TW200827882A - Liquid crystal sealing agent and liquid crystal display cell using the same - Google Patents

Abstract

To provide a liquid crystal sealing agent firstly which is excellent in low temperature curing property, low contamination on a liquid crystal, has a long pot life and good boding strength and is good in coating workability to a substrate and in sticking property, and secondly which is effective for a thermally hardening liquid crystal dropping process, and to provide a liquid crystal display cell using the liquid crystal sealing agent. The liquid crystal sealing agent contains (a) a dihydrazide compound, (b) one or more kinds selected from an epoxy resin, a (meth)acrylated-epoxy resin and a partially (meth)acrylated-epoxy resin, as curable resin, and c a polyvalent carboxylic acid as cure-accelerating agent.

Description

200827882 IX. Description of the Invention: [Technical Field] The present invention relates to a liquid crystal sealing agent and a liquid crystal display unit using the same. More specifically, it relates to a liquid crystal sealing agent which is suitable for liquid crystal dropping injection method and liquid crystal sealing agent manufactured by using the liquid crystal dropping method, and it is not too early to use the liquid crystal display. As a method of manufacturing a liquid crystal display unit, a so-called liquid crystal dropping injection method having a higher mass productivity is popularized. In the liquid crystal dropping injection method, liquid crystal is dropped onto the inside of the liquid crystal sealing agent bank formed on the substrate, and then the liquid crystal is sealed by bonding the other substrate, thereby manufacturing a liquid crystal display unit. However, in the liquid crystal dropping injection method, there is an essential problem that the unhardened liquid crystal sealing agent is in direct contact with the liquid crystal, whereby the components of the liquid crystal sealing agent are dissolved into the liquid crystal, resulting in contamination of the display region of the liquid crystal, and From the standpoint of improving the reliability of the liquid crystal display unit, it is required to have a less polluting liquid crystal sealing agent. In the liquid crystal dropping injection method, three methods of heat hardening, photohardening, and photothermal hardening are generally considered as a method of hardening a liquid crystal sealing agent. In the thermosetting method, there is a problem in that when the viscosity of the sealant is lowered during heating, it is difficult to maintain a sealed shape, or when the liquid crystal sealant which is not hardened is brought into contact with the liquid crystal during heating, the liquid crystal is easily contaminated. On the other hand, the liquid crystal sealing agent used in the photocuring method may be either a cationic polymerization type or a radical polymerization type depending on the type of the photopolymerization initiator. The cationic polymerization type liquid crystal sealing agent has the following disadvantages: when photohardening is used, the 1% ion generated by the knife can be reduced to the liquid crystal, and the specific resistance of the liquid crystal is lowered, so that U can be produced. Further, the radical polymerization type liquid crystal sealing agent has the following problems: Since the curing shrinkage is large at the time of photocuring, the strength is insufficient. Further, the problems associated with the photopolymerization method of the cationic polymerization type and the radical polymerization type are that the liquid wiring portion of the liquid crystal display unit array substrate or the black matrix portion of the color filter substrate is produced in the liquid crystal sealing agent. The light is not irradiated to the light-shielding portion, so that the light-shielding portion is not hardened. Such a thermosetting method and a photohardening method have problems, respectively. Therefore, in practice, photothermal curing is widely used as a practical hardening system. The photothermal encapsulation is characterized in that the liquid crystal sealing agent sandwiched between the substrates is once hardened by light irradiation, and then hardened by heating (see Patent Document 1). As an advantage of the heat curing, there are cases in which the following strength and moisture resistance reliability are remarkably improved, and even if the light-shielding portion is cured, it can be cured by thermal curing. As a characteristic required for the photothermal curing and liquid crystal sealing agent, it is important that the liquid crystal sealing agent does not contaminate the liquid crystal in each step before and after the light irradiation and before and after the heat hardening. Moreover, from the viewpoint of workability, it is desirable that the viscosity change at the time of use at room temperature is small, and the use of good life is good, on the other hand, from the viewpoint of the characteristics and cost of the sealed liquid crystal, In the case of 130, it is below, h), low temperature hardening, and more preferably low temperature hardening under conditions of about 1 〇〇〇c, i hours. In general, a hardening resin for photothermal curing and a liquid crystal sealing agent is a hardening resin having a reactive group having both an epoxy group and a (fluorenyl) acrylonitrile group, and the epoxy group has thermosetting property. And (meth)acryl fluorenyl 121463.doc 200827882 is photocurable. As such a hardened resin system, a mixed resin system of epoxy eucalyptus and %► oxygen (meth) acetoacetate resin or a partially-identified (meth) acrylonitrile-based epoxy resin is used. Then, in the cured resin system, in order to further photoharden the (meth)acryl fluorenyl group, a photopolymerization initiator component is required, and a hardener component is required to thermally cure the epoxy group. As a hardening agent component, diterpene adipate, diterpene sebacate, diammonium isophthalate, and epoxy resin room temperature curing agent VDH (fine flavor) are usually used.

Anthraquinone compound (Ajinomoto-Fine-Techno Co., in). The cerium compound can react not only with the epoxy group but also with the (fluorenyl) acrylonitrile group. Therefore, it is preferable to harden the light-shielding portion, but it may become a change in viscosity at room temperature or the like. the reason. The choice of the hardener is an important factor that has a major influence on the liquid crystals such as liquid crystal sealant and service life. The sealing (4) of the above-mentioned anthracene diterpenic acid diterpene, azelaic acid dioxime, dodecanedioic acid dioxime, isophthalic acid dioxime or the like is excellent in preservation stability. However, due to the high melting point, the low-temperature hardening property is not good. On the other hand, the epoxy resin of the low melting point bismuth compound is excellent in low-temperature curability, but the storage stability is not good. However, the liquid crystal dropping method in which only heat curing is used without photohardening is as described above, and it is not easy to realize because of the shape retention of the so-called seal and the problem of liquid loss. It is considered that when the temperature is 2, the temperature can be quickly reacted and increased from a relatively low temperature, so that it is sufficient to maintain the shape and reduce the pollution. Exist to make the sealant harden quickly, 121463.doc 200827882

In addition, a method of adding a low-temperature hardening hardening accelerator, but generally used as an accelerator of an epoxy resin, such as an imidazole, an amine adduct, a tertiary amine, or a phosphine such as a tridentate, has the following problems. ·································································· Hardening system. As an industrial advantage of performing the liquid crystal dropping injection method only by thermal curing, the following is a high-priced mask and UV lamp which do not need to protect the liquid crystal and the alignment film from UV light during UV curing, and can be reduced. The cost of electricity required to light a uv light. As described above, there is a need for a liquid crystal sealing agent for liquid crystal dropping injection method which can be hardened at a lower temperature and which has a long service life and stable workability. On the other hand, in the case of using a resin composition having a diterpene compound, Patent Document 2 discloses that a plurality of polyphenols are hardly used as a hardening accelerator in a hardened crucible of an epoxy resin and a diterpene hardener. In the case, but Yafei a and this is enough to apply to the liquid crystal sealant. [Patent Document 1] Japanese Patent No. 2684842 [Patent Document 2] Japanese Patent Laid-Open Publication No. SHO 62-172014 SUMMARY OF THE INVENTION [Problems to be Solved by the Invention] An object of the present invention is to provide a liquid crystal sealing agent first. The liquid crystal sealing agent is excellent in low-temperature hardening property, low in liquid crystal contamination, long in service life, and has good coating workability, adhesion, and adhesion strength to the substrate, and secondly provides a liquid crystal sealing agent, the liquid crystal sealing agent The agent is effective for heat 121463.doc 200827882 Hardened liquid crystal dropping injection method. [Means for Solving the Problem] The present inventors have found that a resin composition having a specific composition can achieve the above object as a result of intensive research to solve the above problems, and the present invention has been completed. That is, the present invention relates to: 0) a liquid crystal sealing agent comprising (a) a diterpene compound, (b) a curable resin selected from the group consisting of a bad emulsion resin and a (decyl) acrylated epoxy resin. And one or more of the (meth) acrylated epoxy resins; and (c) a polycarboxylic acid as the hardening accelerator, (2) the liquid crystal sealing agent according to (1), wherein the hardening The resin (b) is a mixture of an epoxy resin and a (meth) acrylated epoxy resin, (3) The liquid crystal sealing agent according to (1) or (2), wherein the polybasic acid (c) is twelve (2) The liquid crystal sealing agent according to (1) or (2) wherein the polybasic acid (c) has isomeric cyanuric acid represented by the following formula (1) Polycyclic acid compound of the ring skeleton, [Chemical 1]

121463.doc •10- 0 200827882 [In the formula, T1 to T3 each independently represent hydrogen or a molecular skeleton represented by the following formula (2): [Chem. 2] ΌΗ (2) wherein the polycarboxylic acid (C) is as follows CH24—

II ο (wherein η represents an integer of 1 to 6)] (5) The liquid crystal sealant (3) as described in (4), [Chemical 3]

(6) The liquid crystal sealing agent according to (4), wherein the polycarboxylic acid (c) is a compound represented by the following formula (4), [Chemical 4], CH2-C-OH^II 0 h2c 0> HO—C-II 0 "h2 H2 ,Ν N, 丫h2 , C—C—OH H2 II o (4) 0 121463.doc -11- 200827882 (7)-Liquid liquid crystal display unit, which is from (1) to (6) The method of manufacturing a liquid crystal display unit according to the invention, wherein the liquid crystal display unit comprises a liquid crystal display unit comprising two substrates, on one of the substrates The liquid crystal sealing agent according to any one of (1) to (6), forming a sealing pattern, and dropping the liquid crystal into the sealing pattern or on the opposite substrate, and then bonding the opposite substrate to the liquid crystal sealing agent. (9) The method for manufacturing a liquid crystal display unit according to (8), wherein the hardening is performed once by ultraviolet rays and/or visible rays, and then hardening is performed by heating' (10) as described in (8) A method of manufacturing a liquid crystal display unit in which hardening is performed without ultraviolet rays and/or visible rays, but only by heating. [Effects of the Invention] The liquid crystal sealing agent of the present invention is particularly excellent in low-temperature curability, and at the same time, liquid crystal has low dyeability and long service life, and has good coating workability, adhesion, and strength to the substrate. . By using the liquid crystal sealing agent of the present invention for a liquid crystal dropping injection method, the yield and productivity of a liquid crystal display unit can be improved. [Embodiment] Hereinafter, the present invention will be described in detail. The liquid crystal sealing agent used in the present invention contains a diterpene compound (a) as a hardening agent. The diterpenoid refers to a compound having two fluorenyl groups in the molecule, and specific examples thereof include, for example, diterpene oxalate, diammonium malonate, diterpene dioxime, adipic acid. Diterpenoid, diammonium adipate, Geng II 121463.doc -12· 200827882 Diterpenoid acid, dicaptanic acid dioxime, - acid monoterpene, azelaic acid diterpenoid, eleven burned diacid Diterpenoid, +丄, p _ 十, 垸-acid diterpene, maleic acid

a bismuth, bismuth fumarate, bismuth diglycolate, bismuth tartaric acid, bismuth phthalate, diammonium isophthalate, diterpene terephthalate, 2, 6-naphthoic acid di-branched ruthenium, 4,4·bis-benzene-distilled ruthenium, μ-extracted formic acid diterpene, 2, ... diterpene, 1 > 3, decylaminoethyl carbendazim, etc. 'but not (d) in these. (4) When the second transfer is used as the hardening second, it is better to reduce the particle size so that it is uniformly dispersed. In the second brewing, from the viewpoint of crystal contamination, it is especially preferred that the adipic acid is not brewed. The second brewed bismuth, bis(indenylethyl)_5_isopropyl B. (A:re VDH). When the average particle diameter is too large, when the narrow gap liquid crystal is formed 70 degrees earlier, when the upper and lower glass substrates are bonded together, the gap may not be formed smoothly. Therefore, it is preferably 3 Å or less, and more preferably 2 Call the following. Further, similarly, the maximum particle diameter is preferably 8 or less, more preferably 5 μη or less. The particle size of the hardener is determined by a laser diffraction/scattering particle size distribution analyzer (dry type) (manufactured by ENTERPRISE C〇., LTD; LMs_3〇). It is important that the liquid crystal sealing agent hardener of the liquid crystal dropping method is such that, when heated after light irradiation, the liquid crystal sealing agent starts to react uniformly and rapidly without contaminating the liquid crystal, and when used, the viscosity at room temperature changes little and Good service life. In the case of a solid dispersion type latent heat curing agent, if the particle diameter is not uniform and the particle diameter is large, or the dispersion is insufficient, the curing may not proceed uniformly, which may cause a cell gap defect or cause liquid crystal contamination. Miscellaneous, resulting in poor display of the liquid crystal panel. In view of the above problems, the diterpene compound used in the invention of 121463.doc • 13-200827882 is preferably measured by a laser diffraction/scattering particle size distribution analyzer to be finely ground to an average particle diameter of 3 μm or less. More preferably, the average particle diameter is 2 μηη or less, and the lower limit of the average particle diameter is about 〇·1 μπι. Further, similarly, the maximum particle diameter is preferably 8 or less, more preferably 5 μm or less. The use of a sealant with a diterpene compound has an excellent service life at room temperature, on the other hand, even at 12 Torr. Under the conditions of 〇 and i, it also showed moderate hardenability. Since the diterpene compound has almost no solubility to the liquid crystal, the contamination to the sealed liquid crystal is extremely low. The amount of the diterpene compound (a) to be used as the curing agent is preferably i parts by weight or more and 2 parts by weight or less based on 100 parts by weight of the curable resin (b). As the curable resin of the present invention, one type or two or more types of curable resins selected from the group consisting of epoxy resins, (meth)acrylated epoxy resins, and partially (meth)acrylated epoxy resins are used. For example, an epoxy resin, a mixture of an epoxy resin and a (meth)acrylated epoxy resin, a (meth)acrylic epoxy resin, a partial (meth)acrylated epoxy resin, or the like can be given. (herein, "(meth)acrylic" means "acrylic" and/or "methylpropionic acid", and the same applies to the curable resin used in the present invention, and any of the preferred ones are preferred. In order to reduce the contamination and solubility of the liquid crystal, examples of preferred epoxy resins include bisphenol s type epoxy resin, meta-phenylene diglycidyl ether polymer, and ethylene oxide addition. Diglycidyl ether of bisphenol S is exclusively used, but is not limited to these. (Methyl)-propylated epoxy resin and a partially (meth)acryl-based oxime epoxy resin can be obtained by reacting an epoxy resin with (meth)acrylic acid. The epoxy resin as a raw material is not limited to 121,463.doc •14-200827882, but it is preferably a good bismuth bisphenol A type epoxy resin furnace ρ, which is exemplified by Eucalyptus, bisphenol F-type epoxy resin, double fat, phenolic phenolic aldehydes and sputum gt; gonadophene type 8% oxygen tree 庐雔 衣 乳 曰 曰, cresol novolac type epoxy pepper曰 曰, 双 酴 A A A A A A A A A A A A A & & 生 生 生 生 生 生 生 生 生 生 生 生 生 生 生 生 生 生 生 生 生 生 生 生 生 生 生 生 生 生 生 氧 氧 氧 氧 氧 氧 氧 氧 氧 氧 氧 A A A A A Resin: Glycidylamine type ring system (4) Varnish type epoxy tree 2 = "There is a fragrant eucalyptus tree with a two-beautiful simmered skeleton. In addition, there are also two: two glycerin ducks, two-functional Alcohols are dihydrated::: 2, such sclerosing compounds, hydrogenated compounds, etc. Among these, from the viewpoint of liquid crystal pollution, from the point of view, 'better is double-type epoxy resin, (four) varnish-type ring The ratio of the epoxy group to the (meth)acrylonitrile group is not limited, and can be appropriately selected from the viewpoints of V-stability and liquid crystal contamination. In order to further control the reactivity and the viscosity of the curable resin, it is also possible to use a monomer and/or an oligomer which is a (meth)acrylic acid s. As such a monomer or oligomer, for example, two different The reaction product of pentaerythritol and (meth)acrylic acid, the reaction product of a pentaerythritol, and the (meth)acrylic acid, etc., is not particularly limited if the contamination to the liquid crystal is low. In the invention, the amount of the curable resin (b) used can be used within a range that does not affect the workability and physical properties of the obtained liquid helium sealant, which is usually 25 to 8 in the liquid crystal sealing agent. In the liquid crystal sealing agent of the present invention, when a curable resin containing a (meth)acryl fluorenyl group is used, the photocuring property is imparted to the liquid crystal sealing agent, and a radical reactive type is used. Photopolymerization 121463.doc -15- 200827882 Initiator. If the initiator has sensitivity near the 丨 line (365 nm) which has a relatively small influence on the liquid crystal characteristics, and the liquid crystal contamination is low, it can be used = As a free radical reaction type photopolymerization initiator Specific = for example, benzoin amitraz, ... (4) cyclohexylphenyl _, ^ ethyl 嗓 、, benzophene _, 2 _ ethyl ", 2 _ base 2 曱 曱 stupid Acetone, 2-methyl-[4.(methylthio)phenyl]_2•morpholinylpropane, 2,4,ditrimethylbenzene,f-yldiphenylphosphine oxide, 2-acrylic acid Reaction product of ethyl vinegar with isophora diisocyanate and 2-hydroxyhydroxyethoxy)phenyl]-2-methylpropane-1 Ketone, and 2-isocyanate ethyl methacrylate and 2-hydroxyl group a reaction product of -l-[4-(2-hydroxyethoxy)phenyl]-2-methylpropane-indole-one. When a radically reactive photopolymerization initiator is added, the amount thereof to be used is usually about 0.1 to 5% by weight in the liquid crystal sealing agent. In the liquid crystal sealing agent of the present invention, a polycarboxylic acid (C) is added as a curing accelerator to improve low-temperature hardenability. Specific examples of the polyvalent carboxylic acid include aromatic acid buffers such as decyl monocarboxylic acid, isophthalic acid, terephthalic acid, trimellitic acid, benzophenone tetraweisic acid, azelaic acid, and twelve. An aliphatic carboxylic acid such as a succinic acid or a polyvalent carboxylic acid having a heterocyanogenic ring skeleton represented by the above formula (1). Specific examples of the polyvalent carboxylic acid having a hetero-cyanur ring skeleton represented by the formula (?) include gin(2-carboxymethyl)iso-cyanuric acid vinegar (the following formula (5)), Ginseng (2- oxoethyl) iso-cyanuric acid vinegar (the following formula (3)), ginseng (2-carboxypropyl) iso-cyanate (the following formula (4)), double (2- Carboxyethyl)isocyanate (formula (6) below). [Chemical 5] 121463.doc -16- 200827882 _e一 oh IIo

•N HO—C a 1!o 丫 0 (5) -G—OH II o

[Chemical 6]

HO—C—C I! h2 0 [化8] H〇一 C一II ο ο.

• N h2c, Ν 丫

O

H

, CH2-C-OH O , 0 (4) N, H2 c - h2 • C — OHIIo , c h2

VN, (6) Ο H2 "C-OH II o 121463.doc -17- 200827882 Among the hardening accelerators, it is better in the present invention from the viewpoint of miscellaneous, hydrazine, and one meter. Diacid, 12, ^# raw and liquid crystalline cyanide ring polybasic acid. ~-Diacid, and the addition amount of hardening accelerator, (_ part by weight is more than (four) parts by weight and 10 weight ^The curable resin is a liquid crystal sealing agent of the present invention to improve the adhesion, moisture resistance, etc., and to prepare an inorganic filler.

There is no particular limitation, but specifically, it can be exemplified by a spherical shape: a machine filler 'and-^ 』 竿竦-shaped cerium oxide, molten 氮化 nitriding, crystalline dioxotomy, titanium oxide, titanium black, carbon cut, nitrogen 'Boron boron, calcium carbonate, magnesium carbonate, barium sulfate: stone, sticky... Ming, oxidation town, oxidation fault, gas oxidation Ming, nitrogen and oxygen: town, Shixi acid , Shixi acid, barium titanate, glass fiber, carbon fiber, dithizone, asbestos, etc., but preferably spherical 2, fossil eve, molten dioxotomy, crystalline dioxotomy, oxidation, Qin, Chaotic stone eve, nitriding butterfly, carbon _, barium sulfate, sulfur (four), mica, talc, clay, oxidized Ming, hydrazine, Shi Xi _, Shi Xi acid Ming. The above inorganic filler may be used in combination of two or more kinds. The average particle diameter of the inorganic filler used in the present invention is preferably 3 μm or less. When the average particle diameter is more than 3 μm, the gap formation may be hindered in the production of the upper and lower glass substrates in the production of the liquid crystal cell. The lower limit of the average particle diameter of the inorganic filler is usually about 0·01 μηι. The inorganic filler used in the present invention is contained in the liquid crystal sealing agent, which is usually 2 to 60 weights! %, preferably 5 to 5 % by weight. When the filler content is less than 2% by weight, the adhesion strength to the glass substrate is lowered, and 121463.doc -18-200827882 _ wet reliability is also poor', so the adhesion strength after moisture absorption is also greatly reduced, and the filler content is When it is more than 60% by weight, the content of the filler is too large, and there is a possibility that it is difficult to grind and the gap of the liquid crystal cell cannot be formed. Further, in the liquid crystal sealing agent of the present invention, an organic filler may be further added in a range which does not affect the liquid crystal sealing property. The organic filler 'is a polymer bead, a core-shell type rubber filler, or the like. Two or more of these fillers may be used in combination. The liquid crystal sealing agent of the present invention preferably contains a decane coupling agent in order to increase the adhesion strength thereof. Examples of the decane coupling agent which can be used include 3 glycidoxypropyl trifoxy (tetra), 3-glycidoxypropylmethyldimethoxy (tetra), and 3-glycidoxypropylmethyl. : methoxy oxime, 2_(3,4-epoxycyclohexyl)ethyltrimethoxydecane, n-phenylaminopropyldimethoxyspar, N_(2•aminoethyl) 3-aminopropylmethyldimethoxycarbazide, N-(2-aminoethyl) 3-aminopropylmethyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3 _Mercaptopropyltrimethoxydecane, vinyltrimethoxydecane, N_(2-(vinylbenzylamino)ethyl)> Aminopropyldimethoxydecane hydrochloride, 3-mercapto A ruthenium coupling agent such as propylene methoxypropyltrimethoxy zeoxime, 3-chloropropylmethyldimethoxy decane, > chloropropyltrimethoxy zeshi. These decane coupling agents may be used in combination of two or more kinds. In order to obtain good adhesion strength, it is preferred that the decane coupling agent is a decane coupling agent having an amine group. A liquid crystal sealing agent which is improved in strength and excellent in moisture resistance reliability can be obtained by using decane coupling ^. When a coupling agent is added, the amount of the coupling agent used is usually about 1 to 15 121463.doc -19·200827882% by weight in the liquid crystal sealing agent. According to the liquid crystal sealing agent of the present invention, an organic solvent, an additive such as a pigment, a leveling agent, or an antifoaming agent may be blended. In order to obtain the liquid crystal sealing agent of the present invention, first, in the case where the resin component is dissolved and mixed, the filler component is mixed by a well-known mixing device such as a 3-roll mill, a sand mill, a ball mill, or a planetary mixer f. The heat hardener 'by this can manufacture the liquid crystal sealing agent of this invention. In order to remove inclusions after the end of the mixing, it is preferred to carry out a filtration treatment. In the liquid crystal cell of the present invention, a pair of substrates of a special electrode are formed on a counter substrate disposed at a predetermined interval, and the periphery of the substrate is sealed by the liquid crystal sealing agent of the present invention, and liquid crystal is sealed in the gap. The type of liquid crystal to be enclosed is not particularly limited. Here, the substrate is composed of a composite substrate composed of glass, quartz, plastic, tantalum or the like and at least one of them has light transmissivity. For example, after a spacer such as a glass fiber (gap control material) is added to the liquid crystal sealing agent of the present invention, the liquid crystal sealing agent is applied to one of the pair of substrates by a dispenser or the like. In the shape of a crucible, the liquid crystal is dropped into the inside of the liquid crystal encapsulant cofferdam, and another glass substrate is superposed in a vacuum, thereby forming a gap. After the gap is formed, the liquid crystal sealing portion is irradiated with ultraviolet rays by an ultraviolet ray irradiator to harden the light. The ultraviolet irradiation amount is usually 200 mJ/cm 2 to 6000 mJ/cm 2 , preferably 500 mJ/cm 2 to 4000 mJ/cm 2 . Thereafter, curing is carried out at a temperature of 9 Torr to 140 ° C for 1 to 2 hours, whereby a liquid crystal display unit of the present invention can be obtained. Or in the present invention, after forming the gap, the ultraviolet light is not directly irradiated at 90 to 140 ° C for 1 to 2 hours, and the liquid crystal display unit of the present invention can be obtained by 12U63.doc • 20-200827882. . Examples of the spacer include glass fiber, Shi Xizhu, and polymer beads. The diameter varies depending on the purpose of use', but is usually 2 to 8 μΓη, preferably 4 to 7 μηη. The liquid crystal sealant (10) by weight f is usually in the range of 〇 to 4 parts by weight, preferably about 5 to 2 parts by weight. The liquid crystal sealing agent of the present invention has extremely low staining property to the liquid crystal after the manufacturing step, and the coating workability, the conformability, the bonding strength, and the use of the φ to the temperature of the substrate are used. Lifetime) and low temperature hardenability. The liquid crystal display unit of the present invention obtained in the above manner is excellent in adhesion and moisture resistance reliability. There is no display failure due to liquid crystal contamination. (Embodiment) Hereinafter, the present invention will be described in further detail based on examples. [Example 1] 75 parts by weight of epoxy acrylate resin kayara D R-94220 (manufactured by Nippon Chemical Co., Ltd.; double ρ epoxy resin epoxy φ acrylate), 25 parts by weight of epoxy resin RE -203 (manufactured by Nippon Kayaku Co., Ltd.; epoxy equivalent 233 g/eq, ethylene oxide addition bisphenol s type epoxy resin), 5 parts by weight of photopolymerization initiator KAYACURE rPI-4 (Japanese - Pharmaceutical Co., Ltd.; reaction of 2-isocyanate ethyl methacrylate with 2-hydroxy-l-[4-(2-hydroxyethyl)phenyl] 2-methylpropane-1 Ketone And 1.5 parts by weight of a decane coupling agent sila-Ace S-510 (manufactured by Chisso Co., Ltd.; 3-glycidoxypropyltrimethoxydecane) to obtain a resin liquid. Next, 17.5 parts by weight of Nanotec alumina SPC (manufactured by ci Kasei Co., Ltd.; spherical oxygen 121463.doc • 21 · 200827882, T average particle size 50 nm) was uniformly mixed by a bead mill. 3 parts by weight of butadiene-alkyl methacrylate-styrene copolymer (manufactured by Rohm and Haas Co., Ltd.; PARALOID EXL-265 5) 'as a filler, and further mixes 7.5 parts by weight of benzene Di-n-bisaluminum dicarboxylate fine product (manufactured by Otsuka Chemical Co., Ltd., iDH_s is finely ground to a mean particle size of μπι, maximum particle size of 5 4111 by a jet mill), and 75 parts by weight of dodecane Diacid-grinding mouth (manufactured by Yusho Co., Ltd.; finely ground dodecanedioic acid by jet mill to an average particle size of 丨.5 μπι, maximum particle size of 5 μιη), The 3-roll mill was kneaded to obtain the liquid crystal sealing agent of the present invention. The viscosity of the liquid crystal sealing agent (25 ° C), 32 〇 Pa.s (25 < t, sizing viscometer (manufactured by Toki Sangyo Co., Ltd.)). [Example 2] 75 parts by weight of epoxy acrylate resin kayara D R-94220 (manufactured by Nippon Kayaku Co., Ltd.; epoxy acrylate of bisphenol F epoxy resin), 25 parts by weight of epoxy resin RE_2〇 3 (manufactured by Nippon Kayaku Co., Ltd.; epoxy equivalent 233 g/eq, ethylene oxide addition bisphenol s type epoxy resin), 5 parts by weight of photopolymerization initiator KAYACURE RPI-4 (Japanese chemical) Manufactured by Yueshou Co., Ltd.; the reaction product of 2-isocyanate ethyl methacrylate with 2_light base 1 [4 (2-ethoxy)phenyl] 2 -methylpropanone · 1 _ _) And 1.5 parts by weight of a decane coupling agent sila_Aee s-510 (manufactured by Chisso Co., Ltd.; 3-glycidoxypropyltrimethoxydecane) to obtain a resin liquid. Next, 175 parts by weight of Nanotec alumina SPC (manufactured by Cl Kasei Co., Ltd.; spherical oxidation, average particle diameter of 5 〇nm), and 3 parts by weight were uniformly mixed by a bead mill. Butadiene • A 121463.doc -22- 200827882 Acrylic acid alkyl benzoate copolymer (made by Rohm and Haas Co., Ltd.; PARALOID EXL-2655) as a filler, and further mixed 7_55 parts by weight Bismuth isophthalate finely ground product (manufactured by Otsuka Chemical Co., Ltd.; finely ground IDH-S by jet mill to an average particle size of i · 5 μπι, maximum particle size of 5 μηι), and 3 Parts by weight of ginseng (2-carboxyethyl) iso-cyanurate (manufactured by Shikoku Chemical Industry Co., Ltd.; finely ground CIC acid to a mean particle size of 15 μηι, maximum particle size by a jet mill The liquid crystal sealant of the present invention was obtained by kneading by a 3-roll mill. The viscosity (25 〇c) of the liquid crystal sealing agent was 34 〇 Pa s (25 ° C, R type viscosity meter (manufactured by Toki Sangyo Co., Ltd.)). [Example 3] 75 parts by weight of epoxy acrylate resin kayaRAD R-94220 (manufactured by Sakamoto Chemical Co., Ltd.; epoxy acrylate of bisphenol ρ epoxy resin), 25 parts by weight of epoxy resin RE -2〇3 (manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 233 g/eq, ethylene oxide addition bisphenol s type epoxy resin)' 5 parts by weight of photopolymerization initiator KAYACURE κρι·4 ( Manufactured by Nippon Kayaku Co., Ltd.; reaction of 2-Isocyanate ethyl methacrylate with 2_hydroxyl 1 [4-(2-ethoxylated) benzyl] 2-methylpropanone _ _ ketone And 1.5 parts by weight of a decane coupling agent Sila-Ace s 1 (manufactured by Chisso Co., Ltd.; 3-glycidyl oleyloxypropyltrimethoxydecane) to obtain a resin liquid. Secondly, 'mixed evenly by the bead mill〗 7.5 parts by weight

Nanotec Oxidation SPC (manufactured by ci Kasei Co., Ltd.; spherical alumina, average particle size 50 nm), and 3 parts by weight of butadiene•alkyl methacrylate•styrene copolymer ( Rohm and Haas Co., Ltd.; 121463.doc • 23- 200827882 PARALOID EXL-2655) As a filler, a mixture of 7·55 parts by weight of a finely divided bismuth phthalate product (manufactured by Otsuka Chemical Co., Ltd.) ; IDH_S is finely ground to a mean particle size of 1.5 μηη, a maximum particle size of 5 μπι by a jet mill, and 3 parts by weight of a ginseng (2-carboxypropyl) iso-cyanurate milled product (four) Manufactured by Guohuacheng Industrial Co., Ltd.; the C3-CIC acid is finely ground to a mean particle size of 丨.5 μπι and the maximum particle size is 5 μιη by a jet mill, and kneaded by a 3-roll mill. Thus, the liquid crystal sealing agent of the present invention is obtained. The viscosity (25 ° C) of the liquid crystal sealing agent was 38 〇Pa_s (25 ° C, R type viscosity meter (manufactured by Toki Sangyo Co., Ltd. [Example 4] 75 parts by weight of epoxy acrylate resin KAYARAD R- 94220 (manufactured by Sakamoto Chemical Co., Ltd.; epoxy acrylate of bisphenol ρ epoxy resin), 25 parts by weight of epoxy resin rE_203 (manufactured by Nippon Kayaku Co., Ltd.; epoxy equivalent 233 g/eq, ring Oxygen bromide addition double age s type epoxy resin), 5 parts by weight of photopolymerization initiator KAYACURE rPI_4 (manufactured by Nippon Kayaku Co., Ltd.; methacrylic acid 2 · isocyanate ethyl ester and 2-hydroxy-l- [4-(2-hydroxyethoxy)phenyl]_2-methylpropan-1-one reaction product), and 1.5 parts by weight of Shixi-burning coupler Sila-Ace S-51〇 (Zhisuo shares) Co., Ltd.; 3-glycidoxypropyltrimethoxydecane) to obtain a resin liquid. Secondly, 17.5 parts by weight of iNan〇tec alumina SPC was uniformly mixed by a bead mill (Li Kasei Co., Ltd. limited) Company made; spherical alumina, average particle size 50 rim), and 3 parts by weight of butadiene • alkyl methacrylate • styrene Copolymer (manufactured by Rohm and Haas Co., Ltd.; PARALOIDE XL-2655) as a filler, and further mixed with 7 parts by weight of 121463.doc -24-200827882 diacetate di- finely pulverized finely ground product (manufactured by Otsuka Chemical Co., Ltd.) ; ADH-S is finely ground to a particle size of l5 μπι with a maximum particle size of 5 μπι by a jet mill, and 0.75 parts by weight of dodecanedioic acid milled product (made by Ube Industries, Ltd.): The dodecanedioic acid is finely ground to a particle size of L5 μm and the maximum particle diameter is 5 μm by a jet mill, and kneaded by a 3-roll mill to obtain the liquid crystal sealing of the present invention. The viscosity (25. 〇) of the liquid crystal sealing agent was 300 Pa.s (25 ° C, R type viscometer (manufactured by Toki Sangyo Co., Ltd.).) [Example 5] 75 parts by weight of epoxy acrylate was mixed. Ester resin KAYARAD R-94220 (manufactured by Sakamoto Chemical Co., Ltd.; epoxy acrylate vinegar of bisphenol ρ epoxy resin), 25 parts by weight of epoxy resin RE-203 (manufactured by Nippon Kayaku Co., Ltd., epoxy Equivalent 233 g/eq, Ethylene Ethylene Bake Addition 5 parts by weight of photopolymerization initiator kayacure κρΐ-4 (manufactured by Nippon Kayaku Co., Ltd.; 2-isocyanate ethyl methacrylate and 2-hydroxy-1-[4-(2-perethoxy) ) a reaction product of phenyl]-2-methylpropan-1-yl ketone), and 1.5 parts by weight of a decane coupling agent Sila_Ace s_51〇 (manufactured by Chisso Co., Ltd.; 3-glycidoxypropyltrimethoxy) Based on the base stone, the resin liquid is obtained. Next, 175 parts by weight of 2Nan〇tec Oxide SPC (manufactured by Cl Kasei Co., Ltd.; spherical oxidation, average particle diameter of 50 nm), and 3 parts by weight were uniformly mixed by a bead mill. Diene-methacrylic acid alkyl ester styrene copolymer (manufactured by Rohm and Haas Co., Ltd.; PARALOIDE XL-2655) as a filler, and further mixed with 7 parts by weight of a dipyridinium diacetate fine abrasive product (Otsuka Chemical Co., Ltd.) Co., Ltd.; by spraying I21463.doc -25- 200827882, the grinding machine is used to grind ADH_S fine 硌舔 仏 / / / 〇 、 、 、 、 研磨 研磨 研磨 研磨 研磨 研磨 研磨 研磨 研磨 研磨 研磨 研磨 研磨 研磨 研磨 研磨 研磨 研磨 研磨 、 、 、 、 、 、 、 、 、 、 、 、 5 μπι), and 1畲晷々Α $ 伤 之 ( (2-carboxyethyl) iso-cyanate grinding products (Four countries into the industrial stocks of your female \ 1 _ ^ slave injury company: The CIC acid is finely ground to a fineness by a jet mill to an average particle size of 1 · 5 μm and a maximum particle diameter of 5 μπι, and the alum is kneaded by a 3-roll mill to obtain the present. The invention is a liquid crystal sealing agent. The viscosity of the liquid crystal sealing agent (25. 〇 is 320 Pa.s (25 Χ:, R type viscosity meter (manufactured by Toki Sangyo Co., Ltd.)). [Example 6] Mixed 75 parts of epoxy acrylate resin KAYARAD R-94220 (manufactured by Nippon Kayaku Co., Ltd.; epoxy acrylate of bisphenol F epoxy resin), 25 parts by weight of epoxy resin RE_2〇3 (manufactured by Nippon Kayaku Co., Ltd.; epoxy equivalent 233 g/ Eq, ethylene oxide addition bisphenol S type epoxy resin), 5 parts by weight of photopolymerization initiator KAYACURE Rpi_4 (manufactured by Nippon Kayaku Co., Ltd.; 2-isocyanate ethyl methacrylate and 2_jing a reaction product of bis-l-[4-(2-ethoxy)phenyl]-2-methylpropane- ketone), and 1.5 parts by weight of a decane coupling agent sila_Ace S-51〇 Co., Ltd.; 3-glycidoxypropyltrimethoxydecane) to obtain a resin liquid. Secondly, 7.5 parts by weight of Nanotec alumina SPC was uniformly mixed by a bead mill (Xiai Huacheng ( Cl Kasei) Co., Ltd.; spherical emulsification, average particle size of 50 nm), and 3 parts by weight of butadiene/methacrylic acid a styrene copolymer (manufactured by Rohm and Haas Co., Ltd.; PARALOIDE XL-2655) as a filler, and further mixed 7 parts by weight of a fine adipic acid dipper product (manufactured by Otsuka Chemical Co., Ltd.; by spraying In the grinder, the ADH-S is finely ground to an average particle size of 1.5 μm, the most 121,463.doc -26 - 200827882 has a large particle size of 5 μm, and 1 part by weight of the ginseng (2-carboxypropyl) heterotrimer. Cyanate-based abrasive product (manufactured by Shikoku Chemical Industry Co., Ltd.: C3-CIC acid is finely ground to a mean particle size of 1.5 μm and a maximum particle size of 5 μm by a jet mill), and is passed by 3 rolls. The liquid crystal sealing agent of the present invention was obtained by kneading with a grinder to obtain a liquid crystal sealing agent of the present invention. The viscosity of the liquid crystal sealing agent (25 〇 is 350 Pa.s (25 ° C, R type viscosity meter (manufactured by Toki Sangyo Co., Ltd.)). Example 1 75 parts by weight of epoxy acrylate resin KAYARAD R_ 94220 (manufactured by Sakamoto Chemical Co., Ltd.; epoxy acrylate of bisphenol ρ epoxy resin), and 25 parts by weight of epoxy resin rE_203 (曰本化Pharmaceutical Co., Ltd.; epoxy equivalent 233 g / eq, epoxy B Alkyl addition bisphenol S type epoxy resin), 5 parts by weight of photopolymerization initiator KAYACURE RPI-4 (manufactured by Nippon Kayaku Co., Ltd.; 2-isocyanate ethyl methacrylate and 2-amino-hydroxyl) a reaction product of ethoxy)phenyl]-2-methylpropan-one), and 1.5 parts by weight of a decane coupling agent Sila-Ace S-51〇 (manufactured by Chisso Co., Ltd.; 3-glycidoxypropyl Base trimethoxy decane), obtained from the tree sputum. Secondly, the hunter was uniformly mixed with a bead mill and 17 wt% of Nanotec alumina SPC (manufactured by ci Kasei Co., Ltd.; spherical alumina, average particle size of 5 〇 nm), 3 weights a portion of butadiene-alkyl methacrylate-styrene copolymer (manufactured by Rohm and Haas Co., Ltd., PARALOIDEXL-2655) as a filler, and further knead 7.55 parts by weight of benzene by a three-clamp mill Dithifin diacetate finely-grinded product (manufactured by Otsuka Chemical Co., Ltd.; finely ground to a fine particle diameter of L5 pm and a maximum particle diameter of 5 μm by a jet mill) to obtain the present invention Liquid 121463.doc -27- 200827882 day in the sealant. The viscosity of the liquid crystal sealing agent (25 Å) was 32 〇Pa s (25 (> c, sizing viscometer (manufactured by Toki Sangyo Co., Ltd.)). Comparative Example 2 w and 75 parts by weight of epoxy acrylate resin kayaraD R-94220 (manufactured by Nippon Kayaku Co., Ltd.; epoxy acrylate of bisphenol F epoxy resin), 25 parts by weight of epoxy resin rE_2〇3 (manufactured by Nippon Kayaku Co., Ltd.; epoxy equivalent 233 g/eq, ethylene oxide addition bisphenol s type epoxy resin), 5 parts by weight of photopolymerization initiator kayaCURE RPI-4 (manufactured by Nippon Kayaku Co., Ltd.; 2-methacrylic acid 2-isocyanate ethyl ester) a reaction product with 2_hydroxyl·[4ethoxy)carbenyl]-2-mercaptopropen-1-one, and 1.5 篁 之 石 ia j j ia ia ia ia ia ia ia ( ( ( Manufactured by Chisso Co., Ltd.; 3 - glycidoxypropyltrimethoxy sulphate, to obtain a resin solution. Next, a 7:5 parts by weight of Nanotec alumina SPC (manufactured by CI Kasei Co., Ltd.; spherical oxidation, average particle diameter of 50 nm), and 3 were uniformly mixed by a bead mill. Parts by weight of butadiene-alkyl methacrylate-styrene copolymer (manufactured by Rohm and Haas Co., Ltd.; PARALOIDEXL-2655) as a filler, and further kneaded by 7 parts by weight in a 3-roll mill A disulfide finely-grinded product (manufactured by Otsuka Chemical Co., Ltd.; the ADH-S is finely ground to have an average particle diameter of 15 μm and a maximum particle diameter of 5 μπι by a jet mill) to obtain the liquid crystal of the present invention. Sealants. The viscosity (25 ° C) of the liquid crystal sealing agent was 300 Pa.s (25 ° C, R type viscosity meter (manufactured by Toki Sangyo Co., Ltd.)). The compositions of the liquid crystal sealing agents disclosed in Examples 1 to 6 and Comparative Examples 1 to 2 are shown in Table 1. 121463.doc -28- 200827882 Liquid crystal contamination (uv irradiation and heat hardening) Put 0.5 g of liquid crystal sealing agent in the vial and add 1 g of liquid crystal (Merke (Merck), MLC-6866_1〇〇) Ultraviolet rays of 3000 mj/cm2 were irradiated by an irradiation machine, and then placed in an i2〇〇c oven for 1 hour. After standing at room temperature for 30 minutes, the liquid crystal was taken out from the sample bottle, and the amount of elution (ppm) of the sealant component was measured by gas chromatography. The results are shown in Table 2 (liquid crystal contamination (Uv irradiation and thermosetting): amount of dissolution (PPm)) 〇 liquid crystal contamination (thermal hardening only) 0.5 g of liquid crystal sealing agent was placed in the sample bottle, and 1 was added. g liquid crystal (manufactured by Merck Co., Ltd., MLC-6866-100) was put into 120. 1 hour in the oven. Immediately after taking out from the oven, the liquid crystal was taken out from the sample bottle, and the amount of the sealant component was measured by gas chromatography (howling. The results are shown in Table 3 (liquid crystal contamination (heat hardening only): The amount of elution (ρριη)). Next, a liquid crystal sealant obtained by adding 100 g of ig as a spacer was mixed and stirred, and the liquid crystal sealant was applied to a glass of 5 mm×50 mm. On the substrate, a glass piece of mmxl.5 mm is attached to the liquid crystal sealing agent, and the ultraviolet light of 3 ^.^ is irradiated by a *uv irradiation machine, and then put into an oven to be thermally hardened. The thermosetting condition is iOOti. Hour and 12 (2 hours of TC 1 hour. The shear strength of the glass piece was measured by a Western-made bond strength tester. The results are shown in Table 4." Service life 121463.doc -29- 200827882 The viscosity of the obtained liquid crystal sealing agent at 25 ° C. The viscosity increase rate (%) with respect to the initial viscosity is shown in Table 4. The liquid crystal cell was evaluated for evaluation (photothermal and liquid crystal dropping method) with a transparent electrode On the substrate, The cloth alignment liquid (pIA_554〇_ 05A; manufactured by Chisso Co., Ltd.) was fired and subjected to rubbing treatment. The liquid crystal sealing agent of the examples and the comparative examples was bonded to the substrate to have a line width of 1 mm. 'The seal pattern and the temporary seal pattern were formed by the dispenser, and the liquid crystal (JC-5015LA; manufactured by Chisso Co., Ltd.) droplets were dropped into the seal pattern frame. Further, the in-plane spacers were Nat〇c〇 spacer KSEB-525F; manufactured by NATOCO Co., Ltd.; gap width after bonding is 5 μm) Dispersion heat fixation on another rubbed substrate, and using a bonding device to make it in a vacuum The film is bonded to the substrate on which the liquid crystal is dropped. After the gap is formed in the air, the sealant portion is irradiated with 3 J/cm 2 (100 mW/cm 2 ) by a metal element lamp (manufactured by USHIO Motor Co., Ltd.). , 30 seconds) of ultraviolet rays, hardened, and then put into a 120 C oven for heat curing for one hour, thereby making a liquid crystal test unit for evaluation. Preparation of liquid crystal cell for evaluation (thermal hardening liquid crystal drop injection method) On the substrate of the transparent electrode, an alignment film solution (PIA.554〇-〇5A; manufactured by Chisso Co., Ltd.) was applied and fired, and rubbing treatment was performed. The liquid of the examples and the comparative examples was bonded to the substrate. The line width after the sealant reaches 1mm in the daytime 'by the dispenser to form the seal pattern and the temporary seal pattern, and secondly, the liquid crystal (K:-5〇15LA; manufactured by Chisso Co., Ltd.) Into the seal pattern frame. In turn, the in-plane spacers (gauge (10) 121463.doc -30- 200827882 partition KSEB-525F; made by NATOCO Co., Ltd.; gap width after bonding is 5 μιη) The film is placed on another substrate which has been subjected to rubbing treatment, and is bonded to the substrate on which the liquid crystal has been previously dropped in a vacuum using a bonding device. After being placed in the air to form a gap, it was directly put into a 12 (TC oven) without being hardened by υ, and heat-hardened for one hour to prepare an evaluation liquid crystal test unit. The liquid crystal for evaluation which has been prepared by a polarizing microscope observation The sealing shape of the unit and the alignment of the liquid crystal were disordered. The results are shown in Table 5. The evaluation was divided into the following four grades: 〇 (near the seal, no alignment disorder) △ (near the seal, slightly aligned disorder) x (liquid crystal flows into the seal, or there is alignment disorder in the vicinity of the seal) xx (sealing crack fails to form a unit) As shown in Table 2 and Table 3, the liquid crystal sealants of the examples and comparative examples of the present invention are liquid crystals. A liquid crystal sealing agent having a low degree of contamination. Then, as shown in Table 4, it can be seen that the liquid crystal sealing agent of the example can obtain a bonding strength larger than that of the comparative example even if it is cured by low temperature (1 〇〇. 4 hours). It is excellent in low-temperature hardening property, and it is also known that the service life is not inferior to the comparative example. According to Table 5, the liquid crystal sealing agent of the embodiment can form a liquid crystal cell by a thermosetting liquid crystal dropping injection method. And also less contamination near the seal, the liquid crystal sealant of Comparative Example can not be dropped by a thermosetting liquid crystal forming a liquid crystal cell injection method [Table 1] 121463.doc -31 -. 200827882 121463.doc * n3

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Claims (1)

200827882 X. Patent application scope: 1 · A liquid crystal sealing agent characterized by: (a) a second brewing compound; (b) a curable resin selected from the group consisting of epoxy resins, (meth)acrylated epoxy resins, and One or two or more kinds of (meth)acrylated epoxy tree, and (c) a polybasic acid as a curing accelerator. 2. The liquid crystal sealant of claim 1, wherein the curable resin is a mixture of an epoxy resin and a (meth)acrylated epoxy resin. 3. The liquid crystal encapsulant of claim 1 or 2, wherein the polycarboxylic acid (c) is dodecanoic acid or sebacic acid. 4. The liquid crystal sealing agent according to claim 1 or 2, wherein the polyvalent carboxylic acid (c) is a polycarboxylic acid compound having a hetero-cyanuric acid ring skeleton represented by the formula (1), [Chem. 9] T1 to T3 each independently represent nitrogen or a molecular bone represented by the following formula (2) [in the formula: [Chemical 10] OH -----^CH24 (2) Ο 121463.doc 200827882 (wherein η represents An integer from 1 to 6)]. 5. The liquid crystal sealing agent of claim 4, wherein the polycarboxylic acid (c) is a compound represented by the following formula (3): [Chem. 11] 6. The liquid crystal sealing agent of claim 4, wherein the polycarboxylic acid (c) is a compound represented by the following formula (4): [Chemical 12] Η2〇 XH2-C-OH 〇 Ο 7. 8. A liquid crystal display unit which is sealed by a hardener of a liquid crystal sealant according to any one of claims 1 to 6. A method of manufacturing a liquid crystal display unit, characterized in that, in one of the liquid crystal display units of the S 2 substrate, one of the liquid crystal sealing agents of any one of claims 1 to 6 is used, and two or two sealing openings are used. The pattern 'and drops the liquid crystal into the sealing pattern or on the opposite substrate, 121463.doc -2- 200827882 and then adheres to the opposite substrate, followed by hardening the liquid crystal sealing agent. 9. The method of producing a liquid crystal display unit according to claim 8, wherein the curing is performed once by ultraviolet rays and/or visible rays, and then secondary hardening is performed by heating. 1 如 · The liquid crystal g§ of the claim 8; 曰., the manufacturing method of the member is not early, and the line and/or the visible light is subjected to ^Ahu 4 hardening' and hardened only by heating. 121463.doc 200827882 VII. Designated representative map: (1) The representative representative of the case is: (none) (2) The symbol of the symbol of the representative figure is simple: Φ 8. If there is a chemical formula in this case, please reveal the characteristics that can best show the invention. Chemical formula: (none) 121463.doc