JP2006195450A - Resin composition for liquid crystal panel, and color filter and liquid crystal panel using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition for liquid crystal panel capable of simultaneously solving the occurrence of uneven coating and the occurrence of uneven drying, and to provide a color filter and a liquid crystal panel using the resin composition. <P>SOLUTION: The resin composition for liquid crystal panel comprises a binder resin, a surfactant and a solvent, wherein the contact angle θ(degree) of a droplet of the resin composition with a clean glass surface and the surface tension σ(mN/m) of the resin composition satisfy the following formulas (1), (2) and (3); θ≤5×(σ<SB>0</SB>-σ) (1), σ≤σ<SB>0</SB>-1 (2), θ≤15 (3). The color filer is formed by using the resin composition for liquid crystal panel and the liquid crystal panel is formed by using the resin composition for liquid crystal panel. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a resin composition for a liquid crystal panel, and a color filter and a liquid crystal panel using the same.

  Conventionally, in manufacturing a liquid crystal panel, a pixel, a black matrix, a photo spacer, a rib material (liquid crystal division alignment protrusion), an overcoat, and the like, which are parts of the liquid crystal panel, are formed by the following procedure. That is, (1) A liquid crystal panel resin composition containing a photosensitive component, a binder resin, a color material, a solvent, and the like is applied to a substrate. (2) The coating film of the resin composition is dried to form a resin composition layer. (3) The resin composition layer is exposed and developed to form a resist image for a liquid crystal panel.

  In the processes (1) and (2), the occurrence of coating unevenness in the application of the resin composition to the substrate becomes a problem. In order to prevent this, means for adding various surfactants has been adopted. For example, especially in the die coating method, since the resin composition has a low solid content concentration and low viscosity, “drying unevenness” such as pin marks, Benard cell, blown rough, yuzu skin, maragony, and edge bulge (frame) occurs. easy. On the other hand, measures such as increasing the amount of the surfactant added or using a surfactant having a high surface tension reducing ability are employed. However, these dry unevenness preventing means, on the other hand, cause “coating unevenness” of the resin composition. Such coating unevenness is, for example, lateral unevenness, streak unevenness, thin spot, streak, or the like that occurs when the wettability of the resin composition with respect to the glass substrate deteriorates or the leveling property deteriorates. These coating unevenness and drying unevenness are in a trade-off relationship, and it is difficult to prevent the occurrence of both unevenness at the same time.

On the other hand, for example, in Patent Document 1, as a surfactant contained in the color filter polymerizable composition, a silicon-based surfactant having a phenyl group and a molecular weight of 3,000 to 4,000 is used. It is supposed that it is possible to prevent the formation of a horn-shaped thick film portion at the end of the coating surface during slit coating. However, according to the study by the present inventor, it has been found that simply using the above-mentioned silicon-based surfactant is insufficient for preventing uniform occurrence of unevenness including other types of unevenness. Further, for example, in Patent Document 2, it is said that good coating property can be realized in a spinless coater by setting the surface tension of the colored photosensitive resin composition to 25.5 mN / m or more and 29.0 mN / m or less. However, according to the study of the present inventor, simply defining the surface tension within a specific range is not sufficient to solve the problem of the wettability with the glass surface, particularly the liquid breakage characteristic of the spinless coater. There was found.
JP 2004-29261 A JP 2004-126549 A

  The present invention has been made in view of the above-described prior art, and provides a resin composition for a liquid crystal panel capable of simultaneously solving the occurrence of coating unevenness and drying unevenness, and a color filter and a liquid crystal panel using the same. For the purpose.

As a result of diligent research to solve the above problems, the present inventor has particularly selected the type, amount, combination, etc. of the binder resin, surfactant and solvent, and the hydrophilicity / hydrophobicity and lipophilicity of the surfactant. The present invention has found that a resin composition having a specific relationship between a contact angle with a glass surface and a surface tension can solve the above problems by adjusting the oleophobicity, the balance between the molecular weight and the polarity of the solvent. It has been reached. Therefore, the gist of the present invention is as follows.
(I) A resin composition for a liquid crystal panel comprising a binder resin, a surfactant, and a solvent, wherein a contact angle θ (degree) of a droplet of the resin composition with respect to a clean glass surface, and the surface of the resin composition A resin composition for a liquid crystal panel, wherein the tension σ (mN / m) satisfies the following formulas (1), (2), and (3):

θ ≦ 5 × (σ ₀ −σ) (1)
σ ≦ σ ₀ −1 (2)
θ ≦ 15 (3)
[In the above formula, σ ₀ is the surface tension (mN / m) of the solvent alone used in the resin composition. ]
(Ii) A color filter formed using the resin composition for a liquid crystal panel described in (i).
(Iii) A liquid crystal panel formed by using the liquid crystal panel resin composition described in (i).

  ADVANTAGE OF THE INVENTION According to this invention, the resin composition for liquid crystal panels which can solve simultaneously generation | occurrence | production of a coating nonuniformity and a dry nonuniformity, a color filter using the same, and a liquid crystal panel can be provided.

[1. Resin composition for liquid crystal panel]
The resin composition for a liquid crystal panel containing the binder resin, surfactant and solvent of the present invention preferably contains a photopolymerizable monomer and a photopolymerization initiation system as a photosensitive component. Further, it contains a coloring material, a dispersing agent, other components and the like as necessary. Below, the structural component of the resin composition for liquid crystal panels of this invention is demonstrated.
[1-1. (Photopolymerizable monomer)
The resin composition for a liquid crystal panel of the present invention preferably contains a photopolymerizable monomer. The photopolymerizable monomer is not particularly limited as long as it is a low molecular weight compound that can be polymerized, but it may be an addition-polymerizable compound having at least one ethylenic double bond (hereinafter referred to as “ethylenic compound”). Is preferred). The ethylenic compound is a compound having an ethylenic double bond that undergoes addition polymerization and cures by the action of a photopolymerization initiation system described later when the resin composition for a liquid crystal panel of the present invention is irradiated with actinic rays. is there. In addition, the monomer in this invention means the concept opposite to what is called a polymeric substance, and also contains a dimer, a trimer, and an oligomer other than a monomer in a narrow sense.

  Examples of the ethylenic compound include unsaturated compounds such as (meth) acrylic acid (in the present invention, “(meth) acryl” means “acryl” and / or “methacryl”). Carboxylic acid, ester of monohydroxy compound and unsaturated carboxylic acid, ester of aliphatic polyhydroxy compound and unsaturated carboxylic acid, ester of aromatic polyhydroxy compound and unsaturated carboxylic acid, unsaturated carboxylic acid and polyvalent Urethane obtained by reacting a carboxylic acid and an ester, polyisocyanate compound and a (meth) acryloyl group-containing hydroxy compound obtained by an esterification reaction with a polyvalent hydroxy compound such as the above-mentioned aliphatic polyhydroxy compound and aromatic polyhydroxy compound. Examples include ethylenic compounds having a skeleton.

Esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate , Pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) Examples include (meth) acrylic acid esters such as acrylate and glycerol (meth) acrylate. Moreover, itaconic acid ester in which the (meth) acrylic acid portion of these acrylates is replaced with itaconic acid portion, crotonic acid ester in which crotonic acid portion is replaced, or maleic acid ester in which maleic acid portion is replaced. Examples of the ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include hydroquinone di (meth) acrylate, resorcin di (meth) acrylate, pyrogallol tri (meth) acrylate and the like. The ester obtained by the esterification reaction of an unsaturated carboxylic acid with a polyvalent carboxylic acid and a polyvalent hydroxy compound is not necessarily a single substance but may be a mixture. Representative examples are condensates of (meth) acrylic acid, phthalic acid and ethylene glycol, condensates of (meth) acrylic acid, maleic acid and diethylene glycol, condensation of (meth) acrylic acid, terephthalic acid and pentaerythritol. Products, (meth) acrylic acid, adipic acid, butanediol, and glycerin condensates.

  Examples of the ethylenic compound having a urethane skeleton obtained by reacting a polyisocyanate compound with a (meth) acryloyl group-containing hydroxy compound include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; alicyclic rings such as cyclohexane diisocyanate and isophorone diisocyanate. Formula diisocyanates; aromatic diisocyanates such as tolylene diisocyanate and diphenylmethane diisocyanate, and (meth) such as 2-hydroxyethyl (meth) acrylate and 3-hydroxy [1,1,1-tri (meth) acryloyloxymethyl] propane A reaction product with an acryloyl group-containing hydroxy compound is exemplified.

In addition, examples of the ethylenic compound used in the present invention include (meth) acrylamides such as ethylene bis (meth) acrylamide; allyl esters such as diallyl phthalate; vinyl group-containing compounds such as divinyl phthalate. .
The ethylenic compound may be a monomer having an acid value. The monomer having an acid value is, for example, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound. A polyfunctional monomer having an acid group is preferred, and in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol. One of these monomers may be used alone, but since it is difficult to obtain a single compound in production, two or more of these monomers may be mixed and used. Moreover, you may use together the polyfunctional monomer which does not have an acid group as a monomer, and the polyfunctional monomer which has an acid group as needed.

A preferable acid value of the polyfunctional monomer having an acid group is 0.1 to 40 mg · KOH / g, and particularly preferably 5 to 30 mg · KOH / g. If the acid value of the polyfunctional monomer is too low, the developing dissolution properties are lowered, and if it is too high, the production and handling are difficult, the photopolymerization performance is lowered, and the curability such as the surface smoothness of the pixel is deteriorated. Accordingly, when two or more polyfunctional monomers having different acid groups are used in combination, or when a polyfunctional monomer having no acid group is used in combination, the acid groups as the entire polyfunctional monomer are within the above range. It is preferable to adjust so that it may enter. In the present invention, more preferred polyfunctional monomers having an acid group are dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentaacrylate which are commercially available as “TO1382” manufactured by Toagosei Co., Ltd. It is a mixture mainly composed of an acid ester. A combination of this polyfunctional monomer and another polyfunctional monomer can also be used.

In the resin composition for a liquid crystal panel of the present invention, the content ratio of these ethylenic compounds is the total solid content [in the present invention, the “total solid content” is a resin composition for a liquid crystal panel other than the solvent described later. All ingredients in it shall be said. ], Usually 0% by weight or more, preferably 5% by weight or more, more preferably 10% by weight or more, and usually 80% by weight or less, preferably 70% by weight or less, more preferably 50% by weight or less, Preferably it is 40 weight% or less. The ratio to the colorant described later is usually 0% by weight or more, preferably 5% by weight or more, more preferably 10% by weight or more, particularly preferably 20% by weight or more, and usually 200% by weight or less, preferably Is 100% by weight or less, more preferably 80% by weight or less.
[1-2. Photopolymerization initiation system)
The resin composition for a liquid crystal panel of the present invention preferably contains a photopolymerization initiation system. The photopolymerization initiation system is usually used as a mixture of a photopolymerization initiator and an additive such as a sensitizing dye and a polymerization accelerator that are added as necessary, and directly absorbs light or is photosensitized. It is a component having a function of generating a polymerization active radical by causing a decomposition reaction or a hydrogen abstraction reaction.

  Examples of the photopolymerization initiator constituting the photopolymerization initiation system include titanocene derivatives described in JP-A Nos. 59-152396 and 61-151197, JP-A-10-300922, Hexaarylbiimidazole derivatives described in JP-A Nos. 11-174224 and 2000-56118, halomethylated oxadiazole derivatives and halomethyl-s-triazine derivatives described in JP-A-10-39503, etc. , Radical activators such as N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acid salts, N-aryl-α-amino acid esters, α-aminoalkylphenone derivatives, Examples thereof include oxime ester derivatives described in Japanese Utility Model Publication No. 2000-80068.

  Specifically, for example, titanocene derivatives include dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis (2,3,4,5,6-pentafluoro Phen-1 monoyl), dicyclopentadienyl titanium bis (2,3,5,6-tetrafluorophen-1-yl), dicyclopentadienyl titanium bis (2,4,6-trifluoropheny- 1-yl, dicyclopentadienyltitanium di (2,6-difluorophen-1-yl), dicyclopentadienyltitanium di (2,4-difluorophen-1-yl), di (methylcyclopentadi Enyl) titanium bis (2,3,4,5,6-pentafluorophen-1-yl), di (methylcyclo Tantadienyl) titanium bis (2,6-difluorophen-1-yl), dicyclopentadienyltitanium [2,6-di-fluoro-3- (pyro-1-yl) -phen-1-yl] and the like In addition, biimidazole derivatives include 2- (2′-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (2′-chlorophenyl) -4,5-bis (3′-methoxy). Phenyl) imidazole dimer, 2- (2′-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (2′-methoxyphenyl) -4,5-diphenylimidazole dimer, (4 '-Methoxyphenyl) -4,5-diphenylimidazole dimer and the like, and halomethylated oxadiazole derivatives include 2-trichloromethyl-5- (2'-benzo Ryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- [β- (2′-benzofuryl) vinyl] -1,3,4-oxadiazole, 2-trichloromethyl-5- [ β- (2 ′-(6 ″ -benzofuryl) vinyl)]-1,3,4-oxadiazole, 2-trichloromethyl-5-furyl-1,3,4-oxadiazole, etc. Examples of halomethylated triazine derivatives include 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl)- s-triazine, 2- (4-ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -s-to Riazine and the like, and α-aminoalkylphenone derivatives include 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1 -(4-morpholinophenyl) -butanone-1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 4-dimethylaminoethylbenzoate, 4-dimethyl Aminoisoamyl benzoate, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino- 3- (4-Diethylaminobenzoyl) coumarin, 4- (diethylamino) cal As oxime ester derivatives, 1,2-octanedione, 1- [4- (phenylthio) phenyl], 2- (o-benzoyloxime), ethanone, 1- [9-ethyl- 6- (2-methylbenzoyl) -9H-carbazol-3-yl], 1- (o-acetyloxime) and the like.

  In addition, benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, benzoin isopropyl ether; 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone, etc. Anthraquinone derivatives; benzophenone derivatives such as benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone; 2,2-dimethoxy-2 -Phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-me Ruphenylpropanone, 1-hydroxy-1-methylethyl- (p-isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl- (4′-methylthiophenyl) -2- Acetophenone derivatives such as morpholino-1-propanone and 1,1,1-trichloromethyl- (p-butylphenyl) ketone; thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethyl Thioxanthone derivatives such as thioxanthone, 2,4-diethylthioxanthone, and 2,4-diisopropylthioxanthone; Benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate; 9-phenylacridine, 9- (P Metoki Examples thereof include acridine derivatives such as (cyphenyl) acridine; phenazine derivatives such as 9,10-dimethylbenzphenazine; and anthrone derivatives such as benzanthrone.

  Examples of the polymerization accelerator used as necessary include N, N-dialkylaminobenzoic acid alkyl esters such as N, N-dimethylaminobenzoic acid ethyl ester; 2-mercaptobenzothiazole, 2-mercaptobenzo Examples include mercapto compounds having a heterocyclic ring such as oxazole and 2-mercaptobenzimidazole, and mercapto compounds such as aliphatic polyfunctional mercapto compounds. Each of these photopolymerization initiators and polymerization accelerators may be used alone or in combination of two or more.

  In the resin composition for a liquid crystal panel of the present invention, the content ratio of these photopolymerization initiation systems is usually 0.1% by weight or more, preferably 0.5% by weight or more, and usually 40% by weight in the total solid content. Hereinafter, it is preferably 30% by weight or less. If this content is extremely low, the sensitivity to exposure light may be reduced. On the other hand, if it is extremely high, the solubility of the unexposed portion in the developer may be reduced, leading to poor development.

Moreover, as a sensitizing dye used according to the wavelength of the image exposure light source for the purpose of increasing the sensitivity as required, xanthene dyes described in JP-A-4-221958, JP-A-4-219756, etc. And coumarin dyes having a heterocyclic ring described in JP-A-3-239703, JP-A-5-289335, etc., and 3-ketocoumarin described in JP-A-3-239703, JP-A-5-289335, etc. Dyes, pyromethene dyes described in JP-A-6-19240, JP-A-47-2528, JP-A-54-155292, JP-B-45-37377, JP-A-48-84183, Japanese Utility Model Laid-Open Nos. 52-112681, 58-153503, 60-88005, 59-56403, 2-69, 57-16808 No., JP-A-5-107761, JP-A-5-210240, it may be mentioned dyes having a dialkyl aminobenzene skeleton described in JP-A 4-288818 Patent JP-like.

  Among these sensitizing dyes, preferred are amino group-containing sensitizing dyes, and more preferred are compounds having an amino group and a phenyl group in the same molecule. Particularly preferred are, for example, 4,4′-dimethylaminobenzophenone, 4,4′-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4′-diaminobenzophenone, 3,3′-diaminobenzophenone. Benzophenone compounds such as 3,4-diaminobenzophenone; 2- (p-dimethylaminophenyl) benzoxazole, 2- (p-diethylaminophenyl) benzoxazole, 2- (p-dimethylaminophenyl) benzo [4,5 Benzoxazole, 2- (p-dimethylaminophenyl) benzo [6,7] benzoxazole, 2,5-bis (p-diethylaminophenyl) -1,3,4-oxazole, 2- (p-dimethylaminophenyl) ) Benzothiazole, 2- (p- Ethylaminophenyl) benzothiazole, 2- (p-dimethylaminophenyl) benzimidazole, 2- (p-diethylaminophenyl) benzimidazole, 2,5-bis (p-diethylaminophenyl) -1,3,4-thiadiazole, (P-dimethylaminophenyl) pyridine, (p-diethylaminophenyl) pyridine, (p-dimethylaminophenyl) quinoline, (p-diethylaminophenyl) quinoline, (p-dimethylaminophenyl) pyrimidine, (p-diethylaminophenyl) pyrimidine P-dialkylaminophenyl group-containing compounds such as Of these, 4,4'-dialkylaminobenzophenone is most preferred. A sensitizing dye may also be used individually by 1 type, and 2 or more types may be mixed and used for it.

In the resin composition for a liquid crystal panel of the present invention, the content ratio of these sensitizing dyes is usually 0% by weight or more, preferably 0.2% by weight or more, more preferably 0.5% by weight or more in the total solid content. Moreover, it is usually 20% by weight or less, preferably 15% by weight or less, and more preferably 10% by weight or less.
[1-3. Color material)
The resin composition for a liquid crystal panel of the present invention contains a color material as required (for example, when used for applications of pixels and black matrix). As the color material, a pigment or a dye can be used, but a pigment is preferable from the viewpoint of heat resistance, light resistance, and the like. As the pigment, pigments of various colors such as a red pigment, a blue pigment, a green pigment, a yellow pigment, a purple pigment, an orange pigment, and a brown pigment can be used. The chemical structure includes organic pigments such as azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, and perylene. In addition, various inorganic pigments can be used. Hereinafter, specific examples of usable pigments are indicated by pigment numbers. The following “CI” means a color index (CI).

  Examples of red pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 1 9, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276. Of these, C.I. I. Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, more preferably C.I. I. Pigment red 177, 209, 224, 254.

  Examples of blue pigments include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79. Of these, C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, and more preferably C.I. I. Pigment Blue 15: 6.

Examples of green pigments include C.I. I. Pigment green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55. Of these, C.I. I. Pigment Green 7 and 36.
Examples of yellow pigments include C.I. I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 17 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202 , 203, 204, 205, 206, 207, 208. Of these, C.I. I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, and more preferably C.I. I. Pigment yellow 83, 138, 139, 150, 180.

  Examples of purple pigments include C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50. Of these, C.I. I. Pigment violet 19 and 23, and more preferably C.I. I. Pigment Violet 23.

  Examples of orange pigments include C.I. I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79. Of these, C.I. I. Pigment oranges 38 and 71.

Examples of the inorganic pigment include barium sulfate, lead sulfate, titanium oxide, yellow lead, red iron oxide, chromium oxide and the like.
A plurality of the above-mentioned various pigments can be used in combination. For example, in order to adjust the chromaticity, a green pigment and a yellow pigment can be used in combination, or a blue pigment and a violet pigment can be used in combination. The average particle size of these pigments is usually 1 μm or less, preferably 0.5 μm or less, more preferably 0.25 μm or less. Moreover, it is 0.001 micrometer or more normally, Preferably it is 0.005 micrometer or more.

Examples of the dye that can be used as the colorant include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.
Examples of the azo dye include C.I. I. Acid Yellow 11, C.I. I. Acid Orange 7, C.I. I. Acid Red 37, C.I. I. Acid Red 180, C.I. I. Acid Blue 29, C.I. I. Direct Red 28, C.I. I. Direct Red 83, C.I. I. Direct Yellow 12, C.I. I. Direct Orange 26, C.I. I. Direct Green 28, C.I. I. Direct Green 59, C.I. I. Reactive Yellow 2, C.I. I. Reactive Red 17, C.I. I. Reactive Red 120, C.I. I. Reactive Black 5, C.I. I. Disperse Orange 5, C.I. I. Disperse thread 58, C.I. I. Disperse blue 165, C.I. I. Basic Blue 41, C.I. I. Basic Red 18, C.I. I. Molded Red 7, C.I. I. Moldant Yellow 5, C.I. I. Examples thereof include Moldant Black 7.

Examples of anthraquinone dyes include C.I. I. Bat Blue 4, C.I. I. Acid Blue 40, C.I. I. Acid Green 25, C.I. I. Reactive Blue 19, C.I. I. Reactive Blue 49, C.I. I. Disperse thread 60, C.I. I. Disperse Blue 56, C.I. I. Disperse Blue 60 etc. are mentioned.
Examples of phthalocyanine dyes include C.I. I. Pad Blue 5 and the like are quinone imine dyes such as C.I. I. Basic Blue 3, C.I. I. Basic Blue 9 and the like are quinoline dyes such as C.I. I. Solvent Yellow 33, C.I. I. Acid Yellow 3, C.I. I. Disperse Yellow 64 and the like are nitro dyes such as C.I. I. Acid Yellow 1, C.I. I. Acid Orange 3, C.I. I. Disperse Yellow 42 and the like.

  Moreover, when forming the resin black matrix of a color filter using the resin composition for liquid crystal panels of this invention, a black color material can be used. The black color material may be a single black color material or a mixture of red, green, blue, and the like. These color materials can be appropriately selected from inorganic or organic pigments and dyes. In the case of inorganic and organic pigments, the average particle size is preferably 1 μm or less, preferably 0.5 μm or less.

Examples of the black color material that can be used alone include carbon black, acetylene black, lamp black, bone black, graphite, iron black, aniline black, cyanine black, and titanium black. Among these, carbon black and titanium black are preferable from the viewpoints of light shielding rate and image characteristics.
Examples of carbon black include, for example, MA7, MA8, MA11, MA100, MA100R, MA220, MA230, MA600, # 5, # 10, # 20, # 25, # 30, # 32 as products manufactured by Mitsubishi Chemical Corporation. , # 33, # 40, # 44, # 45, # 47, # 50, # 52, # 55, # 650, # 750, # 850, # 950, # 960, # 970, # 980, # 990, # 1000, # 2200, # 2300, # 2350, # 2400, # 2600, # 3050, # 3150, # 3250, # 3600, # 3750, # 3950, # 4000, # 4010, OIL7B, OIL9B, OIL11B, OIL30B, OIL31B Etc. are products made by Degussa, such as Printex3, Printex3OP, Printex30, P intex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, Printex A, Printex L, Printex G, Printex P, Printex U, Printex V, PrintexG, SpecialBlack550, SpecialBlack350, SpecialBlack250, SpecialBlack100, SpecialBlack6, SpecialBlack5, Special Black4, Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black W18, Color Black FW200, Color Black S160, Color Black S170, etc. are products manufactured by Cabot Corporation: Monarch120, Monarch280, Monarch460, Monarch800, Monarch880, Monarch900, Monarch1000, Monarch1000, Monarch1000, Monarch1000, MonL REGAL415R, REGAL250, REGAL250R, REGAL330, REGAL400R, REGAL55R0, REGAL660R, BLACK PEARLS480, PEARLS130, VULCAN XC72R, ELFTEX- 8 etc. are the products made by Colombian Carbon Co., Ltd. as Raven11, Raven14, Raven15, Raven16, Raven22Raven30, Raven35, Raven40, Raven410, Raven420, Raven450, Raven500, Raven780, Raven10R, Raven10R, Raven10H, Raven80H, Raven80H , RAVEN1170, RAVEN1190U, RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000 and the like. It is particularly preferable to use resin-coated carbon black for the production of a resin black matrix having a high optical density and a high surface resistivity.

  In addition, titanium black is obtained by a method in which a mixture of titanium dioxide and metal titanium is heated and reduced in a reducing atmosphere (Japanese Patent Laid-Open No. 49-5432), or by high-temperature hydrolysis of titanium tetrachloride. A method of reducing the obtained ultrafine titanium dioxide in a reducing atmosphere containing hydrogen (Japanese Patent Laid-Open No. 57-205322), a method of reducing titanium dioxide or titanium hydroxide at a high temperature in the presence of ammonia (Japanese Patent Laid-Open No. 60-65069). And a method of attaching a vanadium compound to titanium dioxide or titanium hydroxide and reducing it at high temperature in the presence of ammonia (Japanese Patent Laid-Open No. 61-201610). It is not limited to. Examples of commercially available titanium black include Titanium Black 10S, 12S, 13R, 13M, and 13M-C manufactured by Mitsubishi Materials Corporation.

  As another example of the black pigment, three color materials of red, green, and blue can be mixed and used as a black pigment. Color materials that can be mixed for preparing a black color material include Victoria Pure Blue (42595), Auramin O (41000), Catillon Brilliant Flavin (Basic 13), Rhodamine 6GCP (45160), Rhodamine B (45170). Safranin OK 70: 100 (50240), Erioglaucine X (42080), No. 120 / Lionol Yellow (21090), Lionol Yellow GRO (21090), Shimla First Yellow 8GF (21105), Benzidine Yellow 4T-564D (21095), Shimler First Red 4015 (12355), Lionol Red 7B4401 (15850), Fast Gen Blue TGR-L (74160), Lionol Blue SM (26150), Lionol Blue ES (Pigment Blue 15: 6), Lionogen Red GD (Pigment Red 168), Lionol Green 2YS (Pigment Green 36), etc. Is mentioned. The numbers in parentheses above indicate the color index (CI). Further, other pigments that can be used in combination are described in C.I. I. For example, C.I. I. Yellow pigments 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166, C.I. I. Orange pigments 36, 43, 51, 55, 59, 61, C.I. I. Red pigments 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, C.I. I. Violet pigments 19, 23, 29, 30, 37, 40, 50, C.I. I. Blue pigment 15, 15: 1, 15: 4, 22, 60, 64, C.I. I. Green pigment 7, C.I. I. Examples thereof include brown pigments 23, 25, and 26.

In the resin composition for a liquid crystal panel of the present invention, the content ratio of these coloring materials is usually 1% by weight or more, preferably 10% by weight or more, and usually 70% by weight or less, preferably 60% by weight in the total solid content. % Or less. If the ratio of the color material is too small, the film thickness with respect to the color density becomes too large, which adversely affects the gap control and the like when forming a liquid crystal cell. On the other hand, if the proportion of the color material is too large, sufficient image formability may not be obtained.
[1-4. (Dispersant)
The resin composition for liquid crystal panels of this invention contains the dispersing agent used as needed. The dispersant is not particularly limited, but a urethane-based dispersant is preferable, and the urethane-based dispersant includes a polyisocyanate compound, a compound having one or two hydroxyl groups in the same molecule, and the same molecule. A urethane resin obtained by reacting an active hydrogen with a compound having a tertiary amino group therein is particularly preferred.
Yes.

  Examples of the polyisocyanate compounds include aromatics such as paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, and tolidine diisocyanate. Aliphatic diisocyanate, hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate and other aliphatic diisocyanates, isophorone diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), ω, ω ' -Alicyclic diisocyanates such as diisocyanate dimethylcyclohexane, xylylene diisocyanate, α, α, α ', α'-tetramethyl Aliphatic diisocyanates having aromatic rings such as xylylene diisocyanate, and lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylene Examples include triisocyanates such as triisocyanate, bicycloheptane triisocyanate, tris (isocyanatephenylmethane), tris (isocyanatephenyl) thiophosphate, trimers thereof, water adducts, and polyol adducts thereof. Preferred as the polyisocyanate is a trimer of an organic diisocyanate, and most preferred is a trimer of tolylene diisocyanate and a trimer of isophorone diisocyanate, which may be used alone or in combination.

  As a method for producing an isocyanate trimer, the polyisocyanate may be converted into an isocyanate group using an appropriate trimerization catalyst such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylates and the like. And the trimerization is stopped by adding a catalyst poison, and then the unreacted polyisocyanate is removed by solvent extraction and thin-film distillation to obtain the desired isocyanurate group-containing polyisocyanate.

In addition, examples of the compound having one or two hydroxyl groups in the same molecule include polyether glycol, polyester glycol, polycarbonate glycol, polyolefin glycol, and the like, and one terminal hydroxyl group of these compounds is an alkyl group having 1 to 25 carbon atoms. And a mixture of two or more thereof.
Polyether glycols include polyether diols, polyether ester diols, and mixtures of two or more of these. As the polyether diol, those obtained by homopolymerizing or copolymerizing alkylene oxide, for example, polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol, And mixtures of two or more thereof. Examples of the polyether ester diol include those obtained by reacting a mixture of an ether group-containing diol or other glycol with a dicarboxylic acid or an anhydride thereof, or reacting polyester glycol with an alkylene oxide. (Polyoxytetramethylene) adipate and the like. Most preferred as the polyether glycol is polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, or a compound in which one terminal hydroxyl group of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms.

  Examples of the polyester glycol include dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, and phthalic acid, or anhydrides thereof, for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene. Glycol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,5-pentanediol, neo Pentyl glycol, 2-methyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentane Diol, 1,6-hexanediol, 2-methyl-2 4-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 1,8-octamethylene Aliphatic glycols such as glycol, 2-methyl-1,8-octamethylene glycol and 1,9-nonanediol, alicyclic glycols such as bishydroxymethylcyclohexane, aromatic glycols such as xylylene glycol and bishydroxyethoxybenzene , Obtained by polycondensation with a diol such as N-alkyldialkanolamine such as N-methyldiethanolamine, such as polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polyethylene / propylene adipate, etc. Diols or charcoal Polylactone diol or polylactone monool obtained by using a number from 1 to 25 monovalent alcohol as an initiator, for example, polycaprolactone glycol, polymethyl valerolactone, and mixtures of two or more thereof. Most preferred as the polyester glycol is a polycaprolactone glycol or polycaprolactone starting from an alcohol having 1 to 25 carbon atoms, more specifically, a compound obtained by ring-opening addition polymerization of ε-caprolactone to a monool. is there.

Examples of the polycarbonate glycol include poly (1,6-hexylene) carbonate and poly (3-methyl-1,5-pentylene) carbonate. Polyolefin glycols include polybutadiene glycol, hydrogenated polybutadiene glycol, hydrogenated polyisoprene glycol, and the like.
Of these compounds having one or two hydroxyl groups in the same molecule, polyether glycol and polyester glycol are particularly preferred. In addition, the number average molecular weight of the compound having one or two hydroxyl groups in the same molecule is usually 300 to 10,000, preferably 500 to 6,000, and more preferably 1,000 to 4,000.

  In the compound having an active hydrogen and a tertiary amino group in the same molecule, the active hydrogen, that is, a hydrogen atom directly bonded to an oxygen atom, a nitrogen atom, or a sulfur atom includes a hydroxyl group, an amino group, and a thiol. Examples thereof include a hydrogen atom in a functional group such as a group, and among them, an amino group, particularly a primary amino group hydrogen atom is preferable. As the tertiary amino group, for example, a dialkylamino group having an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, isopropyl, n-butyl, or the like, and the dialkylamino group are linked to form a heterocyclic structure. More specifically, an imidazole ring or a triazole ring can be mentioned. Among them, a dimethylamino group and an imidazole ring are preferable because of excellent dispersion stability.

  Examples of such compounds having an active hydrogen and a tertiary amino group in the same molecule include N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, N , N-dipropyl-1,3-propanediamine, N, N-dibutyl-1,3-propanediamine, N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N-dipropylethylenediamine, N, N -Dibutylethylenediamine, N, N-dimethyl-1,4-butanediamine, N, N-diethyl-1,4-butanediamine, N, N-dipropyl-1,4-butanediamine, N, N-dibutyl-1 , 4-butanediamine and the like.

  As the tertiary amino group is a nitrogen-containing heterocycle, pyrazole ring, imidazole ring, triazole ring, tetrazole ring, indole ring, carbazole ring, indazole ring, benzimidazole ring, benzotriazole ring, benzoxazole ring, benzo Examples thereof include nitrogen-containing hetero 5-membered rings such as thiazole ring and benzothiadiazole ring, nitrogen-containing hetero 6-membered rings such as pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, acridine ring and isoquinoline ring. Specific examples of these compounds having an imidazole ring and a primary amino group include 1- (3-aminopropyl) imidazole, histidine, 2-aminoimidazole, 1- (2-aminoethyl) imidazole and the like. It is done. Further, specific examples of the compound having a triazole ring and a primary amino group include 3-amino-1,2,4-triazole, 5- (2-amino-5-chlorophenyl) -3-phenyl-1H. -1,2,4-triazole, 4-amino-4H-1,2,4-triazole-3,5-diol, 3-amino-5-phenyl-1H-1,3,4-triazole, 5-amino Examples include -1,4-diphenyl-1,2,3-triazole and 3-amino-1-benzyl-1H-2,4-triazole. Among these, N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, 1- (3-aminopropyl) imidazole, 3-amino-1,2,4- Triazole and the like are preferable.

  The preferred use ratio of these urethane resin dispersant raw materials is that the compound having one or two hydroxyl groups in the same molecule is usually 10 to 200 parts by weight, preferably 20 to 190 parts by weight per 100 parts by weight of the polyisocyanate compound. Parts, more preferably 30 to 180 parts by weight, and the compound having an active hydrogen and a tertiary amino group in the same molecule is usually 0.2 to 25 parts by weight, preferably 0.3 to 24 parts by weight.

  The urethane resin dispersant is produced according to a known method for producing a urethane resin. As a solvent for production, usually, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, isophorone, esters such as ethyl acetate, butyl acetate, cellosolve acetate, benzene, toluene, xylene, hexane Hydrocarbons such as diacetone alcohol, isopropanol, secondary butanol, tertiary butanol, etc., halogenated hydrocarbons such as methylene chloride and chloroform, ethers such as tetrahydrofuran and diethyl ether, dimethylformamide An aprotic polar solvent such as N-methylpyrrolidone or dimethyl sulfoxide is used. Moreover, as a catalyst at the time of manufacture, a normal urethanization reaction catalyst is used. For example, tin such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate, stanas octoate, iron such as iron acetylacetonate and ferric chloride, tertiary amine such as triethylamine and triethylenediamine, etc. Can be mentioned. Further, the amount of the compound having an active hydrogen and a tertiary amino group in the same molecule is preferably controlled in the range of 1 to 100 mgKOH / g, more preferably 5 to 80 mgKOH, based on the amine value of the dispersion resin after the reaction. / G, more preferably in the range of 10-60 mg KOH / g. When the amine value is less than the above range, the dispersing ability tends to decrease, and when it exceeds the above range, the developability tends to decrease. In addition, when an isocyanate group remains in the dispersion resin by the above reaction, it is preferable to further crush the isocyanate group with an alcohol or an amino compound because the stability of the dispersion resin with time increases.

  The weight average molecular weight in terms of polystyrene measured by GPC of these urethane resin dispersants is usually 1,000 to 200,000, preferably 2,000 to 100,000, more preferably 3,000 to 50,000. Range. When the molecular weight is 1,000 or less, the dispersibility and dispersion stability are poor, and when it is 200,000 or more, the solubility is lowered and the dispersibility is deteriorated, and at the same time, the reaction is difficult to control.

In the resin composition for a liquid crystal panel of the present invention, the content of these dispersants is usually 10% by weight or more, preferably 20% by weight or more, and particularly preferably 30% by weight or more with respect to the color material component. Also, it is usually 300% by weight or less, preferably 100% by weight or less, particularly preferably 80% by weight or less. If the amount of the dispersant is too small, the adsorption to the coloring material is insufficient, aggregation cannot be prevented, and the viscosity may increase or gel, and conversely if too large, the film thickness becomes too thick, Since a cell gap control defect may occur in the liquid crystal cell forming process after the color filter is formed, neither is preferable.
[1-5. Binder resin)
The resin composition for a liquid crystal panel of the present invention contains a binder resin as an essential component. Examples of the binder resin include JP-A-7-207211, JP-A-8-259876, JP-A-10-300922, JP-A-11-140144, JP-A-11-174224, JP-A-2000-56118, and JP-A-2000-56118. Known polymer compounds described in JP-A-2003-233179 and the like can be used, and among them, a polymer compound not containing a nitrogen atom is preferable, and an epoxy group-containing (meth) acrylate of 5 to 90 mol% and An unsaturated monobasic acid is added to 10 to 100 mol% of the epoxy group of the copolymer with another radical polymerizable monomer 10 to 95 mol% which can be copolymerized, and further 10 to 10 of the resulting hydroxyl group. A resin obtained by adding a polybasic acid anhydride to 100 mol% is particularly preferred.

  Examples of the epoxy group-containing (meth) acrylate include glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. ) Acrylate glycidyl ether and the like, among which glycidyl (meth) acrylate is preferred. These epoxy group-containing (meth) acrylates may be used alone or in a combination of two or more.

  Moreover, as another radical polymerizable monomer that can be copolymerized with the epoxy group-containing (meth) acrylate, one or two mono (meth) acrylates having a structure represented by the following general formula (I): It is preferable to use the above.

[In the formula (I), R ^{1 to} R ⁶ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ⁷ and R ⁸ each independently represent a hydrogen atom or carbon number. 1 to 3 alkyl groups may be represented or linked to form a ring. ]
In the general formula (I), the ring formed by connecting R ⁷ and R ⁸ is preferably an aliphatic ring, which may be saturated or unsaturated, and has 5 to 6 carbon atoms. Preferably there is. Of these, the structure of the general formula (I) is preferably a structure represented by the following formula (Ia), (Ib), or (Ic). By introducing these structures into the binder resin, the heat resistance and strength of the liquid crystal panel resin composition can be increased. In addition, the mono (meth) acrylate which has these structures may be used individually by 1 type, and may mix and use 2 or more types.

  As the mono (meth) acrylate having the structure represented by the general formula (I), various known ones can be used as long as it has the structure represented by the general formula (I). Those represented by II) are preferred.

[In the formula (II), R ⁹ represents a hydrogen atom or a methyl group, and R ¹⁰ represents the structure of the general formula (I). ]
In the present invention, the copolymer of the epoxy group-containing (meth) acrylate and another radical polymerizable monomer copolymerizable therewith is derived from another copolymerizable monomer capable of copolymerization. Among the structural repeating units, it is preferable that the structural repeating unit derived from the mono (meth) acrylate having the structure represented by the general formula (I) is contained in an amount of 5 to 90 mol%, preferably 10 to 70 mol%. More preferably, it is more preferably 15 to 50 mol%.

  The other radical polymerizable monomer that can be copolymerized other than the mono (meth) acrylate having the structure represented by the general formula (I) is not particularly limited. Is, for example, vinyl aromatics such as styrene, styrene α-, o-, m-, p-alkyl, nitro, cyano, amide, ester derivatives; butadiene, 2,3-dimethylbutadiene, isoprene, chloroprene, etc. Dienes; methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid-n-propyl, (meth) acrylic acid-iso-propyl, (meth) acrylic acid-n-butyl, (meth) Acrylic acid-sec-butyl, (meth) acrylic acid-tert-butyl, (meth) acrylic acid pentyl, (meth) acrylic acid neopentyl, (meth) acrylic acid iso Mill, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylic 2-methylcyclohexyl acid, dicyclohexyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, (meth ) Naphthyl acrylate, Anthracenyl (meth) acrylate, Anthraninonyl (meth) acrylate, Piperonyl (meth) acrylate, Salicyl (meth) acrylate, Furyl (meth) acrylate, Furfuryl (meth) acrylate, ( (Meth) acrylic acid tetrahydride Furyl, pyranyl (meth) acrylate, benzyl (meth) acrylate, phenethyl (meth) acrylate, cresyl (meth) acrylate, (meth) acrylic acid-1,1,1-trifluoroethyl, (meth) acrylic Perfluoroethyl acid, perfluoro-n-propyl (meth) acrylate, perfluoro-iso-propyl (meth) acrylate, triphenylmethyl (meth) acrylate, cumyl (meth) acrylate, (meth) acrylic (Meth) acrylic acid esters such as acid 3- (N, N-dimethylamino) propyl, (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2-hydroxypropyl; (meth) acrylic acid amide , (Meth) acrylic acid N, N-dimethylamide, (meth) acrylic acid N, N-diethylamide, (meth) (Meth) acrylic amides such as acrylic acid N, N-dipropylamide, (meth) acrylic acid N, N-di-iso-propylamide, (meth) acrylic acid anthracenyl amide; (meth) acrylic acid anilide Vinyl compounds such as (meth) acryloylnitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinyl pyrrolidone, vinyl pyridine, vinyl acetate; diethyl citraconic acid, diethyl maleate, diethyl fumarate Unsaturated dicarboxylic acid diesters such as diethyl itaconate; monomaleimides such as N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, N- (4-hydroxyphenyl) maleimide; N- (meth) acryloylphthalimide Etc.

  Among these other radically polymerizable monomers, at least one selected from styrene, benzyl (meth) acrylate, and monomaleimide is used to impart excellent heat resistance and strength to the resin composition. In the constitutional repeating unit derived from other radical polymerizable monomer that can be copolymerized in the copolymer, at least one selected from these styrene, benzyl (meth) acrylate, and monomaleimide The content ratio of the derived structural repeating unit is preferably 1 to 70 mol%, and more preferably 3 to 50 mol%.

A known solution polymerization method is applied to the copolymerization reaction between the epoxy group-containing (meth) acrylate and the other radical polymerizable monomer copolymerizable therewith. The solvent to be used is not particularly limited as long as it is inert to radical polymerization, and a commonly used organic solvent can be used.
Specific examples of the solvent include ethylene glycol monoalkyl ether acetates such as ethyl acetate, isopropyl acetate, cellosolve acetate and butyl cellosolve acetate; diethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, carbitol acetate and butyl carbitol acetate. Propylene glycol monoalkyl ether acetates; acetate esters such as dipropylene glycol monoalkyl ether acetates; ethylene glycol dialkyl ethers; diethylene glycol dialkyl ethers such as methyl carbitol, ethyl carbitol, and butyl carbitol; triethylene glycol Dialkyl ethers; propylene glycol dialkyl Ethers; dipropylene glycol dialkyl ethers; ethers such as 1,4-dioxane and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; hydrocarbons such as benzene, toluene, xylene, octane and decane Petroleum petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha; lactic acid esters such as methyl lactate, ethyl lactate and butyl lactate; dimethylformamide, N-methylpyrrolidone and the like. These solvents may be used alone or in combination of two or more. The amount of these solvents used is usually 30 to 1000 parts by weight, preferably 50 to 800 parts by weight, with respect to 100 parts by weight of the resulting copolymer. When the amount of the solvent used is outside this range, it becomes difficult to control the molecular weight of the copolymer.

  The radical polymerization initiator used in the copolymerization reaction is not particularly limited as long as it can initiate radical polymerization, and a commonly used organic peroxide catalyst or azo compound catalyst should be used. Can do. Examples of the organic peroxide catalyst include those classified into known ketone peroxides, peroxyketals, hydroperoxides, diallyl peroxides, diacyl peroxides, peroxyesters, and peroxydicarbonates. Specific examples thereof include benzoyl peroxide, dicumyl peroxide, diisopropyl peroxide, di-t-butyl peroxide, t-butyl peroxybenzoate, t-hexyl peroxybenzoate, and t-butyl peroxy-2-ethyl. Hexanoate, t-hexylperoxy-2-ethylhexanoate, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-bis (T-butylperoxy) hexyl-3,3-isopropyl hydroperoxide, t-butyl hydroperoxide, dicumyl peroxide, dicumyl hydroperoxide, acetyl peroxide, bis (4-t-butylcyclohexyl) peroxide Oxydicarbonate, diisopropyl -Oxydicarbonate, isobutyl peroxide, 3,3,5-trimethylhexanoyl peroxide, lauryl peroxide, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, 1,1- Bis (t-hexylperoxy) 3,3,5-trimethylcyclohexane and the like can be mentioned. Examples of the azo compound catalyst include azobisisobutyronitrile and azobiscarbonamide. Among these, one or more radical polymerization initiators having an appropriate half-life are selected and used depending on the polymerization temperature. The usage-amount of a radical polymerization initiator is 0.5-20 weight part with respect to a total of 100 weight part of the said monomer used for a copolymerization reaction, Preferably it is 1-10 weight part.

  The copolymerization reaction may be performed by dissolving the monomer used in the copolymerization reaction and the radical polymerization initiator in a solvent and raising the temperature while stirring, or by adding the monomer to which the radical polymerization initiator is added. Alternatively, the reaction may be performed dropwise in a solvent that has been heated and stirred. Alternatively, the monomer may be added dropwise while the temperature is raised by adding a radical polymerization initiator to the solvent. The reaction conditions can be freely changed according to the target molecular weight.

  In the present invention, as the copolymer of the epoxy group-containing (meth) acrylate and the other radical polymerizable monomer copolymerizable therewith, the structural repeating unit 5 derived from the epoxy group-containing (meth) acrylate is used. It is preferable to comprise 10 to 95 mol% of structural repeating units derived from other radically polymerizable monomers copolymerizable therewith, and the former 20 to 80 mol% and the latter 80 to 20 mol%. %, More preferably 30 to 70 mol% of the former and 70 to 30 mol% of the latter. When the former epoxy group-containing (meth) acrylate is too little and the other radically polymerizable monomer is too much, it is not preferable because the addition amount of the polymerizable component and the alkali-soluble component becomes insufficient. If there is too much (meth) acrylate and the latter other radical polymerizable monomer is too little, heat resistance and strength may be lowered.

  As the unsaturated monobasic acid to be added to the epoxy group of the copolymer of the epoxy group-containing (meth) acrylate and the other radical polymerizable monomer copolymerizable therewith, a known one is used. And unsaturated carboxylic acids having an ethylenically unsaturated double bond, and specific examples include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, (meta ) Monocarboxylic acids such as α-position haloalkyl, alkoxyl, halogen, nitro, and cyano substituents of acrylic acid. Of these, (meth) acrylic acid is preferred. One of these may be used alone, or two or more may be mixed and used.

  These unsaturated monobasic acids are added to 10 to 100 mol% of the epoxy group of the copolymer, preferably 30 to 100 mol%, more preferably 50 to 100 mol%. If the addition ratio of the unsaturated monobasic acid is too small, there are concerns about adverse effects due to residual epoxy groups such as stability over time. In addition, a well-known method is employable as a method of adding unsaturated monobasic acid to the epoxy group of a copolymer.

  Furthermore, as the polybasic acid anhydride to be added to the hydroxyl group generated when an unsaturated monobasic acid is added to the epoxy group of the copolymer, known ones can be used, such as maleic anhydride, succinic anhydride, itaconic anhydride. Dibasic acid anhydrides such as acid, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride; trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, biphenyltetracarboxylic anhydride And polybasic acid anhydrides. Of these, tetrahydrophthalic anhydride and / or succinic anhydride are preferable. These polybasic acid anhydrides may be used alone or in a combination of two or more. By adding such components, alkali solubility can be imparted to the binder resin used in the present invention.

  These polybasic acid anhydrides are added to 10 to 100 mol% of the hydroxyl group produced when an unsaturated monobasic acid is added to the epoxy group of the copolymer, preferably 20 to 90 mol%, more preferably Is added to 30 to 80 mol%. When the addition ratio is too large, the remaining film ratio at the time of development may decrease, and when it is too small, the solubility becomes insufficient. In addition, a well-known method is employable as a method of adding a polybasic acid anhydride to the hydroxyl group produced when an unsaturated monobasic acid is added to the epoxy group of a copolymer.

  Further, in the present invention, in order to further improve the photosensitivity, glycidyl ether having a glycidyl (meth) acrylate or a polymerizable unsaturated group in a part of the generated carboxyl group after the addition of the polybasic acid anhydride described above. In order to add a compound or improve developability, a glycidyl ether compound having no polymerizable unsaturated group can be added to a part of the generated carboxyl group, or both of them can be added. good. Specific examples of the glycidyl ether compound having no polymerizable unsaturated group include a glycidyl ether compound having a phenyl group or an alkyl group, and as a commercial product, for example, trade name “Nagase Kasei Kogyo Co., Ltd.” Denacol EX-111, Denacol EX-121, Denacol EX-141, Denacol EX-145, Denacol EX-146, Denacol EX-171, Denacol EX-192, etc. . These resin structures are described in, for example, JP-A-8-297366 and JP-A-2001-89533, and are already known.

  As a weight average molecular weight (Mw) of polystyrene conversion measured by GPC of the above binder resin, 3000-100000 are preferable and 5000-50000 are especially preferable. If the molecular weight is less than 3000, the heat resistance and film strength are inferior, and if it exceeds 100,000, the solubility in the developer is insufficient, which is not preferable. Further, the weight average molecular weight (Mw) / number average molecular weight (Mn) ratio, as a measure of the molecular weight distribution, is preferably 2.0 to 5.0.

Moreover, as the binder resin in the present invention, a resin obtained by adding an epoxy group-containing unsaturated compound to the carboxyl group portion of the carboxyl group-containing resin is also particularly preferable.
The carboxyl group-containing resin is not particularly limited as long as it has a carboxyl group, and is usually obtained by polymerizing a carboxyl group-containing polymerizable monomer. Examples of the carboxyl group-containing polymerizable monomer include (meth) acrylic acid, maleic acid, crotonic acid, itaconic acid, fumaric acid, 2- (meth) acryloyloxyethyl succinic acid, and 2- (meth) acryloyloxyethyl. Adipic acid, 2- (meth) acryloyloxyethylmaleic acid, 2- (meth) acryloyloxyethylhexahydrophthalic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyloxypropylsuccinic acid, 2 -(Meth) acryloyloxypropyladipic acid, 2- (meth) acryloyloxypropylmaleic acid, 2- (meth) acryloyloxypropylhydrophthalic acid, 2- (meth) acryloyloxypropylphthalic acid, 2- (meth) acryloyl Oxybutyl succinic acid, 2- (meta To vinyl monomers such as acryloyloxybutyladipic acid, 2- (meth) acryloyloxybutylmaleic acid, 2- (meth) acryloyloxybutylhydrophthalic acid, 2- (meth) acryloyloxybutylphthalic acid, acrylic acid Monomers obtained by adding lactones such as ε-caprolactone, β-propiolactone, γ-butyrolactone, δ-valerolactone, and hydroxyalkyl (meth) acrylate to succinic acid, maleic acid, phthalic acid Or monomers added with acids or anhydrides such as anhydrides thereof. Among these, (meth) acrylic acid and 2- (meth) acryloyloxyethyl succinic acid are preferable, and (meth) acrylic acid is more preferable. A plurality of these may be used.

  In addition, the carboxyl group-containing resin may be copolymerized with the above-described carboxyl group-containing polymerizable monomer with another polymerizable monomer having no carboxyl group. Other polymerizable monomers include, but are not limited to, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate , Benzyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxymethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxy (Meth) acrylic esters such as ethyl (meth) acrylate, glycerol mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate; vinyl aromatics such as styrene and its derivatives Vinyl compounds such as N-vinylpyrrolidone; N-substituted maleimides such as N-cyclohexylmaleimide, N-phenylmaleimide, N-benzylmaleimide; polymethyl (meth) acrylate macromonomer, polystyrene macromonomer, poly-2-hydroxyethyl Examples thereof include macromonomers such as (meth) acrylate macromonomer, polyethylene glycol macromonomer, polypropylene glycol macromonomer, and polycaprolactone macromonomer. Particularly preferred are styrene, methyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, They are butyl (meth) acrylate, isobutyl (meth) acrylate, N-cyclohexylmaleimide, N-benzylmaleimide, and N-phenylmaleimide. These may be used in combination.

  Further, the carboxyl group-containing resin preferably further has a hydroxyl group from the viewpoint of the dispersibility of the pigment. Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate and hydroxypropyl (meth). Examples thereof include acrylates, hydroxyalkyl (meth) acrylates such as 4-hydroxybutyl (meth) acrylate, and glycerol mono (meth) acrylate.

  Specific examples of these carboxyl group-containing resins include (meth) acrylic acid, methyl (meth) acrylate, benzyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, cyclohexyl (meth) ) A polymerizable monomer not containing a hydroxyl group such as acrylate or cyclohexylmaleimide, and a hydroxyl group-containing monomer such as 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate or 4-hydroxybutyl (meth) acrylate (Meth) acrylic acid, methyl (meth) acrylate, benzyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, 2-hydroxyethyl methacrylate, and the like (meth) acrylic acid Esther and Copolymer, copolymer of (meth) acrylic acid and styrene, copolymer of (meth) acrylic acid, styrene and α-methylstyrene, copolymer of (meth) acrylic acid and cyclohexylmaleimide, etc. Can be mentioned.

  The acid value of the carboxyl group-containing resin in the present invention is usually 30 to 500 KOH mg / g, preferably 40 to 350 KOH mg / g, and more preferably 50 to 300 KOH mg / g. Moreover, the weight average molecular weight in GPC is 2000-20000 normally in polystyrene conversion, Preferably it is 4000-50000, More preferably, it is 5000-30000. When the weight average molecular weight is too small, the liquid stability is inferior, and when it is too large, the solubility of the resin composition for liquid crystal panels tends to deteriorate.

The epoxy group-containing unsaturated compound to be added to the carboxyl group portion of the carboxyl group-containing resin is not particularly limited as long as it has an ethylenically unsaturated group and an epoxy group in the molecule. Glycidyl (meth) acrylate, allyl glycidyl ether, glycidyl-α-ethyl acrylate, crotonyl glycidyl ether, (iso) crotonic acid glycidyl ether, N- (3,5-dimethyl-4-glycidyl) benzylacrylamide, 4-hydroxy Acyclic epoxy group-containing unsaturated compounds such as butyl (meth) acrylate glycidyl ether can also be mentioned, but alicyclic epoxy group-containing unsaturated compounds are preferred from the viewpoint of heat resistance and dispersibility.

  Here, as the alicyclic epoxy group-containing unsaturated compound, as the alicyclic epoxy group, for example, 2,3-epoxycyclopentyl group, 3,4-epoxycyclohexyl group, 7,8-epoxy [tricyclo [5 .2.1.0] dec-2-yl] group, and the like, and the ethylenically unsaturated group is preferably derived from a (meth) acryloyl group, and is a suitable alicyclic epoxy. Examples of the group-containing unsaturated compound include compounds represented by the following general formulas (IIIa) to (IIIm).

[In the formulas (IIIa) to (IIIm), R ¹¹ represents a hydrogen atom or a methyl group, R ¹² represents an alkylene group, R ¹³ represents a divalent hydrocarbon group, and n represents an integer of 1 to 10. . ]
In the general formulas (IIIa) to (IIIm), the alkylene group for R ₂ preferably has 1 to 10 carbon atoms, and specifically includes a methylene group, an ethylene group, a propylene group, a butylene group, and the like. Examples thereof include a methylene group, an ethylene group, and a propylene group. In addition, the hydrocarbon group for R ¹³ preferably has 1 to 10 carbon atoms, and examples thereof include an alkylene group and a phenylene group.

These alicyclic epoxy group-containing unsaturated compounds can be used in combination of two or more. Among them, the compound represented by the general formula (IIIc) is preferable, and 3,4-epoxycyclohexylmethyl (Meth) acrylate is particularly preferred.
In order to add the epoxy group-containing unsaturated compound to the carboxyl group portion of the carboxyl group-containing resin, a known method can be used. For example, the carboxyl group-containing resin and the epoxy group-containing unsaturated compound are triethylamine, In the presence of tertiary amines such as benzylmethylamine, quaternary ammonium salts such as dodecyltrimethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, benzyltriethylammonium chloride, pyridine, triphenylphosphine, etc. An epoxy group-containing unsaturated compound can be introduced into the carboxyl group of the resin by reacting in an organic solvent at a reaction temperature of 50 to 150 ° C. for several hours to several tens of hours.

The acid value of the carboxyl group-containing resin into which the epoxy group-containing unsaturated compound is introduced is usually 10
It is -200KOHmg / g, Preferably it is 20-150KOHmg / g, More preferably, it is 30-150KOHmg / g. Moreover, the weight average molecular weight in GPC is 2000-100000 normally in polystyrene conversion, Preferably it is 4000-50000, More preferably, it is 5000-30000.

In the present invention, as the binder resin, one of the aforementioned binder resins may be used alone, or two or more of them may be mixed and used. In combination, it is preferable that an undissolved substance does not remain in the non-image area on the substrate, and an effect of forming a high-density color pixel having excellent adhesion to the substrate can be formed.
In the resin composition for a liquid crystal panel of the present invention, the content ratio of these binder resins is usually 0.1% by weight or more, preferably 1% by weight or more, and usually 80% by weight or less, preferably in the total solid content. Is 60% by weight or less. When the content of the binder resin is less than this range, the film becomes brittle and the adhesion to the substrate may be lowered. On the other hand, when the amount is larger than this range, the permeability of the developing solution to the exposed portion increases, and the surface smoothness and sensitivity of the pixel may deteriorate.
[1-6. Surfactant]
The resin composition for a liquid crystal panel of the present invention contains a surfactant as an essential component. Various surfactants such as anionic, cationic, nonionic, and amphoteric surfactants can be used as surfactants, but they may adversely affect various properties such as voltage holding ratio and compatibility with organic solvents. It is preferable to use a nonionic surfactant in terms of low properties.

  Examples of anionic surfactants include alkyl sulfate ester surfactants such as “Emar 10” manufactured by Kao Corporation, alkyl naphthalene sulfonate surfactants such as “Perex NB-L”, and the like. Special polymeric surfactants such as “Homogenol L-18”, “Homogenol L-100” and the like can be mentioned. Of these, special polymer surfactants are preferred, and special polycarboxylic acid type polymer surfactants are more preferred.

Examples of the cationic surfactant include alkylamine salt surfactants such as “Acetamine 24” manufactured by Kao Corporation, and “Cotamine 24P” and “Cotamine 86W”.
And quaternary ammonium salt surfactants. Of these, quaternary ammonium salt surfactants are preferred, and stearyltrimethylammonium salt surfactants are more preferred. Examples of the nonionic surfactant include silicone surfactants such as “SH8400” manufactured by Torre Silicone Co., Ltd. and “KP341” manufactured by Silicone Co., Ltd., “FC430” manufactured by Sumitomo 3M Co., Ltd. Fluorine surfactants such as “F470” manufactured by Dainippon Ink & Chemicals, Inc. and “DFX-18” manufactured by Neos Co., Ltd. Polyoxyethylenes such as “Emulgen 104P” and “Emulgen A60” manufactured by Kao Corporation And surface active agents. Of these, silicone surfactants are preferable, and so-called polyether-modified or aralkyl-modified silicone surfactants having a structure in which a side chain of a polyether group or an aralkyl group is added to polydimethylsiloxane are more preferable.

  Two or more kinds of surfactants may be combined. Silicone surfactant / fluorine surfactant, silicone surfactant / special polymer surfactant, fluorine surfactant / special polymer surfactant Examples include combinations of agents. Of these, silicone surfactants / fluorine surfactants are preferred. Examples of the silicone surfactant / fluorine surfactant combination include polyether-modified silicone surfactant / oligomer-type fluorine surfactant. Specifically, for example, “TSF4460” manufactured by GE Toshiba Silicone / “DFX-18” manufactured by Neos, “BYK-300” manufactured by BYK Chemie / “S-393” manufactured by Seimi Chemical Co., “KP340 manufactured by Shin-Etsu Silicone Co., Ltd.” ”/“ F-478 ”manufactured by Dainippon Ink,“ SH7PA ”manufactured by Tore Silicone,“ DS-401 ”manufactured by Daikin,“ L-77 ”manufactured by Nihon Unicar, and“ FC4430 ”manufactured by Sumitomo 3M. It is done.

In the resin composition for a liquid crystal panel of the present invention, the content of these surfactants is generally 0.001% by weight or more, preferably 0.005% by weight or more, more preferably 0.01% by weight, based on the total solid content. Above, particularly preferably 0.02% by weight or more, usually 10% by weight or less, preferably 1% by weight or less, more preferably 0.1% by weight or less, particularly preferably 0.05% by weight or less. It is done.
[1-7. Other components other than solvents)
In addition to the above components, the resin composition for a liquid crystal panel of the present invention includes a dispersion aid, an organic carboxylic acid or / and an organic carboxylic acid anhydride, a plasticizer, a thermal polymerization inhibitor, a storage stabilizer, a surface protective agent, It may contain an adhesion improver, a development improver, and the like.

The dispersion aid is used for improving the dispersibility of the colorant, improving the dispersion stability, etc. Examples of the dispersion aid include azo, phthalocyanine, quinacridone, benzimidazolone, and quinophthalone. And derivatives such as diazodine pigments, isoindolinone, dioxazine, anthraquinone, indanthrene, perylene, perinone, diketopyrrolopyrrole, and dioxazine pigments. Examples of the substituent of these pigment derivatives include a sulfonic acid group, a sulfonamide group and a quaternary salt thereof, a phthalimidomethyl group, a dialkylaminoalkyl group, a hydroxyl group, a carboxyl group, an amide group, and the like. It may be bonded to the skeleton directly or via an alkyl group, aryl group, heterocyclic group or the like, preferably a sulfonamide group and a quaternary salt thereof, a sulfonic acid group, more preferably a sulfonic acid group. is there. In addition, a plurality of these substituents may be substituted on one pigment skeleton, or a mixture of compounds having different numbers of substitutions. Specific examples of pigment derivatives include sulfonic acid derivatives of azo pigments, sulfonic acid derivatives of phthalocyanine pigments, sulfonic acid derivatives of quinophthalone pigments, sulfonic acid derivatives of anthraquinone pigments, sulfonic acid derivatives of quinacridone pigments, diketo Examples include sulfonic acid derivatives of pyrrolopyrrole pigments and sulfonic acid derivatives of dioxazine pigments. Among these, sulfonic acid derivatives of Pigment Yellow 138, sulfonic acid derivatives of Pigment Yellow 139, sulfonic acid derivatives of Pigment Red 254, sulfonic acid derivatives of Pigment Red 255, sulfonic acid derivatives of Pigment Red 264, and sulfonic acid of Pigment Red 272 are preferable. A sulfonic acid derivative of Pigment Red 209, a sulfonic acid derivative of Pigment Violet 23, and a sulfonic acid derivative of Pigment Yellow 138, and a sulfonic acid derivative of Pigment Red 254.

  In the resin composition for a liquid crystal panel of the present invention, the content ratio of these dispersion aids is usually 0.1% by weight or more, and usually 30% by weight or less, preferably 200% with respect to the color material component. % By weight or less, more preferably 10% by weight or less, particularly preferably 5% by weight or less. This is because if the addition amount is small, the effect is not exhibited, and conversely if the addition amount is too large, dispersibility and dispersion stability are deteriorated.

  In addition, the resin composition for a liquid crystal panel of the present invention has an organic carboxylic acid having a molecular weight of 1000 or less and / or an organic carboxylic acid in order to further reduce the remaining undissolved resin composition while maintaining high pattern adhesion. An acid anhydride may be contained, and these are preferably contained when the aforementioned dispersant is a urethane resin dispersant. Specific examples of the organic carboxylic acid include aliphatic carboxylic acids and aromatic carboxylic acids. Aliphatic carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, glycolic acid, (meth) acrylic acid, monocarboxylic acid, succinic acid, malonic acid, succinic acid, glutaric acid And dicarboxylic acids such as adipic acid, pimelic acid, cyclohexanedicarboxylic acid, cyclohexene dicarboxylic acid, itaconic acid, citraconic acid, maleic acid and fumaric acid, and tricarboxylic acids such as tricarbaric acid and aconitic acid. Examples of the aromatic carboxylic acid include a carboxylic acid in which a carboxyl group is directly bonded to a phenyl group such as benzoic acid and phthalic acid, and a carboxylic acid in which a carboxyl group is bonded to the phenyl group through a carbon bond. Among these, those having a molecular weight of 600 or less, particularly those having a molecular weight of 50 to 500, specifically maleic acid, malonic acid, succinic acid, and itaconic acid are preferred. Examples of organic carboxylic acid anhydrides include aliphatic carboxylic acid anhydrides and aromatic carboxylic acid anhydrides. Specific examples include acetic anhydride, trichloroacetic anhydride, trifluoroacetic anhydride, tetrahydrophthalic anhydride, and succinic anhydride. Aliphatic carboxylic acids such as acid, maleic anhydride, citraconic anhydride, itaconic anhydride, glutaric anhydride, 1,2-cyclohexene dicarboxylic anhydride, n-octadecyl succinic anhydride, 5-norbornene-2,3-dicarboxylic anhydride An acid anhydride is mentioned. Examples of the aromatic carboxylic acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and naphthalic anhydride. Among these, those having a molecular weight of 600 or less, particularly those having a molecular weight of 50 to 500, specifically maleic anhydride, succinic anhydride, citraconic anhydride, and itaconic anhydride are preferred.

In the resin composition for a liquid crystal panel of the present invention, the content ratio of these organic carboxylic acids or / and organic carboxylic anhydrides is usually 0.01% by weight or more, preferably 0.03% by weight or more in the total solid content. More preferably, it is 0.05% by weight or more, and is usually 10% by weight or less, preferably 5% by weight or less, more preferably 3% by weight or less.
The resin composition for a liquid crystal panel of the present invention may contain a plasticizer. Examples of the plasticizer include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, Examples include cresyl phosphate, dioctyl adipate, dibutyl sebacate, and triacetyl glycerin. The content of these plasticizers is preferably in the range of 10% by weight or less based on the total solid content.

The resin composition for a liquid crystal panel of the present invention may contain a thermal polymerization inhibitor. Examples of the thermal polymerization inhibitor include hydroquinone, p-methoxyphenol, pyrogallol, catechol, 2,6- Examples include t-butyl-p-cresol, β-naphthol and the like. The content of these thermal polymerization inhibitors is preferably in the range of 3% by weight or less based on the total solid content.
[1-8. solvent〕
The resin composition for a liquid crystal panel of the present invention contains a solvent as an essential component. The solvent has a function of adjusting the viscosity by dissolving or dispersing each component, and examples of the solvent include diisopropyl ether, mineral spirit, n-pentane, amyl ether, ethyl caprylate, and n-hexane. , Diethyl ether, isoprene, ethyl isobutyl ether, butyl stearate, n-octane, valsol # 2, apco # 18 solvent, diisobutylene, amyl acetate, butyl acetate, apcocinner, butyl ether, diisobutyl ketone, methylcyclohexene, methyl nonyl ketone , Propyl ether, dodecane, soak solvent no. 1 and no. 2, amyl formate, dihexyl ether, diisopropyl ketone, Solvesso # 150, (n, sec, t-) butyl acetate, hexene, shell TS28 solvent, butyl chloride, ethyl amyl ketone, ethyl benzoate, amyl chloride, ethylene glycol diethyl ether , Ethyl orthoformate, methoxymethylpentanone, methyl butyl ketone, methyl hexyl ketone, methyl isobutyrate, benzonitrile, ethyl propionate, methyl cellosolve acetate, methyl isoamyl ketone, methyl isobutyl ketone, propyl acetate, amyl acetate, Amylformate, bicyclohexyl, diethylene glycol monoethyl ether acetate, dipentene, methoxymethylpentanol, methylamino Luketone, methyl isopropyl ketone, propyl propionate, propylene glycol-t-butyl ether, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, carbitol, cyclohexanone, ethyl acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether Acetate, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether acetate, 3-methoxypropionic acid, 3-ethoxypropionic acid, 3-ethoxy Methyl propionate, 3-ethoxypropyl Ethyl pionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, ethylene glycol acetate, ethyl carbitol, butyl carbitol, ethylene glycol monobutyl ether Propylene glycol-t-butyl ether, 3-methyl-3-methoxybutanol, tripropylene glycol methyl ether, methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate and the like. Among these, propylene glycol monomethyl ether acetate, methoxybutyl acetate, and ethyl 3-ethoxypropionate are preferable. These solvents may be used alone or in combination of two or more. Examples of preferable solvent combinations include a solvent containing propylene glycol monomethyl ether acetate and methoxybutyl acetate, a solvent containing propylene glycol monomethyl ether acetate and ethyl 3-ethoxypropionate, and the like.

In the resin composition for a liquid crystal panel of the present invention, the content of these solvents is not particularly limited, but the upper limit is usually 99% by weight or less. When the solvent exceeds 99% by weight, the concentration of each component excluding the solvent becomes too small, which is inappropriate for forming a coating film. On the other hand, the lower limit of the solvent content is usually 75% by weight or more, preferably 80% by weight or more, and more preferably 82% by weight or more in consideration of viscosity suitable for coating.
[2. Preparation of resin composition for liquid crystal panel]
Next, a method for preparing the resin composition for a liquid crystal panel of the present invention will be described.
In the present invention, when using a color material as an optional component, first, a predetermined amount of each of the color material, the dispersant, and the solvent is weighed, and the color material is dispersed into a liquid ink-like liquid in the dispersion treatment step. In this dispersion treatment step, a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, or the like can be used. By performing this dispersion treatment, the color material is made fine particles, so that the coating characteristics of the resin composition for liquid crystal panels are improved, and the transmittance of the product color filter substrate and the like is improved. When the color material is subjected to a dispersion treatment, it is preferable to appropriately use a binder resin, a dispersion aid, and the like. Moreover, when performing a dispersion process using a sand grinder, it is preferable to use glass beads or zirconia beads having a diameter of 0.1 to several mm. The temperature during the dispersion treatment is usually set to 0 ° C. or higher, preferably room temperature or higher, and usually 100 ° C. or lower, preferably 80 ° C. or lower. The dispersion time needs to be appropriately adjusted because the appropriate time varies depending on the composition of the ink-like liquid and the size of the sand grinder apparatus.

In addition to the ink-like liquid obtained by the dispersion treatment, a binder resin and a solvent as essential components, and a surfactant, and in some cases, a photopolymerizable monomer and a photopolymerization initiation system as optional components, and others Are mixed to obtain a uniform dispersion solution. In addition, in each process of a dispersion | distribution process and mixing, since fine refuse may mix, it is preferable to filter the obtained ink-like liquid with a filter etc.
[3. Physical properties of resin composition for liquid crystal panel]
The resin composition for a liquid crystal panel of the present invention has a contact angle θ (degrees) and a surface tension σ (mN / m) of droplets of the resin composition on the clean glass surface represented by the following formulas (1), (2), And (3) is satisfied. If any of the following formulas (1), (2), and (3) is not satisfied, it is difficult to solve the occurrence of coating unevenness and drying unevenness at the same time.

θ ≦ 5 × (σ ₀ −σ) (1)
σ ≦ σ ₀ −1 (2)
θ ≦ 15 (3)
[In the above formula, σ ₀ is the surface tension (mN / m) of the solvent alone used in the resin composition. ]
Further, the resin composition for a liquid crystal panel of the present invention preferably satisfies the following formulas (1 ′), (2 ′), and (3 ′), and the following formulas (1 ″), (2 ″) And (3 ″) are more preferable, and the following formulas (2 ′ ″) and (3 ′ ″) are particularly preferable.

θ ≦ 4 × (σ ₀ −σ) (1 ')
σ ≦ σ ₀ −1.5 (2 ')
θ ≦ 12 (3 ')
θ ≦ 3 × (σ ₀ −σ) (1 '')
σ ≦ σ ₀ -2 (2``)
θ ≦ 9 (3``)
σ ≦ σ ₀ -2 (2 ''')
θ ≦ 5 (3 ''')
In addition, the liquid crystal panel resin composition of the present invention has a surface tension σ ′ (mN / m) when diluted with a solvent used in the resin composition until the solvent weight is doubled from the viewpoint of leveling properties. ) And surface tension σ (mN / m) before dilution preferably satisfy the following formula (4), more preferably satisfy the following formula (4 ′), and satisfy the following formula (4 ″): It is particularly preferable to do this.

｜ σ−σ ′ | ≦ 0.4 (4)
｜ σ−σ ′ | ≦ 0.3 (4 ′)
｜ σ−σ ′ | ≦ 0.2 (4 '')
In the present invention, the contact angle and the surface tension are each measured by the following methods. The dilution is performed by the following method.
<Contact angle>
(I) The glass substrate for liquid crystal panel is cleaned with a cleaning agent and then subjected to light cleaning by UV ozone treatment. By the cleaning, the contact angle with pure water is 0 (zero), that is, a clean glass substrate that spreads out completely. Examples of the cleaning agent include a surfactant-containing type alkaline cleaning agent, and among them, an inorganic alkali is preferable. Specific examples include “Sunwash TL-100” manufactured by Lion Corporation, “Semi-clean KG” manufactured by Yokohama Oil Co., Ltd., and the like. UV ozone treatment is performed with a low-pressure mercury lamp irradiation device (for example, “VUM” manufactured by Oak Manufacturing Co., Ltd.) at an illuminance of usually 1 to 100 mW / cm ² , preferably 5 to 20 mW / cm ² for 10 to 300 seconds, preferably 30 to 120. It is performed on condition of second.

(Ii) The static contact angle of the resin composition with respect to the glass substrate produced by (i) is measured at 23 ° C. using a contact angle measuring device by a droplet method. Here, the “static contact angle” refers to a contact angle under a condition in which a state change with time due to flow or the like does not occur. The droplet method is usually performed by measuring within 1 minute after forming a droplet, preferably by measuring within 5 to 20 seconds. As the contact angle measuring device, for example, a direct reading method, an image processing method, or the like is used. Examples of the direct reading contact angle measuring device include “CA-DT” manufactured by Kyowa Interface Science Co., Ltd. Examples of the image processing type contact angle measuring device include “MCA-2” manufactured by Kyowa Interface Science Co., Ltd. and “DSA100” manufactured by KRUSS.
<Surface tension>
A platinum plate whose surface is fully red hot with an alcohol lamp or the like and cleaned is prepared, and the static surface tension of the resin composition is measured at 23 ° C. using a surface tension meter by a flat plate method. Here, “static surface tension” refers to surface tension under conditions in which state change with time due to flow or the like does not occur. Examples of the surface tension meter include “CBVP-A3” manufactured by Kyowa Interface Science Co., Ltd. and “Sigma 700” manufactured by KSV Corporation.
<Dilution method>
At room temperature, the same solvent as that used in the resin composition is added dropwise to the resin composition in the beaker while stirring and diluted. Specifically, for example, a magnetic stirrer or the like is added dropwise and diluted for 10 to 30 minutes while stirring at about 30 to 120 rpm.

The liquid crystal panel resin composition satisfying the formulas (1), (2), and (3), and (4) of the present invention is prepared by the types of the binder resin, the surfactant, and the solvent described above. It is important to achieve this by selecting the amount, combination, etc., and adjusting the balance between the hydrophilicity / hydrophobicity, lipophilicity / oleophobicity, molecular weight and polarity of the solvent of the surfactant. These adjustments are not simply inferred from the specific molecular structure of the surfactant, but are determined by whether or not the entire composition satisfies the above formula.
[4. Application of resin composition for liquid crystal panel]
The resin composition for a liquid crystal panel of the present invention is usually supplied onto a substrate in a state dissolved or dispersed in a solvent and used as a resist material or the like when forming a liquid crystal panel. As a method for supplying the substrate, a conventionally known method such as a spinner method, a wire bar method, a flow coating method, a die coating method, a roll coating method, or a spray coating method can be used. Above all, according to the die coating method, the amount of coating solution used is greatly reduced, there is no influence of mist adhering to the spin coating method, and the generation of foreign matter is suppressed. To preferred. And the resin composition for liquid crystal panels of the present invention does not cause coating unevenness at the time of application or drying unevenness in the subsequent drying process, and undergoes an exposure process, a development process, a heat treatment process, etc., and has an extremely smooth surface. A layer having can be formed.

Examples of application of the resin composition for a liquid crystal panel of the present invention to a liquid crystal panel include application of a color filter as a black matrix and a pixel, photo spacers and rib materials (liquid crystal split alignment) when the color filter is attached to a liquid crystal display device. Application as projections and liquid crystal display devices (panels) using them will be described.
[4-1. (Black matrix / pixel of color filter)
The transparent substrate of the color filter is not particularly limited as long as it is transparent and has an appropriate strength. Examples of the material include polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, polycarbonate resins, acrylic resins such as polymethyl methacrylate, thermoplastic resin sheets such as polysulfone resins, epoxy resins, Examples thereof include thermosetting resin sheets such as unsaturated polyester resins, and various glasses. Among these, glass and heat resistant resin are preferable from the viewpoint of heat resistance. For these transparent substrates, surface treatment such as corona discharge treatment or ozone treatment, thin film formation treatment with various resins such as silane coupling agents or urethane resins, etc. Etc. may be performed. The thickness of the transparent substrate is usually 0.05 mm or more, preferably 0.1 mm or more, and usually 10 mm or less, preferably 7 mm or less. In the case of performing a thin film forming treatment with various resins, the film thickness is usually 0.01 μm or more, preferably 0.05 μm or more, and usually 10 μm or less, preferably 5 μm or less.

A color filter can be produced by providing a black matrix on the above-described transparent substrate and forming red, green, and blue pixel images. The black matrix is formed on a transparent substrate using a light-shielding metal thin film or the resin composition for a liquid crystal panel of the present invention.
As the light shielding metal material, chromium compounds such as metal chromium, chromium oxide and chromium nitride, nickel and tungsten alloy, etc. are used, and these may be laminated in a plurality of layers. These light shielding metal thin films are generally formed by a sputtering method, and a desired pattern is formed in a film shape by a positive photoresist. For chromium, an etchant mixed with ceric ammonium nitrate and perchloric acid and / or nitric acid is used. For other materials, etching is performed using an etchant according to the material, and finally positive. A black matrix can be formed by stripping the mold photoresist with a dedicated stripper. In this case, first, a thin film of these metals or metal / metal oxide is formed on the transparent substrate by vapor deposition or sputtering. Next, a coating film of a positive photoresist resin composition is formed on the thin film. Next, the coating film is exposed and developed using a photomask having a repeated pattern such as a stripe, a mosaic, and a triangle to form a resist image. Thereafter, this coating film can be etched to form a black matrix.

  When utilizing the resin composition for liquid crystal panels of this invention, a black matrix is formed using the colored resin composition containing a black coloring material. For example, a black color material such as carbon black, graphite, iron black, aniline black, cyanine black, titanium black or the like, or a red, green, blue or the like appropriately selected from inorganic or organic pigments and dyes A black matrix can be formed using a colored resin composition containing a mixed black color material in the same manner as in the following method for forming red, green, and blue pixel images. The colored resin composition is used as a coating solution for forming at least one of these black, red, green, and blue colors. For black resists, on a transparent substrate, for red, green, and blue, a metal black matrix formed on a resin black matrix forming surface formed on the transparent substrate or using a chromium compound or other light shielding metal material On the forming surface, each process of coating, heat drying, image exposure, development and thermosetting is performed to form a pixel image of each color.

  On a transparent substrate provided with a black matrix, a colored resin composition containing a color material of one color of red, green, and blue is applied and dried, and then a photomask is overlaid on the coating film. Then, a pixel image is formed by image exposure, development, and if necessary, heat curing or photocuring to create a colored layer. A color filter image can be formed by performing this operation for each of the three colored resin compositions of red, green, and blue.

Application of the colored resin composition at that time can be performed by any of the methods described above. Among these, the die coating method is preferable, and the coating conditions by the die coating method may be appropriately selected depending on the composition of the resin composition, the type of the color filter to be manufactured, and the like. For example, the lip width at the nozzle tip is preferably 50 to 500 μm, and the distance between the nozzle tip and the substrate surface is preferably 30 to 300 μm. In order to adjust the thickness of the coating film, the running speed of the lip and the discharge amount of the liquid resin composition from the lip may be adjusted. If the thickness of the coating film is too large, pattern development becomes difficult and gap adjustment in the liquid crystal cell forming process may be difficult. On the other hand, if it is too small, it is difficult to increase the pigment concentration. Color expression may be impossible. The thickness of the coating film after drying is usually 0.2 μm or more, preferably 0.5 μm or more, more preferably 0.8 μm or more, and usually 20 μm or less, preferably 10 μm or less, more preferably 5 μm. The range is as follows.

  The coating film after the colored resin composition is applied to the substrate is preferably dried by a drying method using a hot plate, an IR oven, or a convection oven. Usually, after preliminary drying, it is heated again and dried. The conditions for the preliminary drying can be appropriately selected according to the type of the solvent component, the performance of the dryer used, and the like. The drying temperature and drying time are selected according to the type of the solvent component, the performance of the dryer used, and the like. Specifically, the drying temperature is usually 40 ° C. or higher, preferably 50 ° C. or higher, and usually 80 The drying time is usually 15 seconds or longer, preferably 30 seconds or longer, and usually 5 minutes or shorter, preferably 3 minutes or shorter. The reheating drying temperature condition is preferably higher than the preliminary drying temperature. Specifically, it is usually 50 ° C. or higher, preferably 70 ° C. or higher, and usually 200 ° C. or lower, preferably 160 ° C. or lower, particularly preferably. Is in the range of 130 ° C. or lower. The drying time is preferably in the range of usually 10 seconds or more, especially 15 seconds or more, and usually 10 minutes or less, especially 5 minutes, although it depends on the heating temperature. The higher the drying temperature is, the better the adhesion to the transparent substrate is. However, when the drying temperature is too high, the binder resin is decomposed, and thermal polymerization may be induced to cause development failure. In addition, as a drying process of this coating film, you may use the reduced pressure drying method which dries in a reduced pressure chamber, without raising temperature.

  Image exposure is performed by superimposing a negative matrix pattern on the coating film of the colored resin composition and irradiating an ultraviolet or visible light source through this mask pattern. At this time, if necessary, exposure may be performed after an oxygen blocking layer such as a polyvinyl alcohol layer is formed on the photopolymerizable layer in order to prevent a decrease in sensitivity of the photopolymerizable layer due to oxygen. The light source used for said image exposure is not specifically limited. As the light source, for example, a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a fluorescent lamp, a lamp light source, an argon ion laser, a YAG laser, Examples thereof include laser light sources such as excimer laser, nitrogen laser, helium cadmium laser, and semiconductor laser. An optical filter can also be used when used by irradiating light of a specific wavelength.

The color filter can be produced by the following procedure, for example. That is, (i) image exposure is performed on the coating film of the colored resin composition with the light source. (Ii) An image is formed on the substrate by performing development using an organic solvent or an aqueous solution containing a surfactant and an alkaline compound.
This aqueous solution may further contain an organic solvent, a buffering agent, a complexing agent, a dye or a pigment. Here, as the alkaline compound, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate, Inorganic alkaline compounds such as sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide, mono-di- or tri-ethanolamine, mono-di-, or tri-methyl Amine, mono-di-or triethylamine, mono-or diisopropylamine, n-butylamine, mono-di-or tri-isopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), Kori Organic alkali compound and the like. These alkaline compounds may be a mixture of two or more. Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters, and alkylbenzene sulfonic acids. Examples thereof include anionic surfactants such as salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, and sulfosuccinate esters, and amphoteric surfactants such as alkylbetaines and amino acids. Examples of the organic solvent include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol and the like. The organic solvent can be used alone or in combination with an aqueous solution.

There are no particular restrictions on the conditions of the development processing, but the development temperature is usually 10 ° C or higher, especially 15 ° C or higher, more preferably 20 ° C or higher, and usually 50 ° C or lower, especially 45 ° C or lower, more preferably 40 ° C or lower. Is preferred. The developing method can be any one of immersion developing method, spray developing method, brush developing method, ultrasonic developing method and the like.
The color filter according to the present invention is prepared by applying a curable coloring resin composition containing (1) a solvent, a phthalocyanine pigment as a color material, and a polyimide resin as a binder resin to the substrate, in addition to the above-described manufacturing method. However, it can also be produced by a method of forming a pixel image by an etching method. In addition, (2) a method of forming a pixel image directly on a transparent substrate by using a colored resin composition containing a phthalocyanine pigment as a color ink, and (3) a colored resin composition containing a phthalocyanine pigment. A method of depositing a colored film on an ITO electrode which is used as an electrodeposition liquid and dipping the substrate in the electrodeposition liquid and having a predetermined pattern, and (4) a film coated with a colored resin composition containing a phthalocyanine pigment Is attached to a transparent substrate, peeled off, image exposed and developed to form a pixel image, and (5) a pixel image is formed by an inkjet printer using a colored resin composition containing a phthalocyanine pigment as a colored ink. It can also be produced by a method or the like. As a method for producing the color filter, a method suitable for this is employed according to the composition of the resin composition for a liquid crystal panel of the present invention.

  The color filter after development is subjected to heat curing. In this case, the thermosetting treatment conditions are such that the temperature is usually 100 ° C. or more, preferably 150 ° C. or more, and usually 280 ° C. or less, preferably 250 ° C. or less, and the time is 5 minutes or more and 60 minutes or less. Selected by range. Through these series of steps, the patterning image formation for one color is completed. This process is sequentially repeated to pattern black, red, green, and blue to form a color filter. Note that the order of patterning the four colors is not limited to the order described above.

Furthermore, the color filter is used as a part of components such as a color display and a liquid crystal display device by forming a transparent electrode such as ITO on the image as it is, in order to improve surface smoothness and durability. If necessary, a top coat layer such as polyamide or polyimide can be provided on the image. Further, in some applications such as a planar alignment type drive system (IPS mode), the transparent electrode may not be formed. In the vertical alignment type driving method (MVA mode), ribs may be formed. Also, a column structure (photo spacer) made of photolithography may be formed instead of the bead dispersion type spacer.
[4-2. (Photo spacer)
The resin composition for a liquid crystal panel of the present invention is usually supplied onto a substrate in a state dissolved or dispersed in a solvent. As the supply method, any of the above-described coating methods can be used. Among them, the die coating method is preferable, and the coating amount is usually 0.5 μm or more, preferably 1 μm or more as a dry film thickness, and is usually 10 μm or less, preferably 8 μm or less, more preferably 5 μm or less. At that time, it is important that the dry film thickness or the height of the finally formed spacer is uniform over the entire area of the substrate. When the variation is large, a nonuniformity defect occurs in the liquid crystal panel. Further, it may be supplied in a pattern by an inkjet method or a printing method.

  The drying after supplying the resin composition onto the substrate is preferably performed by a drying method using a hot plate, an IR oven, or a convection oven. Moreover, you may combine the reduced pressure drying method of drying in a reduced pressure chamber, without raising temperature. The drying conditions can be appropriately selected according to the type of the solvent component, the performance of the dryer used, and the like. The drying time is usually selected within a range of 15 seconds to 5 minutes at a temperature of 40 to 100 ° C., preferably at a temperature of 50 to 90 ° C., depending on the type of the solvent component, the performance of the dryer used, and the like. It is selected in the range of 30 seconds to 3 minutes.

  The exposure is performed by overlaying a negative mask pattern on the coating film of the resin composition and irradiating an ultraviolet light source or a visible light source through the mask pattern. Further, a scanning exposure method using laser light may be used. At this time, if necessary, exposure may be performed after an oxygen blocking layer such as a polyvinyl alcohol layer is formed on the photopolymerizable layer in order to prevent a decrease in sensitivity of the photopolymerizable layer due to oxygen. As the light source used for the exposure, the same light source as described above in the production of the color filter is used.

After performing the above exposure, an image pattern can be formed on the substrate by development using an aqueous solution containing an alkaline compound and a surfactant or an organic solvent. This aqueous solution may further contain an organic solvent, a buffering agent, a complexing agent, a dye or a pigment. As the alkaline compound, the surfactant, and the organic solvent used at that time, the same ones as described above in the production of the color filter are used. The substrate after development is preferably subjected to a thermosetting treatment. The thermosetting treatment conditions in this case are selected such that the temperature is in the range of 100 to 280 ° C, preferably 150 to 250 ° C, and the time is in the range of 5 to 60 minutes.
[4-3. Rib (Liquid crystal alignment protrusion)
Ribs (liquid crystal split alignment protrusions) are protrusions formed on a transparent electrode in order to improve the viewing angle of a liquid crystal display device. By using the slope of the protrusions, the liquid crystal is locally tilted, The liquid crystal is divided in multiple directions.

  The resin composition for a liquid crystal panel of the present invention is applied by any of the above-described application methods onto a color filter substrate that is produced as described above and on which a transparent electrode such as ITO is formed on an image. The coating film thickness of the resin composition is usually 0.5 to 5 μm. After the coating film made of the composition is dried, a photomask is placed on the dried coating film, and image exposure is performed through the photomask. After exposure, an unexposed uncured portion is removed by development to form a pixel. Usually, an image obtained after development is required to have a fine line reproducibility of a width of 5 to 20 μm, and there is a tendency that a finer fine line reproducibility is required due to a demand for a high-quality display. In order to stably reproduce high-definition fine lines, the cross-sectional shape of the fine line image after development is a rectangular shape with a clear contrast between the non-image and the image area, such as development time, developer aging, physical stimulation of the development shower, etc. A wide development margin is preferable.

In the present invention, the developed image has a cross-sectional shape close to a rectangular shape. In order to obtain an arcuate shape necessary for the rib shape, it is usually 150 ° C. or higher, preferably 180 ° C. or higher, more preferably 200 ° C. or higher, and usually 400 ° C. or lower, preferably 300 ° C. or lower, more preferably 280. The heat treatment is performed at a temperature of not more than 10 ° C. and usually 10 minutes or more, preferably 15 minutes or more, more preferably 20 minutes or more, usually 120 minutes or less, preferably 60 minutes or less, more preferably 40 minutes or less. The cross-sectional shape is deformed into an arch shape to form a rib having a width of 0.5 to 20 μm and a height of 0.2 to 5 μm. As the range of deformation during heating, the resin composition and heating conditions are adjusted as appropriate, and the contact angle (W1) formed from the side surface of the fine line image (rectangular image cross-sectional shape) before heating and the substrate plane is the above heating. The ratio to the contact angle (W2) formed from the side surface of the thin line image after processing and the substrate plane, W1 / W2 is 1.2 or more, preferably 1.3 or more, more preferably 1.5 or more, and usually 10 Hereinafter, it is preferably 8 or less. The higher the heating temperature or the longer the heating time, the higher the deformation rate. Conversely, the lower the heating temperature or the shorter the heating time, the lower the deformation rate.
[4-4. Liquid crystal display device (panel)]
The liquid crystal panel according to the present invention can be constituted by, for example, a structure in which the color filter substrate and a driving substrate made of a thin film transistor (TFT) are opposed to each other with a liquid crystal layer interposed therebetween. More specifically, a color filter substrate coated with an alignment film material and subjected to an alignment process is bonded to a TFT drive substrate through a peripheral sealing material, and a liquid crystal material is injected into the gap, thereby liquid crystal. Can be a panel.

  The liquid crystal panel according to the present invention is generally formed by forming an alignment film on the color filter according to the present invention, spraying spacers on the alignment film, and then bonding to a counter substrate to form a liquid crystal cell. It is manufactured by injecting liquid crystal into a liquid crystal cell and connecting to a counter electrode. The alignment film is preferably a resin film such as polyimide. For the formation of the alignment film, a gravure printing method and / or a flexographic printing method is usually employed, and the thickness of the alignment film is several tens of nm. After the alignment film is cured by thermal baking, it is surface-treated by irradiation with ultraviolet rays or a rubbing cloth to be processed into a surface state in which the tilt of the liquid crystal can be adjusted.

  As the spacer, a spacer having a size corresponding to a gap (gap) with the counter substrate is used, and a spacer of 2 to 8 μm is usually preferable. A photo spacer (PS) of a transparent resin film can be formed on the color filter substrate by a photolithography method, and this can be used instead of the spacer. As the counter substrate, an array substrate is usually used, and a TFT (thin film transistor) substrate is particularly preferable. Further, the bonding gap with the counter substrate varies depending on the use of the liquid crystal panel, but is usually selected in the range of 2 μm or more and 8 μm or less. After being bonded to the counter substrate, portions other than the liquid crystal injection port are sealed with a sealing material such as an epoxy resin. The sealing material is cured by UV irradiation and / or heating, and the periphery of the liquid crystal cell is sealed.

The liquid crystal cell whose periphery is sealed is cut into panel units, then decompressed in a vacuum chamber, the liquid crystal injection port is immersed in liquid crystal, and then the liquid crystal is injected into the liquid crystal cell by leaking in the chamber. . The degree of vacuum in the liquid crystal cell is usually in the range of 1 × 10 ⁻² Pa or more, preferably 1 × 10 ⁻³ Pa or more, and usually 1 × 10 ⁻⁷ Pa or less, preferably 1 × 10 ⁻⁶ Pa or less. . The liquid crystal cell is preferably heated at reduced pressure, and the heating temperature is usually 30 ° C. or higher, preferably 50 ° C. or higher, and usually 100 ° C. or lower, preferably 90 ° C. or lower. The warming holding at the time of depressurization is usually in the range of 10 minutes or more and 60 minutes or less, and then immersed in the liquid crystal. The liquid crystal cell into which the liquid crystal is injected has a liquid crystal display device (panel) completed by sealing the liquid crystal injection port by curing the UV curable resin. The type of liquid crystal is not particularly limited, and is a conventionally known liquid crystal such as an aromatic, aliphatic, or polycyclic compound, and may be any of lyotropic liquid crystal, thermotropic liquid crystal, and the like. As the thermotropic liquid crystal, nematic liquid crystal, smectic liquid crystal, cholesteric liquid crystal and the like are known, but any of them may be used.

EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to a following example, unless the summary is exceeded. In the following examples and comparative examples, the contact angle and the surface tension were measured by the following methods, respectively.
<Contact angle>
After cleaning the glass substrate for liquid crystal panels (“AN100” manufactured by Asahi Glass Co., Ltd.) with a cleaning agent (“Sunwash TL-100” manufactured by Lion Co., Ltd.), UV ozone treatment is performed at 1000 mj, and then contact with pure water is performed. A clean glass substrate having a corner of zero degrees, that is, completely wet spread is prepared. Next, the static contact angle with the resin composition with respect to a glass substrate is measured at 23 degreeC using the commercially available contact angle measuring apparatus by the droplet method ("CA-DT" by Kyowa Interface Science Co., Ltd.).
<Surface tension>
Prepare a platinum plate whose surface is sufficiently red-hot with an alcohol lamp and clean it, and use a commercially available flat plate surface tension meter (“CBVP-A3” manufactured by Kyowa Interface Science Co., Ltd.) to form a resin composition at 23 ° C. Measure the static surface tension.

Example 1
Pigment Red 177 10 g as a coloring material, 13.3 g of “byk-161” (non-volatile content 30%) manufactured by Big Chemie as a dispersing agent, and 46.7 g of propylene glycol monomethyl ether acetate as a solvent are prepared. did. Separately, as a binder resin, a quaternary copolymer of styrene (55 mol%) / α-methylstyrene (15 mol%) / acrylic acid (20 mol%) / constituent repeating unit (10 mol%) having the following structure. 5.0 g of resin (weight average molecular weight 12000), 5.0 g of dipentaerythritol hexaacrylate as a photopolymerizable monomer, and 2- (2-chlorophenyl) -4,5- as a photopolymerization initiator

0.4 g of diphenylimidazole dimer, 0.2 g of 4,4′-bis (diethylamino) benzophenone, 0.4 g of 2-methylbenzothiazole as a polymerization accelerator, and fluorine-based surface activity manufactured by Dainippon Ink Co., Ltd. Clear resist mixed with 0.013 g of agent “F475”, 0.05 g of silicone surfactant “BYK-323” manufactured by BYK-Chemie Co., and 29.5 g of propylene glycol monomethyl ether acetate and 36.6 g of methoxybutyl acetate as a solvent Was made. After further mixing and homogenizing the mixture, 300 g of zirconia beads having a particle diameter of 0.5 mm were added, and the mixture was shaken with a paint conditioner for 5 hours for dispersion treatment, followed by filtration to obtain a uniform resin composition for a liquid crystal panel. Obtained.

This liquid crystal panel resin composition had a contact angle θ of 8 degrees with respect to the clean glass surface of the liquid droplets. The surface tension σ was 25.6 mN / m, and the surface tension σ _{0 of the} solvent alone was 27.6 mN / m. Furthermore, the surface tension σ ′ when diluted with a solvent until the solvent weight was doubled was 25.9 mN / m.
This resin composition for a liquid crystal panel was coated on a glass substrate with a slit die under the conditions of a coating speed of 100 mm / s, a coating gap of 100 μm, and a wet coating thickness of 20 μm, and then an ultimate pressure of 1 Torr in a vacuum drying chamber. Then, it was vacuum dried and further baked on a hot plate at 80 ° C. for 3 minutes. With respect to this coated substrate, the occurrence of coating unevenness and drying unevenness was observed with an interference fringe inspection lamp (Na lamp), and the results shown in Table 1 were obtained.

Example 2
A resin composition for a liquid crystal panel was prepared in the same manner as in Example 1 except that 0.025 g of a silicone surfactant “BYK-323” manufactured by Big Chemie was used as the surfactant. This liquid crystal panel resin composition had a contact angle θ of 3 degrees with respect to the clean glass surface of the liquid droplets. The surface tension σ was 26.2 mN / m, and the surface tension σ _{0 of the} solvent alone was 27.6 mN / m. Furthermore, the surface tension σ ′ when diluted with a solvent until the solvent weight was doubled was 26.5 mN / m. With respect to this coated substrate, the occurrence of coating unevenness and drying unevenness was observed with an interference fringe inspection lamp (Na lamp), and the results shown in Table 1 were obtained.

Example 3
As the surfactant, 0.025 g of a fluorine-based surfactant “F470” manufactured by Dainippon Ink and 0.049 g of a silicone-based surfactant “BYK-330” (non-volatile component 51%) manufactured by Big Chemie are used. In the same manner as in Example 1, a resin composition for a liquid crystal panel was prepared. This liquid crystal panel resin composition had a contact angle θ of 5 degrees with respect to the clean glass surface of the droplet. The surface tension σ was 25.7 mN / m, and the surface tension σ _{0 of the} solvent alone was 27.6 mN / m. Furthermore, the surface tension σ ′ when diluted with a solvent until the solvent weight was doubled was 25.9 mN / m. With respect to this coated substrate, the occurrence of coating unevenness and drying unevenness was observed with an interference fringe inspection lamp (Na lamp), and the results shown in Table 1 were obtained.

Comparative Example 1
A resin composition for a liquid crystal panel was prepared in the same manner as in Example 1 except that 0.013 g of the fluorine-based surfactant “S-393” manufactured by Seimi Chemical Co., Ltd. was used as the surfactant. This liquid crystal panel resin composition had a contact angle θ of 25 ° with respect to the clean glass surface of the droplet. The surface tension σ was 23.8 mN / m, and the surface tension σ _{0 of the} solvent alone was 27.6 mN / m. Furthermore, the surface tension σ ′ when diluted with a solvent until the solvent weight was doubled was 25.0 mN / m. With respect to this coated substrate, the occurrence of coating unevenness and drying unevenness was observed with an interference fringe inspection lamp (Na lamp), and the results shown in Table 1 were obtained.

Comparative Example 2
A resin composition for a liquid crystal panel was prepared in the same manner as in Example 1 except that 0.025 g of a fluorine-based surfactant “DFX-18” manufactured by Neos Co. was used as the surfactant. This liquid crystal panel resin composition had a contact angle θ of 20 degrees with respect to the clean glass surface of the liquid droplets. The surface tension σ was 26.1 mN / m, and the surface tension σ _{0 of the} solvent alone was 27.6 mN / m. Furthermore, the surface tension σ ′ when diluted with a solvent until the solvent weight was doubled was 26.5 mN / m. With respect to this coated substrate, the occurrence of coating unevenness and drying unevenness was observed with an interference fringe inspection lamp (Na lamp), and the results shown in Table 1 were obtained.

Comparative Example 3
A resin composition for a liquid crystal panel was prepared in the same manner as in Example 1 except that 0.05 g of a silicone surfactant “BYK-333” manufactured by Big Chemie was used as the surfactant. This liquid crystal panel resin composition had a contact angle θ of 15 degrees with respect to the clean glass surface of the droplet. The surface tension σ was 25.6 mN / m, and the surface tension σ _{0 of the} solvent alone was 27.6 mN / m. Further, the surface tension σ ′ when diluted with a solvent until the solvent weight was doubled was 26.1 mN / m. With respect to this coated substrate, the occurrence of coating unevenness and drying unevenness was observed with an interference fringe inspection lamp (Na lamp), and the results shown in Table 1 were obtained.

Comparative Example 4
A resin composition for a liquid crystal panel was prepared in the same manner as in Example 1 except that 0.025 g of a silicone surfactant “BYK-331” manufactured by Big Chemie was used as the surfactant. This liquid crystal panel resin composition had a contact angle θ of 6 degrees with respect to the clean glass surface of the liquid droplets. The surface tension σ was 27.3 mN / m, and the surface tension σ _{0 of the} solvent alone was 27.6 mN / m. Furthermore, the surface tension σ ′ when diluted with a solvent until the solvent weight was doubled was 27.5 mN / m. With respect to this coated substrate, the occurrence of coating unevenness and drying unevenness was observed with an interference fringe inspection lamp (Na lamp), and the results shown in Table 1 were obtained.

Claims (6)

A resin composition for a liquid crystal panel comprising a binder resin, a surfactant, and a solvent, wherein the contact angle θ (degree) of the droplets of the resin composition with respect to the clean glass surface and the surface tension σ ( mN / m) satisfies the following formulas (1), (2), and (3): A resin composition for a liquid crystal panel.
θ ≦ 5 × (σ ₀ −σ) (1)
σ ≦ σ ₀ −1 (2)
θ ≦ 15 (3)
[In the above formula, σ ₀ is the surface tension (mN / m) of the solvent alone used in the resin composition. ] The surface tension σ ′ (mN / m) when diluted with the solvent used in the resin composition of the liquid crystal panel according to claim 1 until the solvent weight is doubled and before dilution. A liquid crystal panel resin composition having a surface tension σ (mN / m) satisfying the following formula (4):
｜ σ−σ ′ | ≦ 0.4 (4)   The resin composition for liquid crystal panels of Claim 1 or 2 containing a silicone type surfactant as surfactant.   The resin composition for a liquid crystal panel according to any one of claims 1 to 3, comprising a fluorine-based surfactant as the surfactant.   The color filter formed using the resin composition for liquid crystal panels in any one of Claims 1 thru | or 4.   The liquid crystal panel formed using the resin composition for liquid crystal panels in any one of Claims 1 thru | or 4.