted [Examples] [Synthesis Example 1] Synthesis of a braided epoxy wax (10) Part (10) g of liquid double F-type epoxy resin (-. 24 201132667r YDF-8170C, manufactured by Dongdu Chemical Co., Ltd. , an epoxy equivalent of 16 〇g/eq), 0. 1 g of p-methoxyphenol as a polymerization inhibitor, 〇2 g of triethanolamine as a catalyst, and 81.7 g of methacrylic acid were added to the flask. The reaction was carried out for 5 hours while feeding dry air and stirring at 90 ° C under reflux. The obtained compound was washed 20 times with ultrapure water to obtain a methyl propylene glycol acid modified double-type F-type epoxy resin. Here, the number of epoxy groups contained in the double-presence F-type epoxy resin which is a raw material is 1 mole. The amount of the f-based acrylonitrile contained in the methyl methacrylate to be reacted was 0.95 mol. Therefore, the obtained mercaptoacrylic acid is modified to be a partial methyl acrylate, and the ratio of the equivalent of methyl propyl sulfanyl group to 乳 乳 为 is 0.95 / 0.05 (= ^ 9) . ϋΓ / ^ methyl acrylate acid modified f_F type epoxy resin contains the secret number (虱 性 functional group number) G 95x2 (= glutamic acid modified double expectation F type epoxy resin average molecular weight 483 = 492 χ〇. 95 + 32〇χ〇·05), burial and fighting 瞀 斤 斤 夏 叫 叫 3 3 3 · · 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 The molecular weight of the C-type modified double-type is 320, and the molecular weight of the two [synthesis example 2] type pure resin is

Mercaptoacrylic acid modified bisphenol F methacrylate) Wei generous synthesis (50% part except for the addition of methacrylic acid to obtain methacrylic acid modification ==, and synthesis methacrylate). The number of epoxy groups contained in the bis- phenoxy resin (50% of which is here)

25 S 201132667. Same as above, 1 mu. The methacrylic acid to be reacted contained a number of methyl propylene groups of 〇5 mol. Therefore, the resulting methyl acrylate acid is modified? The type % oxy-resin is a 50% partial methacrylate, and the ratio of the equivalent of the methacryl oxime to the equivalent of the epoxy group is 0.5/0.5 (=1). Further, 1 molecule (hydrogen bond functional group number) 〇·5&gt;&lt;2 (=1.0) contained in one molecule of the thioglycol-modified bisphenol F-type epoxy resin is divided by the thiol acrylic modified double The average molecular weight of the phenolic F-type epoxy resin (406 = 〇·5 +32〇χ〇.5)' is used to calculate the hydrogen bond functional group value of the methyl propylene glycol acid modified double-type F-type epoxy resin. The result was 246.3 (then [Synthesis Example 3] Synthesis of acrylic acid modified phenol novolak type epoxy resin (5 % by weight of acrylate) Π 9 g of liquid phenol novolac type epoxy resin (d 〇w germed company, DEN43 epoxide equivalent of i79 聚合 ^ polymerization inhibitor 〇 · 2 g of p-methoxy oxy, as a catalyst 〇 2 and 368 of acrylic acid added to the flask, - side It is sent to dry ς^ under reflux at 9GC for 5 hours. The resulting compound: two =:::) _ modified material _ varnish type ring here 'become secret varnish (four) oxygen resin contains j Μ Mo The acrylic acid in the reaction contains a propylene group of 5 5 〇. 1 因 = = the resulting acrylic acid modified benzene antiseptic varnish epoxy resin ratio = 5 on the acid 'propyl Equivalent / equivalent of epoxy group 26 ir' 201132667 The base number of the resin, type epoxy tree benzene age lacquer type epoxy tree; two:: ^43〇=179χ2+72), calculated by this The hydrogen bond functional group value of the epoxy resin was changed to m varnish, and the result was an aldehyde varnish [Synthesis Example 4] · 10 (mol/g). Adding 13.4 g of trimethylolpropane g to isophora-diisocyanate @, - side ^ tin and team 6 should be 2 hours. Then, 2.55 Torr: acid-side anti-g s J叼碲U-hydroxyethyl ester and 11.1 ac glycerol (glycid 〇1) were added and the mixture was refluxed for 2 hours. The compound which was chaotic and 9 〇Cir 20々, painful vomiting, etc. was washed with ultrapure water. 20-person obtained secondary urethane modified glycerin. And /^ The number of epoxy groups contained in the glycidol is 0.15. The number of propylene groups contained in the 2 hydroxyethyl group is 〇mol. = The amino group obtained by the fact that the amount of the weak oxy group of the partial (d) acid compound is changed to 0.022 / 0.128 (= 0.172). In addition, 'the average molecular weight of the amino decanoic acid contained in one molecule of the amide carboxylic acid modified partial acrylate from the target bond (hydrogen bond functional group) divided by the amino phthalic acid vinegar modified part of the propylene riding compound# The hydrogen bond functional group value of the amide-modified portion of the amino phthalic acid vinegar was calculated by the calculation, and the result was 3 〇χΐ〇·3 (mol/g). [Synthesis Example 5] Synthesis of methacrylic acid modified bisphenol A type epoxy resin (9%%)

S 27 201132667 ** 丨〆ν» is a methyl propyl acrylate (a) = 185 g liquid bisphenol A epoxy resin (made by Nippon Epoxy Co., Ltd. = 'trade name Epicl〇n YL98〇 , epoxy equivalent is 185), as polymerization __ ai g _ methoxy green, 〇 2 g as a catalyst, diethyl. Alcoholamine and 77.4 g of methyl (tetra) acid were added to the flask, and the reaction was carried out for 5 hours while entering the dry air and refluxing under reflux. The known compound was washed twice with ultrapure water to obtain a acryl-based modified A-type epoxy resin. Here, the bisphenol A type epoxy resin which is a raw material has a number of epoxy groups of 1 mol. The methyl-acid contained in the reaction contains (tetra)-based propyl group 〇 f〇·90 mol. Therefore, the obtained methacrylic acid modified double-prepared A-type epoxy is a 90% partial methyl acrylate, and the equivalent ratio of the equivalent oxy group of the methacryl fluorenyl group is 〇.9〇/01〇 (=9). The methylidene acid modified double-type A-type epoxy resin kg 3 of the base number (虱-functional group number) 〇9χ2 (=^8) divided by = propyl, the opposite substance Α type epoxy tree The average molecular weight of the blue color (5 〇〇 was calculated for the gas-bonded guanidine base value of the methacrylic acid modified bisphenol A type epoxy resin, and the result was 3.6 xi 〇 -3 (m 〇 i / g). [Synthesis Example 6] Synthesis of methyl 3:= double-type A-type epoxy resin (85% part will be 185 g of liquid bisphenol A type epoxy resin (Japan No. 3 product name is Epid°n YL98G, epoxy equivalent is 185 _曰) ), " 0.1 g of p-methoxybenzene, which is an L inhibitor, as a catalyst, 二2 28 201132667r g of diethanolamine and 73.1 g of methacrylic acid were added to the flask while feeding dry air and (9: The reaction was carried out for 5 hours under reflux, and the obtained compound was washed 20 times with ultrapure water to obtain a thioglycol-modified bisphenol A-type epoxy resin. Here, bisphenol A which becomes a raw material The epoxy group contained in the epoxy resin had a number of 1 mol. The methacrylic acid group reacted had a methyl methacrylate group content of 0.85 mol. Therefore, the obtained mercaptopropene group The acid-modified double-prepared a-type epoxy resin is 85% partial methacrylate, and the ratio of the equivalent of the mercaptopropenyl group to the equivalent of the epoxy group is 0.85/0.15 (=5.7). The number of hydroxyl groups (hydrogen bond functional groups) contained in the acrylic acid modified bisphenol A type epoxy resin is 0.85x2 (= 1.7) divided by the average molecular weight of the methacrylic acid modified bisphenol A type epoxy resin (5〇 〇), by which the hydrogen bond functional group value of the methyl acetoacetate modified double-presence type A epoxy resin was calculated to be 3.4 x 10 3 (mol/g). The results obtained in Synthesis Example 1 to Synthesis Example 6 The physical properties of the (meth)acrylic acid-modified epoxy resin are shown in Table 1. [Table 1] Synthesis Example 1 Equivalent of (meth)acryl fluorenyl group: Equivalent 95 of epoxy group: 5 (meth) acrylate group Equivalent hydrogen bond functional group value (mol/g) of the epoxy group - 19 3.93x1 (Γ Synthesis Example 2 50 : 50 1 2.46xl0'j Synthesis Example 3 50 : 50 1 23χ1〇-3~~- Synthesis Example 4 15 . 85 0.172 3 〇χ1〇-3~~~ Synthesis Example 5 90 : 10 9 3.6xlOJ Synthesis Example 6 85 : 15 5.7 3.4x10' [Example 1] s 29 201132667 Using a three-roller kneading machine 'will be 43 weights Share The methacrylic acid-modified bisphenol F-type epoxy resin (95 〇/〇 partial methacrylate) obtained in Synthesis Example 1 and 4 parts by weight of a solid epoxy resin (manufactured by JER Co., Ltd., Epik〇te 1004 'softened) Point: 97 ° C), 20 parts by weight of an acrylic resin (polyethylene glycol monoacrylic acid S, manufactured by Kyoritsu Chemical Co., Ltd., Light acrylate 14EG-A), and 9 parts by weight of adipic acid as a heat hardener Erqi (Sakamoto Kasei Co., Ltd. manufactures 'ADH' melting point of 177. (: ～184 ° C), 2 parts by weight of an alkylphenone-based polymerization initiator (manufactured by Ciba Specialty Chemicals, IRGACURE 651) as a photopolymerization initiator, 13 parts by weight of two 7 parts by weight of thermoplastic resin particles obtained by copolymerizing cerium oxide particles s_1〇〇 (manufactured by Nippon Shokubai Chemical Co., Ltd.), and a monomer obtained by copolymerizing a (fluorenyl) acrylate monomer with a monomer copolymerizable with the monomers ( The curable resin composition composed of the microparticle polymer F351 (manufactured by Zeon Chemical Co., Ltd.) and 2 parts by weight of a decane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-403) was sufficiently mixed to obtain a uniform liquid, and a sealant was obtained. [Example 2] In place of 9 parts by weight of 1,3-bis(decylcarboethyl)-5-isopropylhydantoin (manufactured by Ajinomoto Co., Ltd., Amicure VDH 'melting point is i20 ° C) A sealant was obtained in the same manner as in Example 1 except that diammonium adipate (manufactured by Sakamoto Kasei Co., Ltd., ADH) was used as a thermosetting agent. [Example 3] A sealant was obtained in the same manner as in Example 1 except that the solid epoxy resin was not used. [Comparative Example 1] 30 201132667" In place of the methacrylic acid modified bisphenol F type epoxy resin (50% partial methacrylate) obtained in Synthesis Example 2, instead of the thiol acrylic acid modified double obtained in Synthesis Example 1, A sealant was obtained in the same manner as in Example 1 except for a phenol F-type epoxy resin (95% partial methacrylate). [Comparative Example 2] In place of 9 parts by weight of 1,3-bis(decylcarboethyl)-5-isopropylethylurea (Amicure VDH, Amicure VDH) was used instead of diammonium adipate. (The sealant was obtained in the same manner as in Comparative Example 1 except that 'ADH was manufactured by Nippon Kasei Co., Ltd.) as a heat curing agent. [Comparative Example 3] 43 parts by weight of an acrylic acid-modified phenol novolac type epoxy resin (50% partial acrylate) obtained in Synthesis Example 3, 20 parts by weight of an amine obtained in Synthesis Example 4, using a three-roll kneader Carbamate modified part of acrylate, 4 parts by weight of solid epoxy resin (manufactured by jER,

Epikote 1004, softening point of 97 ° C), 9 parts by weight of 1,3-bis(decylcarboethyl)-5-isopropylethylpyrene as a thermosetting agent (Amicure, Amicure) VDH), 2 parts by weight of 2,2,-diethoxyacetophenone as a photopolymerization initiator, 13 parts by weight of cerium oxide particles s_15〇 (manufactured by Sakamoto Chemical Co., Ltd.), 7 parts by weight The curable resin composition composed of the thermoplastic resin particles (fine particle polymer F351 (manufactured by Zeon Chemical Co., Ltd.)) and i parts by weight of a decane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-403) is sufficiently mixed to obtain a uniform liquid. Sealants. [Comparative Example 4] In place of the methyl group selected in Synthesis Example 1, except that the methyl acrylate acid modified double type 201132667 obtained from the synthesis example 5 was used, 90% partial thiol acrylate was used. A sealant was obtained in the same manner as in Example 1 except for an acrylic acid modified bisphenol F type epoxy resin (95% partial fluorenyl olefinate). [Comparative Example 5] The methacrylic acid modified bisphenol F type obtained in the synthesis example was replaced by using the methacrylic acid modified bisphenol a type epoxy resin (85% partial mercapto acrylate) obtained in Synthesis Example 6. A sealant was obtained in the same manner as in Example 以外 except for an epoxy resin (95 Å/〇 part of fluorenyl olefinate). For the sealants obtained in Example 1 to Example 3 and Comparative Example 丨 to Comparative Example 5, the 方法 viscosity stability was evaluated by the following method, 2) Nq ^ of liquid crystal, 3) f* external hardenability, and 4) liquid crystal display panel The display characteristics are followed by. '1) Method of the weight of the sealant in the viscosity stability = The sealant obtained in the examples and the comparative examples was subjected to a defoaming treatment. The initial viscosity was then measured. Under the same conditions, the bribery of the post, once again in the initial increase in viscosity; The viscosity after one week of storage at this time is evaluated relative to the case where the viscosity after storage is Δ(slightly worse)' the rate of increase is more than 15 times. 2) The defect of the liquid crystal (the phase transition temperature to the material phase) 32 201132667 Put ο" (unhardened) sealant obtained in the examples and comparative examples with 1 g of liquid crystal (Merck, manufactured by Merck, MLC-11900-000) into a glass vial and heat at 120 Torr for 1 hour. A liquid crystal mixture was obtained. Then, the liquid crystal mixture was taken out, and its N-I point was measured by DTA (differential thermal analysis) at a temperature elevation rate of 5 °C/min. Even if a small amount of impurities are present in the liquid crystal, the N-I point of the liquid crystal changes greatly. Therefore, the smaller the amount of change in the N-I point of the liquid crystal mixture after heating relative to the N-I point of the (heated ruthenium) liquid crystal, the less the dissolution of the sealant component in the liquid crystal. The amount of change in the N-I point of the liquid crystal mixture with respect to the liquid crystal (original) N-I point was less than 5. (The sample was evaluated as 〇 (excellent). The sample with a change amount of 5 ° C or higher was evaluated as X (poor). 3) UV curability was obtained using VISCOANALYSER VAR100 manufactured by REOLOGICA INSTRUMENT Co., Ltd., and obtained in the examples and comparative examples. The viscosity rise behavior of the sealant after irradiating ultraviolet rays of 5 mW/cm2. The curing time of the sealant after ultraviolet irradiation with respect to the saturation viscosity value of 50% was measured. The saturated viscosity value refers to the viscosity when the sealant is completely cured. The shorter the hardening time, the more excellent the hardenability can be judged. 4) Display characteristics of the liquid crystal display panel For the sealant obtained in the examples and the comparative examples, a dispenser (Shot Master 'Musashi Engineering) was used, and a 40 mm x 45 mm glass substrate (EHC company) in which a transparent electrode and an alignment film were formed in advance was used. Form a 35 mm x 40 mm square seal on the RT-DM88-PIN)

I 33 201132667 The pattern (cross-sectional area is 3500 μηη2) (main seal), and the same seal pattern (38 mm&gt;&lt;43 mm square seal pattern) is formed on the outer circumference. Then, a liquid crystal material (MLC-119000-000, manufactured by Merck Co., Ltd.) corresponding to the amount of the panel contents after the bonding was precisely dropped into the frame of the main seal by using a dispenser. Then, the pair of glass substrates were bonded under reduced pressure, and then the atmosphere was opened and bonded. Then, the two bonded glass substrates were held in a light-shielded box for 3 minutes, and then irradiated with ultraviolet rays of 2000 mJ/cm2, and then heated at 100 °C for 1 hour. The obtained liquid crystal display panel was stored in a strange temperature bath at 70 ° C and 95% RH for 500 hours, and the chromatic aberration caused by the liquid crystal around the sealing portion before and after storage was visually observed. The case where the chromatic aberration was not confirmed was evaluated as 〇 (excellent), and the case where the chromatic aberration was confirmed was evaluated as X (poor). Further, the liquid crystal display panel taken out in the constant temperature bath is driven by the DC power supply device with a voltage of 5 V, and the liquid crystal display panel in the vicinity of the liquid crystal sealing agent is normally operated from the initial stage of driving to evaluate the display of the liquid crystal display panel. characteristic. Regarding the display characteristics, the case where the liquid crystal display function was normally performed until the sealing edge was normal was evaluated as 〇 (excellent), and the abnormality of the liquid crystal display function was confirmed to be Δ in the range of less than 0.3 mm in the vicinity of the sealing edge. Difference) 'The case where the abnormality of the display function is confirmed within a range of 0.3 mm or more in the vicinity of the sealing edge is evaluated as X (poor). 5) Adhesiveness For the sample of the liquid crystal display panel which was stored in the thermostat in the above 4), the tensile strength was measured by using a tensile test apparatus (manufactured by Intesc®) at a stretching speed of 23 m 32 201132667. The following is evaluated as follows: The strength is 15 MPa or more: 〇 (excellent) The strength is 7 MPa or more and less than 15 MPa : △ (slightly worse) Then the strength is less than 7 MPa: X (poor) Example 1 to Example The evaluation results of 3 and Comparative Example 1 to Comparative Example 5 are shown in Table 2. 201132667 Ja-b ε (take the shed: broom) Comparative example 寸σ\ (Ν ΓΛ CNCN &lt; X &lt;] X 〇寸ΓΟ inch〇\ CN CO 〇 〇&lt;1 〇Ο 〇m ΓΟ inch〇\ CN m Bu XXXX &lt;1 CN inch On (Ν卜CN &lt; X in &lt;&lt; 〇寸〇\ (Ν cn 卜CN 〇X ν-ϊ &lt; X 〇5 Os 卜 CS 〇〇ο 〇0 &lt; (N rn 寸 Os ίΝ m 卜CN &lt; 〇ο ο 〇〇 inch σ\ &lt;Ν cn 1&gt; (N 〇〇 Ο ο 〇〇1 Hydrogen bond functional group value (m〇l/g) 3.93X10'3 2.46χ10&quot;3 2.3 xlO'3 3.0X10'3 3.6X10·3 3.4X10-3 ! Epikote 1004 ADH (dioxalate) i 婳ΝΓ&lt; ^ Q ^ 1* •s *〇一$ IRGACURE 651 Light Acrylate 14EG-A cerium oxide particles S-100 cerium oxide particles S-150 F351 KBM-403 (decane coupling agent) 1) Viscosity stability 2) Ν-I point of liquid crystal 3) UV curability ( Second) After the butterfly drive display characteristic 5) Adhesive equivalent ratio 〇 \ 0.172 卜 ΐ ΐ ΐ Synthesis Example 1 Synthesis Example 2 Synthesis Example 3 Synthesis Example 4 Synthesis Example 5 Synthesis Example 6 4) Display characteristics (A-1) of the liquid crystal display panel ( Acrylate-based acrylic acid modified epoxy resin (A-2) solid epoxy resin (B thermal curing agent (C) photopolymerization initiator (D) acrylic resin (E) filler (F) thermoplastic resin particles (G) Other composition evaluation

9C 201132667 •fit = Table 2 is unknown 'Use ($ base) propylene county equivalent / epoxy 2 篁 ratio of 19 (example of methyl acid modified epoxy resin Γ Sealant and use (A (meth)acrylic acid-modified epoxy tree of the equivalent of propylene oxime/epoxy group when the summer = 9 or less (4) Comparative Example 1 Comparison of the 1 (four) sealant phase with the liquid crystal N·1 dot and the liquid crystal display 1 is good. Generally, the reason is as follows: the density of the examples 1 to 3, the (c) based on the W, and the (meth) contained in the sealant (4) i~ comparison = 5 (10) Acid-modified f epoxy phase comparison, = the content ratio of the unreacted epoxy group is higher, so the solubility in the liquid day is remarkably suppressed. Further, it is known that the sealants of the examples i to 3 are contained. The (meth)acrylic epoxy resin and the (mercapto)acrylic acid of Comparative Example 1 to Comparative Example 5: Compared with the oxygen resin, the content of the 'mercaptopropenylfluorenyl group was large, and the ultraviolet curability was also good. In addition, the comparison between Example 1 and Example 3 reveals that the sealant containing solid epoxy ruthenium has high display property due to driving, so the moisture retention is high. It can be seen that the sealant containing a solid epoxy resin has high adhesion. [Industrial Applicability] This is the day (10) Liquid crystal density _ a large amount of money base, so even at high temperatures and = (4) in liquid day and day Therefore, if the liquid, the sealant, and the cured product of the sealant of the present invention are used as a sealing member (liquid crystal sealing portion), it is possible to provide a liquid crystal which is excellent in reliability without being leaked to the sealing member. The liquid crystal sealing agent of the present invention is suitable for the manufacture of a liquid crystal display panel. Although the invention has been disclosed above in the preferred embodiment, it is not intended to limit the invention, and any one skilled in the art, Within the scope of the present invention, when a slight change can be made with the Run Department, the scope of the application is as follows: the protection of the invention = the protection of the invention [the simple description of the schema] is subject to change. Explanation of main component symbols] None. 38

Claims (1)

201132667^ VII. Patent application scope: L A liquid crystal sealing agent comprising a (meth)acrylic modified epoxy resin obtained by reacting an epoxy resin having two or more epoxy groups in the molecule with (meth)acrylic acid, a heat hardener and a photopolymerization initiator, the (meth)acrylic acid modified epoxy resin having an epoxy resin having two or more epoxy groups in the molecule and the (meth)acrylic acid a hydroxyl group-containing hydrogen bond functional group formed by the reaction, and the equivalent of the (fluorenyl) propylene group of the (meth)acrylic acid modified epoxy resin/equivalent to the epoxy group exceeds 9, the hydrogen bond property The liquid crystal sealing agent according to claim 1, wherein the molecule contains two or more epoxy groups in the molecule. The epoxy resin is a difunctional epoxy resin selected from the group consisting of a biphenyl type oxy-resin, a naphthalene type epoxy resin, and a bisphenol type epoxy resin. 3. As described in claim 2 Liquid crystal sealant, wherein the difunctional epoxy resin is bisphenol A type The epoxy resin or the bisphenol F-type epoxy resin. The liquid crystal sealing agent according to claim 1, wherein the liquid crystal sealing agent further contains 1 part by weight to 2 parts by weight with respect to 100 parts by weight of the liquid crystal sealing agent. The liquid crystal sealing agent of the liquid crystal sealing agent according to claim 1, wherein the photopolymerization initiator is selected from the group consisting of alkyl benzenes. At least one compound selected from the group consisting of a ketone compound, a fluorenyl phosphine oxide compound, a titanocene compound, and an oxime ester compound. 39 201132667 • jt ^ 6. Liquid crystal as described in claim 1 The sealing agent, wherein the thermal hardener has a melting point of 50 ° C or more and 250 ° C or less. 7. The liquid crystal sealing agent according to claim 1, wherein the thermal hardener is selected from the group consisting of organic acids At least one of a group consisting of a quinone compound, a bismuth compound, a dicyandiamide compound, and a polyamine compound. 8. The liquid crystal sealing agent according to claim 1, which is used Liquid using liquid crystal dropping method Manufacturing of a display panel. 9. A method of manufacturing a liquid crystal display panel, comprising the steps of: forming a sealing pattern on a substrate using a liquid crystal sealing agent as described in claim 1; wherein the sealing pattern is not hardened Liquid droplets are dropped on the sealing pattern area of the one substrate or on another substrate paired with the one substrate; the one substrate is overlapped with the other substrate; and the sealing pattern is made After photohardening, thermal curing is performed. 10. A liquid crystal display panel comprising: a display substrate; a facing substrate paired with the display substrate; and a frame shape inserted into the display substrate and the opposite substrate Sealing member; and encapsulation: ====: The hardened material of the liquid crystal dense 201132667 sealant as described in claim 1 is applied to the substrate between the substrates. 201132667 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: No 0 3 201132667 For the first brain 10 Qing Zhongshu book __ 正页 Revision date · June 9th acrylic base equivalent / ring The equivalent of the oxy group is at least a predetermined value, and can be inhibited from being dissolved in the liquid crystal. The present invention is based on such findings. The first invention of the present invention relates to a liquid crystal sealing agent. [1] A liquid crystal sealing agent comprising (meth) propylene modified N. oxyphylla, a thermosetting agent, and a photopolymerization start which are obtained by reacting two or more molecules with (meth)propionic acid in a molecule. The above-mentioned (comparable) acrylic acid-modified epoxy resin contains a bond-containing s-energy group formed by the above-mentioned (meth)acrylic acid anti-filament of the above-mentioned (meth)acrylic acid, which contains two or more kinds of Wei group in the molecule. And the equivalent of the (indenyl) propylene « of the above (τ) (tetra) acid-modified epoxy resin has an equivalent weight of more than 9, and the above-mentioned Lu Luyue base value is 3 x l 〇 · 3 m 〇 i / g 〜 5 x l 〇-3 m〇1/g. [2] The liquid crystal sealing agent according to [1], wherein the epoxy resin having an epoxy group of 2 or more solids or more is selected from the group consisting of biphenyl type epoxy resin, naphthalene type epoxy. A resinous and bis (tetra) cyclopentate composed of a succinct difunctional epoxy resin. [3] The liquid crystal sealing agent according to [2], wherein the difunctional %-resin is a bisphenol eight type epoxy resin or a bisphenol F type epoxy resin. The liquid crystal sealing of the liquid crystal sealing agent according to any one of the items [1] to [3], wherein the liquid crystal sealing agent further contains a softening point of 20 parts by weight of i ring i t. The above-mentioned photopolymerization agent in the liquid crystal sealing according to any one of the items [1] to [4], which is selected from the group consisting of a ketone-based compound, rustic The phosphine-based compound, the titanocene-based compound, and the vinegar-based compound 201132667 i / yuypm are the 100th Chinese version of the specification, and the at least one compound in the group consisting of June 9, 100. [6] The liquid crystal sealing agent according to any one of [1] to [5] wherein the thermal curing agent has a melting point of 5 (TC or more and 250 ° C or less. [7] as in [1] The liquid crystal sealing agent according to any one of the above-mentioned item, wherein the heat hardening agent is selected from the group consisting of an organic acid diterpenoid compound, a salivary compound, a dicyandiamide compound, and a polyamine system. The liquid crystal sealing agent of any one of the above [1] to [7] which is a liquid crystal display panel for performing liquid crystal dropping method. The second invention of the present invention relates to a method of manufacturing a liquid crystal display panel using a liquid crystal sealing agent, etc. [9] A method of manufacturing a liquid crystal display panel, comprising the steps of: using [1] on a substrate The liquid crystal sealing agent according to any one of the items [8], wherein a sealing pattern is formed; in a state in which the sealing pattern is not hardened, in a sealing pattern region of the one substrate or in a pair with the one substrate; Dropping liquid crystal on another substrate; placing the above one substrate with the above The substrate is superposed; and the sealing pattern is photocured and then thermally cured. [10] A liquid crystal display panel comprising a display substrate, a counter substrate paired with the display substrate, and the display substrate and the opposite substrate a frame-shaped sealing member and a liquid crystal layer in a space surrounded by the sealing member filled between the opposite substrates of the display substrate disk, and the sealing member is as described in items [1] to [8] The hardened material of the liquid crystal sealing agent according to any one of the items. 201132667 , j / is the Chinese manual of the 100110150 No-line correction page. Revision date: June 9th, the ester modified three (mercapto propylene oxime) Ethoxyethyl)isocyanate; polyacrylate and/or polymethacrylate of alkyl modified dipentaerythritol; polyacrylate and/or polymethacrylate of caprolactone modified dipentaerythritol ; hydroxypivalic acid neopentyl glycol diacrylate and / or dimethacrylate; caprolactone modified hydroxy pivalic acid neopentyl glycol diacrylate and / or bismuth methacrylate 'epoxy B Burnt modified phosphorus Acid acrylate and/or dimethacrylate; ethylene oxide modified alkylated phosphoric acid acrylate and/or dimethacrylate; new Pentylene glycol, trihydroxydecyl propane, oligoacrylate of pentaerythritol, and/or oligomeric methacrylate. The content of the acrylic resin is also dependent on the degree of photocurability required: preferably 5 parts by weight to 4 parts by weight, more preferably 10 parts by weight to 3 parts by weight, based on 1 part by weight of the liquid crystal sealing agent. Share. (E) Filler: talc, r: a, bismuth;: zinc: the shape of the dioxide, the potassium titanate, the kaolin, and the filler are not particularly limited, and the emulsified stone and talc are used. The regular shape or irregularity (4) may be light, plate-like, or needle-like, and the diameter is I.5 μηι, and is preferable. Preferably, the filler is an average primary particle having a specific surface area of G.5 m2/g~2〇19 201132667^/yuypirl is the first]00110150 Chinese manual without a sizing correction page Revision date: 100 years June 9曰m / g. The average-secondary diffraction of the filler was measured. In addition, it is measured by the BET method described by Ray of the melon 28825-1. The area can be measured by the total amount of JIS Z883〇J relative to (4)) (meth)acrylic acid modified coffee fat, (Α·2) solid epoxy epoxy 榭 匕Μ夂 螂 螂 ( ( ( In the following days, the hard (four) and (8) propionic acid is preferably a part by weight of the resin unit "1" by weight. Knife 5 〇 reset parts, more preferably 1 〇 parts by weight ~ 30 Γ Γ (F) thermoplastic resin particles = ^ = agent may also contain epoxy resin modified = sub- 疋 to contain epoxy groups and The double bond resin is obtained by performing free radical = St row suspension polymerization. The fine resin particles are preferably added in the case of a liquid crystal sealing agent for the i 曰曰 / inlet method. The reason for this is that it is possible to reduce the shrinkage stress generated by the heat in the hardened material. Examples of the resin containing an epoxy group and a double bond include a resin which reacts a bis-based resin with a acryl group in the presence of a tertiary amine. = Examples of the radical polymerizable monomer include butyl acrylate, methyl methacrylate, and divinyl benzene. Since the gap of the liquid crystal cell is mainly 5 or less, it is more preferable that the average particle diameter of the thermoplastic resin particles is usually in the range of μηη to 5 μηη, preferably in the range of 〇7〇ιη to 3 μπι. The thermoplastic resin particles are preferably 1 part by weight to 3 parts by weight based on 100 parts by weight of the resin unit. (G) Other Additives 20 201132667 , j / is No. 100110150 Chinese manual without scribe correction page Revision date: June 9, 100 YDF-8170C, manufactured by Dongdu Chemical Co., Ltd., epoxy equivalent of 16 〇, as a polymerization inhibitor Gl g of p-methoxybenzene, catalyzed 〇2 g of diethanolamine and 81.7 g of methyl methic acid were added to the firing line and sent to the drying line and screamed for 5 hours. The compound of Reid was washed 2G times with ultrapure water to obtain a methyl acrylate riding type F epoxy resin. Bei Ai Cai Here's a raw material that is a raw material (4) epoxy resin containing 1 mole. The f-based acrylic acid to be reacted is (10) mole. Therefore, the obtained methacrylic acid was modified; == the resin became a 95% partial methyl methacrylate compound, and the ratio of the equivalent ratio of j / epoxy group was 0·95/0.05 (= 19). The base of the contact group is divided by one molecule of methacrylic acid modified bis-epenoic acid modified double age F type epoxy resin: base 492 χ 0.95 + 32 〇χ (10) 5), thereby calculating 3.4 (= Ο It is 3.93x10-3 (mol/g). Double _ f "base value, and the result is that the amount of the thiol-acrylic acid modified by both ends is gamma'. [Synthesis Example 2] The molecular weight of the U-oxygen resin is 492. Synthesis of acrylic acid modified double-type F-type cyclomethicone methyl methacrylate) 1 synthesis of enamel tree 曰 (5 〇% part of the addition of methacrylic acid in addition to the same methacrylic acid modified double heart) Example 1 Methacrylate) 1 Aerated resin (5〇〇/0 part here) The number of epoxy groups contained in the double-type epoxy resin as raw material 25 201132667 3/yuypiti Revision date: 1 year 6 On the 9th of the month, the Chinese manual of No. 100110150 has no scribe correction sheet of 1 mol. The methacrylic acid contained in the reaction is a bismuth F-type epoxy resin which is 5〇% partial formazan, and the equivalent of fluorenyl group/ring The equivalent ratio of the oxy group is 05/().5 (=1)/base (4) VIII: Vi methacrylic acid modified bisphenol F type epoxy resin bond The number of functional groups) 〇.5x2 卜1·0) divided by the average molecular weight of methyl acetoacetate modified double-f-type epoxy resin (406 = 7 gas H2 ^ · 5 ) ' The acid-modified double-wrinkle has a renewing functional group value of n., and the result is 2.46xig_3 (Caf [Synthetic Example 3] S------------------------------------------------ Novolak-type epoxy resin (Dow made of yoke, D. New 431, epoxy equivalent of 179 _, g 仏 p-methoxy benzene, as a catalyst 0.2 empty = 3 ^ 36 § propyl acid addition To the inside of the flask, the dried product was fed for 5 hours while refluxing, and the obtained compound = pure water was washed 2 times to obtain an acrylic modified benzophenone resin (50% partial acrylate). The number is the epoxy resin contained in the secret varnish-type county, and the acrylic acid-modified benzene accompli varnish obtained by the reaction of the acetophenic acid contained in the ear is 〇5 5〇%. The epoxy resin is a sulphur-based acrylate, and the equivalent of the acryl-based group/epoxy group is 0.5/0.5^ 〇0.