TW201204749A - Liquid crystal sealant and liquid crystal display cell using the same - Google Patents

Abstract

This invention relates to a liquid crystal sealant for dropping process containing (a) a photosensitizing agent having a (meth) acrylic group in one molecule and (b) a curable resin having a (meth)acrylic group, and preferably further containing at least one of (d) a photo-polymerization starter or (c) a tertiary amine, which causes little liquid crystal contamination, and can be cured with a high width even in a shielded portion which can not be directly irradiated by ultraviolet ray. Therefore, the liquid crystal sealant can be uniformly cured even if the liquid crystal sealant is located under a shadow such as wirings. Moreover, the liquid crystal sealant is extremely appropriately for being used as liquid crystal sealant for dropping process because the liquid crystal sealant can be well cured even by low energy light such as visible rays.

Description

201204749 VI. Description of the Invention: [Technical Field] The present invention relates to a liquid crystal sealing agent for liquid crystal dropping process, which is used in a liquid crystal panel to 'shave light without direct irradiation even in the shadow of wiring or the like. The part also has excellent hardenability, and has good hardenability even under low-energy light such as visible light, and the liquid crystal contamination is extremely low. [Prior Art] In recent years, the liquid crystal display cell has been enlarged. In the manufacturing method of the liquid crystal display unit, a so-called liquid crystal dropping process with higher mass production has been proposed (please refer to the patent). Document 1, Patent Document 2). Specifically, this method is a method in which a liquid crystal display unit in which a liquid crystal is sealed is formed by dropping a liquid crystal on the inside of a dam of a liquid crystal sealing agent formed on one substrate and then bonding the other substrate. However, in the liquid crystal dropping process, since the liquid crystal sealing agent is in contact with the liquid crystal in an uncured state, the composition of the liquid crystal sealing agent is dissolved in the liquid crystal at this time, so that the specific resistance of the liquid crystal is lowered, and The problem near the sealed part is poor. In the liquid crystal dropping process, three methods of heat curing, photohardening, and photothermal curing are known for the method of hardening the liquid crystal sealing agent after the substrate is bonded. In the thermosetting method, there is a problem that liquid crystal is leaked from the liquid crystal sealing agent which is still hardened due to swelling of the liquid crystal due to heating, and a component of the liquid crystal sealing agent having low viscosity is dissolved in the liquid crystal. If the problem is difficult to solve, it is still not practical. On the other hand, the liquid crystal sealing agent used in the photo-curing method may be, for example, a cationic polymerization type or a radical polymerization type, depending on the type of the polymerization initiator of the light 323208 5 201204749. In the liquid crystal sealing agent of the cationic polymerization type (see Patent Document 3), since ions are generated during photocuring, when used in the liquid crystal dropping process, the ion component is eluted in the liquid crystal in the contact state, so that it is lowered. The problem of the specific resistance of the liquid crystal. In addition, as for the radical polymerization type liquid crystal sealing agent (see Patent Document 4), since the curing shrinkage at the time of photocuring is large, there is a problem that the bonding strength is insufficient. Further, the problem that exists in the photo-curing method relating to both the cationic polymerization type and the radical polymerization type is due to the metal wiring portion of the array substrate of the liquid crystal display unit and the color light-receiving sheet substrate (c In the black matrix portion of the filterl〇r filter substrate, the liquid crystal sealing agent does not shine on the light-shielding portion of the light, so that the light-shielding portion is not cured. Therefore, various problems exist in both the thermal hardening method and the photohardening method, and the practical application of the photothermal curing method disclosed in Patent Document 5 is to be the most practical process technology. The photothermal curing method is characterized in that the liquid crystal sealing agent sandwiched between the substrates is once hardened by irradiation with light, and then heated to be secondarily hardened. Generally, such a liquid crystal sealing agent contains a photoreactive resin, a photoinitiator, a thermosetting resin, and a thermosetting agent. Depending on the manner in which the photoreactive resin and the thermosetting agent are selected, the photoreactive resin may be cured by a thermal hardener. For example, as described in Patent Document 6, when an epoxy acrylate is used as the photoreactive resin and an organic acid hydrazide is used as the thermosetting agent, the photoreactive resin can be subjected to a methacryl addition reaction. Heat hardened. When this method is used, the photoreactive resin of the opaque portion which is not hardened by light hardening can be performed at the time of heat hardening 6 323208

S 201204749 is further improved, and since it is coexisting in the liquid crystal display unit, the addition of the light-shielding portion and the exposure light portion is added, and only the thermosetting tree is added; that is, the heat of the light-shielding portion is exposed. The amount of the hardener that the hardener will degrade will cause insufficient hardening. In addition, if too much thermal hardener is added, the exposed part of the knee will be stored, and as a result, the characteristics of the cured product = low ^ this will make the opaque photoreactive resin of the light-shielding part together The method of hardening is not an excellent method. Further, recently, in the liquid crystal dropping process, it is apt to make the above-mentioned visible light to replace the ultraviolet light. Compared with ultraviolet light, since the visible light system has lower energy, it is also required to harden the liquid sealant (m). This is a problem that raises the degree of seizure to be similar. As described above, although the liquid crystal sealing agent for liquid crystal dropping process has been extremely developed, the hair having excellent shading resistance of the light-shielding portion has not been completed. [Prior Art Document] [Patent Document 1] [Patent Document 1] [Patent Document 2] [Patent Document 3] [Patent Document 4] [Patent Document 5] [Patent Document 6] 曰本特开昭63-179323号Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Problem to be solved by the present invention relates to a liquid crystal sealing agent for a liquid crystal dropping process, in which a liquid substrate B is dripped inside a bank of a liquid crystal sealing agent formed on a substrate, and then the other substrate is bonded. After the liquid crystal sealing portion is irradiated with light, it is cured by heat to form a liquid helium sealant used in the liquid crystal dropping process of the liquid crystal display unit. In the process of the liquid crystal sealing agent, the liquid crystal is extremely low in dyeability, and is excellent in coating workability, adhesiveness, and adhesion strength to the substrate, and excellent in light-shielding property, so that it can be applied to liquid crystal of any design. panel. The present invention provides a liquid crystal sealing agent and a liquid aa display unit using the liquid crystal sealing agent, which has good hardenability in a liquid crystal panel even in a shadow of wiring or the like without being directly irradiated with ultraviolet rays. And its liquid crystal contamination is extremely low. (Means for Solving the Problem) As a result of intensive studies, the present inventors have found that when a photosensitizer having acryl in the molecule is used, the reactivity caused by light can be further enhanced, and liquid crystal contamination can be suppressed. The present invention was completed. That is, the present invention relates to the following items (丨) to (17). (1) A liquid crystal sealing agent for liquid crystal dropping process comprising (a) a photosensitizer having a (meth)acryl acryl in a molecule and (b) having a (fluorenyl) acrylonitrile group Curable resin. (2) The liquid crystal sealing agent for liquid crystal dropping process described in the above (1), wherein (a) a photosensitizer having a (fluorenyl) acrylonitrile group in the molecule is

8 323208 S 201204749 Reaction product of thioxanthone carboxylic acid with glycidyl (meth)acrylate compound, or 4-C1 to C4 alkoxy-1 -(2-(Methyl)propenyloxy-2-Ri-ethoxy)naphthalene (wherein K represents a hydrogen atom or a C1 to C2 alkyl group). (3) The liquid crystal sealing agent for a liquid crystal dropping process according to the above (1), wherein the (a) photosensitive agent having a (fluorenyl) acrylonitrile group in the molecule is at least the following formula (1) to ( 3) Any of the compounds shown.

Formula (3)

9 323208 201204749 (4) As in the above (1) to (3), the liquid crystal sealing agent for the process is included. Ba/, 匕3 secondary amine compound. (5) A liquid crystal sealing agent for use in a process according to any one of the above (1) to (4), which further comprises (d) (10) combining start = _ as in the case. Liquid crystal droplets (4) are liquid crystal dense. The photopolymerization initiator (d) is a photopolymerization initiator having a (meth) acrylonitrile group in the molecule. The liquid crystal droplet described in the above-mentioned item is the ring (7). The liquid crystal sealing agent for the process of the above (1) to (6), wherein oxygen (mercapto) acrylate is used. The liquid crystal droplet according to any one of the preceding paragraphs, wherein the curable resin (b) is an intermediate diglycidylether and the acrylic acid (8) is as in the above (1) to (6) liquid crystal sealing agent, wherein (2) A liquid crystal sealing agent for liquid crystal dropping process according to any one of the above (1) to (8), which comprises (e) an epoxy resin, (7) a heat hardening (10) A liquid crystal sealing agent for liquid crystal dropping process according to any one of the above (1) to (9), which further comprises (g) a flaming coupling agent. (11) (1) i (1G) The liquid crystal sealing agent for liquid crystal dropping process described in the above-mentioned item, which further comprises (h) an inorganic filler. (12) The liquid crystal sealing agent for liquid crystal dropping process as described in the above (1) , wherein the first photosensitizer (a) and 30 to 8% by mass of the aforementioned hardenability 323208 are contained in an amount of 1 to 5% by mass based on the total amount of the liquid crystal sealing agent.

S 10 201204749 Resin (b). (C) The liquid crystal sealing agent for liquid crystal dropping process according to the above (12), which further comprises (10) to 5% by mass of (d) a photopolymerization initiator. The liquid crystal male sealant for a liquid crystal dropping process according to the above (12) or (1), which further comprises 1 to 30% by mass of (e) an epoxy resin, and an epoxy group in the epoxy resin. Equivalent to 2 equivalents of (f) thermal hardener. (1) The liquid crystal sealing agent for a liquid crystal dropping process according to any one of the above (12), which further comprises 〇05 to 3% by mass of the (8) decane coupling agent and 10 to 60% by mass (C) The liquid crystal sealing agent for liquid crystal dropping process of any one of the above-mentioned (12) to (15) which further contains 〇 to 6 mass % of tertiary amine compounds. (n) A liquid crystal display unit which is sealed by a cured product obtained by curing a liquid crystal sealing agent for a liquid crystal dropping process according to any one of the above (A) to (16). (Effect of the Invention) The liquid crystal sealing agent of the present invention has less liquid crystal contamination and excellent curability even under low-energy light such as visible light. Therefore, it is sufficiently hardened even under wiring where direct light is hard to reach. In the light-shielding portion where the ultraviolet ray is not directly irradiated, it can be hardened to a wide width, and even if it is shaded by wiring or the like, it can be uniformly cured. Therefore, the degree of freedom in wiring design of the panel and the step of visible light irradiation can be ensured. Degree of freedom, but It is easy to produce a highly reliable liquid crystal display panel. 323208 11 201204749 [Embodiment] The photosensitizer (a) having a (meth) acrylonitrile group in the molecule used in the present invention is as long as it has (meth) propylene The liquid crystal sealing agent of the present invention is generally used in combination with a photopolymerization initiator (d) to be described later. However, the liquid crystal sealing agent of the present invention may be a liquid crystal sealing agent containing the photosensitizer (a) alone without the photopolymerization initiator (d). Examples of the photosensitizer (a) include a thioxanthone compound having a (fluorenyl) acryl-based group in the molecule disclosed in JP-A-2004-224993 (JP2004-224993 A) or Japanese Patent Laid-Open 4-alkoxy-1-(2-(indenyl)propenyloxyalkoxy)naphthalene disclosed in JP-A-2008-1640 (JP2008-1640 A). More specifically, 'Japan Special Opening 2004- The compound disclosed in Japanese Patent Publication No. 224993 can be exemplified by having a glycidyl group and (methyl group) in one molecule. A reaction product of a glycidyl group-containing (meth) acrylate compound and a thioxanthone carboxylic acid, which are both propylene groups, and examples thereof include glycidyl (meth)acrylate or (methyl) a reaction product of 2-glycidoxypropyl acrylate and thioxanone carboxylic acid, etc. Specific examples of the compound include 3-(indenyl) propylene oxy 2 hydroxy propyl group of thioxanthone carboxylic acid 2-(3-propenyloxy-2-hydroxypropoxy)propyl ester of a base or thioxanthone carboxylic acid, etc., wherein a thioxanthone carboxylic acid group is a propylene oxy group 2_ Hydroxypropyl ester is preferred. 4-Alkoxy 1-(2-(methyl) propylene oxiranyloxy) naphthalene disclosed in Japanese Patent Laid-Open Publication No. 2008-1640, with c4 burning oxygen 323208

S 201204749 -1-(2-(indenyl) propylene-based milk base 2 - 1-ethoxy) naphthalene (wherein a 1 atom - or a C to a C2 alkyl group) is preferred. In addition, the term "(meth)acryloyl" in this specification means "acryloyl" (CH2=CH2CO-) and/or "methyl (G3) = CH2CO〇) A - The photosensitive agent (a) having a (meth) acrylonitrile group is preferably a compound represented by the following formulas (1), (2), and (3), and the like.

‘ can be enumerated (1) (2) Γγ°γ^

(3) Further, the compound of the above formula (1) % _ can be produced according to the method disclosed in Japanese Laid-Open Patent Publication No. 2004-224993. The compounds represented by the above formulas (2) and (3) can be produced according to the method disclosed in Japanese Patent Publication No. 2008-1640. 323208 13 201204749 In general, photosensitizers are effective in helping photopolymerization initiators generate free radicals even under low energy light. However, a general photosensitizer is polluting to a liquid crystal, and thus it is difficult to use it as a constituent component of a liquid crystal sealing agent. However, in the present invention, it has been found that by using a photosensitizer having a photoreactive group in the molecule, particularly a (fluorenyl) acrylonitrile group, liquid crystal contamination can be prevented, and it is considered that by having (meth) A acrylonitrile-based photosensitizer is added to the hardened material to prevent liquid crystal contamination. The content of the photosensitizer (a) having a (fluorenyl) acrylonitrile group in the molecule is 〇·〇1% by mass to 5% by mass in the total amount of the liquid crystal sealing agent of the present invention of 1% by mass. Preferably, 0.1% by mass to 3% by mass is more preferably, and 0.7% by mass to 3% by mass is more preferably. Further, the photopolymerization initiator (d) used in the present invention is not particularly limited as long as it is a free radical polymerization initiator. Examples thereof include: benzil dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, diethyl thioxanthone, diphenyl ketone, 2-ethyl hydrazine, 2-hydroxy-2 -methylpropiophenone, 2-mercapto-[4-(methylthio)phenyl]-2_morpholinyl-1-propane, oxidized-2,4,6-trimercaptobenzoquinone diphenyl A phosphine initiator or the like having a (meth) acrylonitrile group as shown in the following formula (A) disclosed in the pamphlet of International Publication No. WO2006/027982. R3 Ο -[3 X-R2-Y- A r (A) 14 323208 s 201204749 where R1 represents a low-order linear, branched or cyclic divalent carbon number 1 to _ ^ . ^ ^ / nt An alkylene group or an alkyl group (xylene); R2 represents a direct bond of a carbon number of 1 to 0, a branch of a velvet. Lower alkyl or aryl, Ar is not extended, R3, known as helium or methyl. Further, X and γ represent 0 or s; z represents a hydroxyl group or the above R1 or R2 is one of C1 to m〇rph〇lin〇. ^C4 alkyl is preferred. From the viewpoint of liquid crystal contamination, it is shown that the photopolymerization initiator having a (fluorenyl) acrylonitrile group in the molecule is used; For example, a preferred photopolymerization initiator is exemplified by the following formula (A-). &

(In the formula, R represents a hydrogen atom or a methyl group; X and Y each independently represent an oxygen atom or a sulfur atom; ζ represents a trans group or a morphine. The compound can be disclosed according to international publication w〇2〇〇6/〇 The method shown in 2798. The compound represented by the above formula u-) (IV) is a compound which is as defined in the above formula, wherein R is a methyl group, χ & γ is an oxygen atom, and a hydroxyl group is a hydroxyl group. The compound can be U from 2_f-propenyl-oxyethyl isocyanate g with 1-[4-(2-carbylethyl)phenyl]_2•transalkyl-2-methylpropane-1 - The ketone is prepared by reacting. The content of the photopolymerization initiator (d) is preferably from 0.01% by mass to 5% by mass in the total amount of the liquid crystal density of the present invention of 100% by mass (U mass% to 3 mass%). , 〇.7 mass% to 3 f%% and better'. When too little time margin is fully cured, there will be 323208 15 201204749 contamination of the liquid crystal. The liquid crystal sealing agent of the present invention The curable resin (b) having a (fluorenyl) acrylonitrile group is exemplified by (meth) decyl acrylate, epoxy (meth) acryl vinegar, etc. (meth) propylene Examples of the basmic vinegar include, for example, benzoin methacrylate, cyclohexyl methacrylate, glyceryl dimercaptopropionate, glycerol dimethacrylate, EO-modified glycerol trimethyl Acrylate, neopentyl alcohol acrylate, trishydroxypropyl propyl triacrylate, ginseng (propylene oxyethyl) isocyanate, dipentaerythritol hexa-butanoic acid Stupid = phenol triacrylate, etc. Epoxy (meth) acrylate is reacted with (meth)acrylic acid by an epoxy resin and is known The epoxy resin as a raw material is not particularly limited, but a difunctional or higher epoxy resin is preferable, and examples thereof include a bisphenol A epoxy resin and a bisphenol F epoxy resin. The moon 曰 曰 $ 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 衣 phenol phenol phenol phenol phenol phenol phenol phenol phenol phenol phenol phenol phenol phenol phenol phenol phenol phenol phenol phenol phenol phenol phenol phenol phenol phenol phenol phenol Double ❹^^varnish type epoxy resin, alicyclic epoxy tree t, lunar enamel, chain-shaped Wei resin, glycidol g-type epoxy resin, glycidol m-tree 曰, 6 hydantoin (hydantGin) Epoxy resin, isocyanurate type epoxy resin, enamel-type epoxy resin with read simmering bone; other such as phthalate (eate phase), (-1) Difunctional _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The ratio of phenol diglycidyl ether a sulfhydryl group is not limited, the system is suitable for the process and the liquid crystal pollution is 3232〇8 16 201204749 Further, the content of the curable resin (b) having a (fluorenyl) acrylonitrile group in the liquid crystal sealing agent is usually from 30 to 80% by mass, more preferably from 40 to 70% by mass. The liquid crystal sealing agent of the present invention may further comprise (c) a tertiary amine compound, and the hardenability of the light-shielding portion can be further improved by including the tertiary amine compound. Here, the tertiary amine compound means three hydrogen atoms in ammonia. The compound which is substituted by a hydrocarbon group may, for example, be a compound represented by the following formula (4).

Z1, Z2 N Z3 (4) In the formula (4), Z1 to Z3 each independently represent a C1 to C4 alkyl group, a hydroxyl group C1 to C4 alkyl group, a hydroxyl group C1 to C4 alkoxy group C1 to C4 alkyl group, a glycidyl group, and a propylene group. An aryloxy C1 to C4 alkyl group, or an aromatic ring group which may have a C1 to C6 alkoxycarbonyl group or a C1 to C3 alkyl group as a substituent (preferably a C6 to C10 aromatic ring group, more preferably a phenyl group). Examples of the above C1 to C4 alkyl group include a mercapto group, an ethyl group and the like. Similarly, examples of the above-mentioned hydroxy group C1 to C4 alkyl group include hydroxymethyl group, hydroxyethyl group, 3-hydroxypropyl group, 2-hydroxypropyl group, 4-hydroxybutyl group, 3-hydroxybutyl group, and 2 - Hydroxybutyl and the like. Similarly, examples of the above-mentioned hydroxy group C1 to C4 alkoxy group C1 to C4 alkyl group include hydroxyethoxy fluorenyl group, 2-hydroxyethoxyethyl group, and 3-(hydroxyethoxy)propyl group. 3-(hydroxyethoxy)butyl, 2-(hydroxyethoxy)butyl and the like. Examples of the above aromatic ring group include a naphthyl group, a phenyl group, a phenyl group substituted by a C1 to C3 alkyl group, a phenyl group substituted with a C1 to C6 alkane 17 323208 201204749 oxycarbonyl group, and the like. A compound in which any one of z1 to z3 is an aromatic ring is one of the preferred compounds. For example, any one of the preferred groups Z1 to Z3 is an aromatic ring group which may have a substituent such as an ei to C6 alkoxycarbonyl group or a C1 to C3 alkyl group (preferably a c6 to CIO aromatic ring group, and a phenyl group). More preferred) compounds. Among them, special

It is preferred to have a compound having a function as a photopolymerization accelerator. Specifically, commercially available products such as KAYACUREtrm DMBI and KAYAeuRETRM EPA (all manufactured by Sakamoto Chemical Co., Ltd.) can be purchased from the market. Further, from the viewpoint of preventing liquid crystal contamination due to the secondary amine compound, it is preferable to have a reactive group such as an acrylonitrile group or an epoxy group in the molecule. Examples of such a compound include, for example, N,N•diglycidyl oleyl o-amine (GOT: manufactured by Nippon Kayaku Co., Ltd.). According to the above, a more preferable compound may be, for example, two of Z to Z of the above formula (4) are a C1 to C3 or a glycidyl group, and the other one may contain a C1 to C6 alkoxycarbonyl group. Or a phenyl group such as a substituent of C1 to a decyl group. In the liquid crystal sealing agent of the present invention, the epoxy resin (1) which can further improve the bonding strength by using the epoxy resin (e) is not particularly limited, and only two or more functional groups are used. Epoxy resin (epoxy resin having at least 2 epoxy groups) is preferred, and examples thereof include: double-presence A type ring resin: double F type epoxy resin, bisphenol s type epoxy resin, enamel paint Type = reading fat, nail 酴 (four) varnish type epoxy resin, double sided A secret, type bad oxygen resin, bisphenol F novolak type epoxy resin, alicyclic ring resin, aliphatic chain epoxy resin, glycidol Ester type epoxy grease: ^ 323208

S 18 201204749 Glyceramine type epoxy resin, Echinoquinone type epoxy resin, iso-cyanuric acid type epoxy resin, varnish type epoxy resin with three-year brothel skeleton; others such as difunctional phenol a diglycidyl ether compound, a diglycidyl ether compound of a difunctional alcohol; and a halide, a hydride or the like. Among these compounds, from the viewpoint of liquid crystal contamination, a double-type epoxy resin or an acid-clear varnish type epoxy resin is preferred. Depending on the case, it is preferred to use a double-type epoxy resin, and a bisphenol A type epoxy resin is preferred. The content of the % oxygen resin (e) in the liquid crystal sealing agent (the ratio of the liquid crystal sealing agent as a whole; the same applies hereinafter) is preferably about 1 to 3 % by mass, and more preferably 7 to 30% by mass. good. The heat hardener (f) used in the liquid crystal sealing agent of the present invention is not particularly limited', but it is preferred to use a solid organic ruthenium. Examples thereof include salicin, benzoquinone, 1-naphthoquinone, terephthalic dihydrazide, dim-phthalic acid dihydrazide, 2,6. - Di-naphthoic acid dioxime, 2,6-pyridine dioxime, 1,2,4-benzenetriazole, 1,4,5,8-naphthoic acid tetraterpene, pyromellitic acid tetraterpene Wait. Further, examples of the aliphatic hydrazine compound include, for example, hydrazine, ethyl hydrazine, acetamidine, oxaloin, propylene dioxime, bismuth succinate, pentane quinone, and hexamethylene quinone.肼, 庚 醯肼, 1,4-cyclohexane hydrazine, bismuth tartrate, diterpene malate, diimine diacetate, N, N / - hexamethylene diamine gland (N,N / -hexamethylene bissemicarbazide ), bismuth citrate tris, trimethyl phthalic acid triterpene, cyclohexane tricarboxylic acid triterpenoid, 1,3-bis(carboxhydrylethyl)-5-isopropyl The ketones and the like include a diterpenoid having a skeleton of the glutamate endogenous gland. 19 323208 201204749 From the standpoint of the balance between hardenability and latent potential, it is more preferable to use a divalent quinone having two carboxyl groups on a C3 to C6 hydrocarbon. It is also better to use dipyridamole or isophthalic acid dioxime. In addition, depending on the situation, it is better to be better. When the thermal curing agent (f) is used, when the epoxy equivalent of the epoxy group of the epoxy resin (e) is 1, it is preferably about 〇5 to 2.0 equivalents, more preferably about 0.8 to 1.2 equivalents. . In the liquid crystal sealing agent of the present invention, when the Shixiyuan coupling agent (g) is used, the adhesion strength and moisture resistance can be further improved. Examples of the dream-burning coupling agent include, for example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyl-decyldimethoxy sulphide, and 3-shrinkage. Glyceroxypropylmethyldimethoxy-infraline, 2-(3,4-epoxycyclohexyl)ethyltrimethoxynonane, N-phenyl-τ-aminopropyldimethoxydecane, Ν·(2-Aminoethyl)3-aminopropylmethyldidecyldecane, Ν-(2-aminoethyl)3-aminopropylmercaptotrimethoxy decane, 3- Aminopropyltriethoxydecane, 3-mercaptopropyltrimethoxydecane, ethyltrimethoxysulfate, ruthenium (2-(vinyl albenyl)ethyl)ethyl) Internal group trimethoxy residual hydrochloride, 3-methylpropyl methoxy propyl trimethoxy sulphur, 3 · propyl propyl methyl dimethoxy sulphur, 3 chloropropyl trimethoxy sulphur Wait. Among them, glycidoxypropyl three C1 to C3 alkoxylate or glycidoxypropyl group to C3 alkyldiC1 to C3 alkoxylate is preferred. When the total amount of the liquid crystal sealing agent of the present invention is 10 G% by mass, the content of the copolymer (g) in the liquid crystal sealing agent is preferably 0.05 to 3% by mass. When the inorganic liquid filling 1 (h) is used in the liquid crystal sealing agent of the present invention,

323208 S 201204749 Bayeux. An example of the inorganic filler (h) is a crystalline cerium oxide, cerium carbide, cerium nitride, cerium

Improve adhesion strength and moisture resistance. For example, when the molten oxidized oxide is used, the average particle size of the crystallization is too large, and the gap between the upper and lower substrates when the liquid crystal cell having a small gap is formed is not formed, and the gap is not formed smoothly. Therefore, it is 3/zm or less. Good, 2#m or less is better. The particle size can be measured by a laser diffraction/scattering particle size distribution measuring apparatus (dry type) (manufactured by SEISHIN Co., Ltd.; LMS-30). The inorganic filler (1, in the liquid crystal sealing agent) used in the liquid crystal sealing agent of the present invention is generally 1 to 6 Å in mass when the total amount of the liquid crystal sealing agent of the present invention is 100% by mass. % is preferably 20 to 50% by mass. When the content of the inorganic filler is too small, the adhesion strength to the glass substrate is lowered, and the moisture resistance is also deteriorated, so that the adhesion strength after moisture absorption is also lowered. When the content of the inorganic filler is too large, there is a case where the liquid crystal cell is not easily crushed and the liquid crystal cell is not formed. In the liquid crystal sealing agent of the present invention, the organic filler may be further formulated according to the needs thereof. And pigments, leveling agents, defoamers, solvents, etc. 21 323208 201204749 Additives. The preferred liquid crystal sealants of this month can be summarized as follows: 1 ·- kinds of liquid crystal sealants, including (four) to 5 % by mass of the aforementioned photosensitizer ^a) and 3G to 8% by mass of the aforementioned curable resin (1), and the package 3 is known from (d) photopolymerization initiator, (e) epoxy resin and (7) heat modification And (g) 11 smouldering agents are grouped in la Selection of at least one as the rest. 2. The liquid crystal sealing agent according to the above 1, which comprises 0.01 to 5% by mass of (d) a photopolymerization initiator. 3' The liquid crystal sealing agent according to the above 1 or 2, which comprises i to 3 〇 Θ曰 (6) epoxy resin, and 0.5 to 2 equivalents relative to the epoxy group in the epoxy resin. The proportion of (f) thermal hardener. The liquid crystal sealing agent according to any one of the above 1 to 3, wherein the liquid crystal sealing agent 3 is 〇5 to 3% by mass of the (g) decane coupling agent. The liquid crystal sealing agent according to any one of the above 1 to 4, which contains 10 to 60% by mass of (h) an inorganic filler. The liquid crystal sealing agent according to any one of the above 1 to 5, wherein the liquid crystal sealing agent is 6% by mass, more preferably δ.1 to 5% by mass of the third stage: (c) compound. The liquid crystal sealing agent according to any one of the above-mentioned items 1 to 6, wherein the photosensitizer (a) is a reaction product of a sulfur (tetra) (tetra)-axis (methyl) acid glycidyl ester compound, or 4_C1 to C4. Alkoxy-propylene oxy is a -ethoxy)naphthalene (wherein R1 represents a hydrogen atom or α·;) C2 alkyl). 323208

S 22 201204749 8. As in the above 1 to 7 _ _ a soil secret 丨,, the liquid crystal sealant described in the item, i, narrate the sensitizer U) is selected from the group before At least one of the compounds represented by the formulae (1) to (1). The liquid crystal sealing agent as described in the above paragraphs 1 to 8 and the hardening resin (b) in the case of JL is a ring-shaped milk (methyl) propyl group. An acid ester. The liquid crystal sealing agent acrylate according to the above 9 is resorcinol methyl) glycidyl ether and (meth)acrylic acid 苻. In the liquid crystal sealing agent according to any one of the above items 1 to 10, (4) the photopolymerization initiator is as shown in the above formula (Α'). , base) acrylonitrile-based photopolymerization initiator. 13. As above! The liquid crystal sealing agent according to any one of the preceding claims, wherein the (f) thermal curing agent is diterpene. Eight

The liquid crystal sealing agent according to any one of the above-mentioned items, wherein the third-order amine compound is a C1 to C3 alkyl group of two of 21 to 23 in the above formula (4). The lyophile, and the remaining material may have an amine of a phenyl group of a Q to C6 aerobic group or a substituent such as C1 to C3. The liquid crystal sealing agent of the present invention can be produced by the following process. First, at (1) In the composition, the epoxy resin (4) and/or the Shixia Hyun coupling agent (g) are dissolved and mixed as needed. Secondly, the photosensitizer (1) 323208 23 201204749 and, if necessary, the photopolymerization initiator (d) are dissolved. Thereafter, a thermal hardener (f), and/or an inorganic filler (h), and an organic filler, an antifoaming agent, and a leveling agent, a solvent, etc., as needed, are further added as needed, and are generally known to be mixed. The liquid crystal sealing agent of the present invention can be prepared by mixing a device such as a triaxial mixer, a sand mixer, a ball mill, etc., and then filtering through a metal sieve. The liquid crystal display unit of the present invention will have a predetermined electrode formed on the substrate. a pair of substrates are disposed opposite each other at a predetermined interval, and are surrounded by the present invention The liquid crystal sealing agent is sealed, and then the liquid crystal is sealed in the gap. The type of the liquid crystal to be sealed is not particularly limited. Here, the substrate is made of glass, quartz, plastic, tantalum or the like and is light transmissive by at least one of them. In the liquid crystal sealing agent of the present invention, a spacer (gap control material) such as glass fiber is added to the liquid crystal sealing agent of the present invention, and then one of the pair of substrates is an applicator (diSpenser). Or applying the liquid crystal sealing agent to a screen printing device or the like, and then dropping liquid crystal into the inner side of the dam of the liquid crystal sealing agent, and overlapping the other glass substrate in a vacuum to form a space. The ultraviolet ray irradiator irradiates the liquid crystal sealing portion with ultraviolet rays to harden the light. The ultraviolet ray irradiation amount is preferably from 5 〇〇mj/cm 2 to 6000 mJ/cm, and is 1 〇〇〇 mJ/cm^4 〇〇〇. After mj/cm2 is better, after 90 to 13 as needed (TC hardens for 1 to 2 hours, the liquid crystal of the present invention can be obtained. The liquid 4 of the present invention produced by this operation* is not only 7G' Does not occur by liquid crystal stain The display is defective, and the adhesion and moisture resistance are also excellent. Examples of the spacer include glass fiber, cerium oxide beads, polymer beads, etc. The diameter varies depending on the purpose, and the slave is 2 to 8" m ' is preferably from 4 to 7. The amount of use is relatively high, in comparison with 24 323208 201204749, 100% by mass of the liquid crystal sealing agent of the present invention, generally 〇丨 to 4% by mass, more preferably 〇.5 to 2 〇/❶. More preferably, it is about 0.9 to 1.5 mass%. EXAMPLES Hereinafter, the present invention will be described in more detail based on examples, and the parts in the examples mean the parts by mass % means the mass %. Examples 1 to 6, Comparative Examples 1 to 2 (Preparation of a sealant for liquid crystal dropping process) After mixing and stirring each resin component in the ratio shown in the following Table 1, the photosensitizer (a) and photopolymerization initiator (d) are as needed. The tertiary amine is dissolved by heating. After that, a decane coupling agent, an inorganic filler (h), a thermal curing agent, and the like are appropriately added as needed, and after being stirred, they are dispersed in a triaxial mixer, and filtered through a metal sieve or the like to prepare a liquid crystal dropping process for sealing. Agents (Examples 1 to 6 and Comparative Examples 1 to 2). The contents and results of the evaluation items of the sealant for each liquid crystal dropping process prepared are shown below, and the results are shown in the table. Liquid crystal contamination test At the bottom of each 10 ml vial, liquid crystals which were irradiated with ultraviolet rays of 3000 mJ/cm 2 around i〇〇nlg were applied to the liquid crystal sealing agent for the process. Next, a liquid crystal (MLC-6866-100: manufactured by Merck Co., Ltd.) of 1 〇 of each of the applied sealants was added thereto. The obtained vial was heated and kept at 120 ° C for 1 hour, and then allowed to cool to room temperature over 30 minutes. The supernatant (liquid crystal) was separated by decantation and was measured by a digital ultra-high resistance meter (R834〇: Advantest 25 323208 201204749, manufactured by vant 敎 敎) The specific resistance of the value of the sealant is evaluated according to the following criteria. 〇10E+12 or more △ LOB+ii or more and not up to ι.0Ε+12 X is less than 1.0Ε+11 In addition, the ratio of “1.0Ε+12” of the specific resistance value means “Lowou” and his record also means the same meaning. . The specific resistance values in the respective examples are as follows. Example 1: 2.1E+12 Example 2: 1.6E+12 Example 3: 1.8E+12 Example 4: 7.3E+11 Example 5: 2.3E+12 Example 6: 6.2E+11 Shading The sclerosing test uses a glass substrate in which chrome-plated chrome-plated glass substrate is left in the center of the enamel line (width 0.8 cm), and each liquid crystal sealing agent (in the form of Table 1 is added: == The glass fiber is coated in a circular shape, and the black base substrate is bonded as a counter substrate, and fixed by a clip (dip) to form a light-shielding portion as shown in FIG. Test sample. Each of the test samples was irradiated with ultraviolet rays of 3 〇〇〇 mJ/cm 2 from the side of the chrome-plated glass substrate to cure the sealant (as shown in 1-2 of Fig. 1). Thereafter, the bonded black matrix was peeled off, and the portion of the chrome-plated portion 323208 26 201204749 was observed under a microscope, and the hardened width of the light-shielding portion was measured. Contact strength test 1 g of 5 // m glass fiber was added to a 100 g liquid crystal sealant as a spacer, followed by mixing and stirring. The liquid crystal sealing agent was coated on a glass substrate of 50 mm×50 mm, and a glass piece of 1.5 mm×1.5 mm was adhered to the liquid crystal sealing agent, and irradiated with ultraviolet rays of 3000 mJ/cm 2 by UV irradiation, and then placed in 120 It is hardened in an oven at °C for 1 hour. The shear strength of the glass piece was measured by a bond tester (SS-30WD: manufactured by Xijin Commercial Co., Ltd.). 27 323208 201204749 [Table i] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Component (8) 1 Glycidyl methacrylate and thioxanthone-2-carboxylic acid Reaction product 3 parts 3 parts 3 parts 3 parts 3 parts 2 4-decyloxy-1-(2-propenyloxypropyloxy) oxime 3 parts diethyl thioxanthone 3 parts (b) Reaction product of 4 stilbene diglycidyl diglycidyl ether with acrylic acid 80 parts 80 parts 80 parts 80 parts 80 parts 80 parts 80 parts 5 parts Bisphenol A type epoxy acrylate 80 parts 4-diethylamine stupid Ethyl formate 3 parts 7 2,2-dimethoxyoxy-1,2-diphenylethhen-1-one 3 parts 3 parts 8 b J 9 2-mercaptopropenyloxyethyl isocyanate and 1- Reaction product of [Φ(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propen-1-one: 3 parts 3 parts 3 parts 3 parts bisphenol oxime type epoxy Resin 20 parts 20 parts 20 parts 20 parts 20 parts 20 parts 20 parts 20 parts Dimethoate 5 parts 5 parts 5 parts 5 parts 5 parts 5 parts 5 parts 5 parts 11 3-glycidoxypropyl trioxane Base decane 1.5 1.5 parts 1.5 parts 1.5 parts 1.5 parts 1.5 parts 1.5 parts 1.5 parts 12 bismuth oxide 30 parts 30 parts 30 parts 30 parts 30 parts 30 parts 30 parts 30 parts liquid crystal contamination 〇〇〇 Δ Δ X 〇 shading hardenability 120 "m 120 (/m 100 /zm 150 90 fim 120 120 {im 50 um, then strength 62 MPa 63 MPa 65 MPa 63 MPa 60 MPa 60 MPa 62 MPa 61 MPa 1) Example 1 of JP-A-2004-224993 The compound of the formula (1) synthesized by the method described in the following is a compound of the formula (2) synthesized by the method described in Example 1 of JP-A-2008-1640, SPEEDCURE DETX (manufactured by LAMBSON Co., Ltd.) 4 Japanese Patent No. 392149 Synthesis method 5 YD-8125 (manufactured by Nippon Steel Chemical Co., Ltd.) and acrylic acid reaction product 323208

S 28 201204749 © KAYACURE EPA (manufactured by Sakamoto Chemical Co., Ltd.) 7 Irgacure-651 (manufactured by BASF Corporation) 8 Synthesized 9 YD-8125 by the method disclosed in International Publication WO2006/027982 (manufactured by Shinkai Iron Chemical Co., Ltd.) 10 ADH-S (manufactured by Otsuka Chemical Co., Ltd.) 11Sila-Ace S-510 (manufactured by Chisso Co., Ltd.) 12ADMAFINE SEZ (manufactured by Admatech Co., Ltd.) As apparent from the above, the liquid crystal sealing agent of the present invention is not in the outer line. The light-shielding portion that directly illuminates has a good hardenability even under light energy such as light leakage, so that the range of the design of the liquid crystal panel can be expanded, and the reliability can be improved. ° [Industrial Applicability] Since the liquid crystal sealing agent of the present invention has less liquid crystal contamination, and also has a wide width, the light-shielding portion which is not directly irradiated with ultraviolet rays is hardened to cause a shadow in the distribution line. Directly rubbing the ultraviolet light or the like, the sealant is completely hardened in the same manner, and the strength of the hardened agent is also good. S1 is very useful as a liquid crystal seal. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a diagram of a sample for a hardening test of a light-shielding portion, in which μ to i are viewed from above, and the state of the sample before the hardening is L-shaped; The figure (1_2) of the sample for the purpose of curing the ultraviolet ray in the direction of the ultraviolet ray, and the figure (1-3) showing the curing condition of the liquid crystal sealing agent after curing the liquid crystal sealing agent. 323208 29 201204749 [Description of main component symbols] 1 Black base substrate 1-1 Figure 1-2 of the light-shielding-hardening test sample before the sealant hardening is viewed from above. -3 shows the hardening state of the liquid crystal sealing agent of the sample for the light-shielding hardening test after the sealant is hardened. FIG. 2 shows the chrome-plated layer 3 on the surface of the substrate which is etched by chrome plating. Liquid crystal sealant 5 liquid crystal Hardened portion of the sealant 6 Unhardened portion of the liquid crystal sealant 7 In the light-shielding portion under the chrome layer, the liquid crystal sealant has hardened part of the UV UV 30 323208

S

Claims (1)

201204749 VII. Patent application scope: 1. A liquid crystal sealing agent for liquid crystal dropping process, which comprises: (a) a photosensitizer having a (meth)acryl fluorenyl group in the molecule and (b) having a (fluorenyl) acryl group Curable resin. 2. The liquid crystal sealing agent for liquid crystal dropping process according to Item 1, wherein (a) the photosensitizer having a (fluorenyl) acrylonitrile group in the molecule is thioxanthone carboxylic acid (thioxanthone carboxylic acid). Acid) a reaction product with a (mercapto)acrylic glycidol vinegar compound or 4-C1 to C4 alkoxy-1-(2-(indenyl)propenyloxy-2-Rr ethoxy)naphthalene ( Wherein I represents a hydrogen atom or a C1 to C2 alkyl group). 3. The liquid crystal sealing agent for liquid crystal dropping process according to claim 1, wherein the (a) photosensitive agent having a (fluorenyl) acrylonitrile group in the molecule is at least the following formula (1) to (3) Any of the compounds shown: t 1 323208 201204749 Equation (3) 4. ^ The liquid crystal sealing agent for liquid crystal dropping process described in the item i of the patent application's further comprises (c) a tertiary amine compound. <The liquid crystal "liquid crystal sealing agent for process" as described in the patent application, which comprises (d) a photopolymerization initiator. 6. The liquid crystal drip process as described in claim 5 The liquid crystal sealing agent, wherein the photopolymerization initiator (d) is a photopolymerization initiator having a (meth) acrylonitrile group in the molecule. 7. The liquid crystal dropping process as described in claim 5 The liquid crystal sealing agent used in the liquid crystal instilling process of the liquid crystal instilling process as described in claim 5, wherein the liquid crystal sealing agent is the epoxy resin (meth) acrylate. The curable resin (b) is a reaction product of m-phenylene diglycidyl ether and acrylic acid. 9. The liquid crystal sealing agent for liquid crystal dropping process according to item 5 of claim 5, which comprises e) epoxy resin, (f) thermal hardener. 10. The liquid crystal sealing agent for liquid crystal dropping process according to claim 5, which further comprises (g) a decane coupling agent. Liquid crystal dense 323208 S for liquid crystal dropping process described in the fifth item 2 201204749 A sealing agent, which comprises (h) an inorganic filler. 12. The liquid crystal sealing agent for liquid crystal dropping process according to claim 1, wherein the liquid crystal sealing agent contains 〇 〇1 to 5% by mass of the aforementioned photosensitizer (a) and 30 to 80% by mass of the above-mentioned curable resin (b), which is a liquid crystal sealing agent for liquid crystal dropping process according to claim 12, And (d) a liquid crystal sealing agent for liquid crystal dropping process according to claim 13 of the invention, which further comprises from i to 30% by mass (e) Epoxy resin, and (f) a heat hardening agent with respect to the epoxy group equivalent in the epoxy resin. 15. The liquid crystal dropping process as described in claim 14 A liquid crystal sealing agent comprising a G.G 5 to 3 mass% (g) Wei coupling agent and 10 to 60 mass% of (h) an inorganic filler. W. The liquid crystal droplet as described in claim S 15 A liquid crystal sealing agent for a human process, which comprises 0 to 6% by mass of a hydrazine tertiary amine compound. The crystal display unit is sealed by a cured product obtained by hardening a liquid crystal sealing agent for a liquid crystal dropping process as described in any one of the above-mentioned claims.