KR100752968B1 - Resin composition for liquid-crystal panel, and color filter and liquid-crystal panel using the same - Google Patents

Abstract

The resin composition for liquid crystal panels which can solve the generation | occurrence | production of a coating nonuniformity and a dry nonuniformity simultaneously, and the color filter and liquid crystal panel using the same are provided.

A resin composition for a liquid crystal panel containing a binder resin, a surfactant, and a solvent, wherein the contact angle θ (degrees) with respect to the clean glass surface of the liquid drop of the resin composition and the surface tension σ (mN / m) of the resin composition are as follows. Liquid crystal formed using the resin composition for liquid crystal panels which satisfy | fills Formula (1), (2), and (3), and the color filter formed using this resin composition for liquid crystal panels, and this resin composition for liquid crystal panels. panel.

θ≤5 × (σ ₀ -σ) (1)

θ≤σ ₀ -1 (2)

θ≤15 (3)

Liquid crystal panel, surfactant

Description

RESIN COMPOSITION FOR LIQUID-CRYSTAL PANEL, AND COLOR FILTER AND LIQUID-CRYSTAL PANEL USING THE SAME}

This invention relates to the resin composition for liquid crystal panels, and the color filter and liquid crystal panel using the same.

Conventionally, in the manufacture of a liquid crystal panel, a pixel, a black matrix, a photo spacer, a rib material (liquid crystal division alignment projection), an overcoat, and the like, which are part of the liquid crystal panel, are formed in the following order. That is, (1) the resin composition for liquid crystal panels containing a photosensitive component, binder resin, a color material, a solvent, etc. is apply | coated to a board | substrate. (2) The coating film of said resin composition is dried, and a resin composition layer is formed. (3) The said resin composition layer is exposed and developed, and the resist image for liquid crystal panels is formed.

In the process of said (1) (2), generation | occurrence | production of application | coating nonuniformity in application | coating of the resin composition to the board | substrate especially becomes a problem. Therefore, the means which adds various surfactant is employ | adopted in order to prevent this. For example, especially in the die coat application method, since the resin composition has a low viscosity at low solid content concentration, pin traces, Bernard cells, roughness, roughness, marangoni, and edge protrusion (liquid smoke ( 건)) such as "drying nonuniformity" is likely to occur. On the other hand, the means of increasing the addition amount of surfactant, using the surfactant with a high ability of reducing surface tension, etc. is employ | adopted. However, these drying nonuniformity prevention means became the cause of generating "coating nonuniformity" of a resin composition on the one hand. Such a coating nonuniformity is a crossing nonuniformity, a string nonuniformity, a thin spot, a streak, etc. which arise, for example by deteriorating the wettability of the resin composition with respect to a glass substrate, or leveling property. And these coating nonuniformity and dry nonuniformity have a trade off relationship, and it was difficult to prevent the occurrence of both nonuniformity at the same time.

On the other hand, for example, in patent document 1, the coating surface edge at the time of the slit coat to a board | substrate is used by using the silicon type surfactant whose molecular weight which has a phenyl group is 3000-4000 as surfactant contained in the polymeric composition for color filters. It is supposed that it is possible to prevent the formation of a horn-shaped thick film portion in the portion. However, according to the inventor's examination, it was found that simply using the silicon-based surfactant is insufficient to prevent the occurrence of uniform nonuniformity containing other types of nonuniformity. For example, in patent document 2, when the surface tension of a coloring photosensitive resin composition is made into 25.5 mN / m or more and 29.0 mN / m or less, favorable applicability | paintability can be implement | achieved in a spinless coater. However, according to the examination of the present inventors, it was found that only by defining the surface tension in a specific range, it was insufficient to solve the problem of wettability with the glass surface, in particular, liquid breakup peculiar to a spinless coater.

Patent Document 1: Japanese Unexamined Patent Publication No. 2004-29261

Patent Document 2: Japanese Unexamined Patent Publication No. 2004-126549

Disclosure of the Invention

Problems to be Solved by the Invention

This invention is made | formed in view of the above-mentioned prior art, and an object of this invention is to provide the resin composition for liquid crystal panels which can solve the generation | occurrence | production of a coating nonuniformity and a dry nonuniformity simultaneously, and the color filter and liquid crystal panel using the same.

Means to solve the problem

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching in order to solve the said subject, especially the kind, quantity, combination, etc. of a binder resin, surfactant, and a solvent are selected, and the hydrophilicity, hydrophobicity, lipophilicity, the oil property, molecular weight of surfactant are selected. By adjusting the balance between the polarity of the solvent and the solvent, it has been found that the resin composition having a specific relationship between the contact angle and the surface tension with respect to the glass surface can solve the above problems, and has reached the present invention. Therefore, the summary of this invention is as follows.

(i) The resin composition for liquid crystal panels containing binder resin, surfactant, and a solvent, Comprising: The contact angle (theta) (degree) with respect to the clean glass surface of the liquid droplet of this resin composition, and the surface tension (sigma) (mN / m) of this resin composition. ) Satisfies the following formulas (1), (2) and (3).

θ≤5 × (σ ₀ -σ) (1)

σ≤σ ₀ -1 (2)

θ≤15 (3)

[Wherein, sigma ₀ is the surface tension (mN / m) of the solvent alone used in the resin composition.]

(Ii) The color filter formed using the resin composition for liquid crystal panels as described in said (i).

(Iii) The liquid crystal panel formed using the resin composition for liquid crystal panels as described in said (i).

Effects of the Invention

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

Best Mode for Carrying Out the Invention

[One. Resin composition for liquid crystal panel]

It is preferable that the resin composition for liquid crystal panels containing the binder resin, surfactant, and a solvent of this invention contains a photopolymerizable monomer and a photoinitiator as a photosensitive component. Moreover, a color material, a dispersing agent, another component, etc. are contained as needed further. Below, the structural component of the resin composition for liquid crystal panels of this invention is demonstrated.

[1-1. Photopolymerizable monomer]

It is preferable that the resin composition for liquid crystal panels of this invention contains a photopolymerizable monomer. Although there will be no restriction | limiting in particular if a photopolymerizable monomer is a low molecular compound which can superpose | polymerize, The addition-polymerizable compound which has at least 1 ethylenic double bond (Hereinafter, it may be called "ethylenic compound.") Is preferable. The ethylenic compound is a compound having an ethylenic double bond such as addition polymerization and curing by the action of the photopolymerization initiation system described later when the resin composition for a liquid crystal panel of the present invention receives irradiation with actinic light. In addition, the monomer in this invention means the concept corresponding to what is called a high molecular substance, and also contains a dimer, a trimer, and an oligomer other than a narrow monomer.

As an ethylenic compound, For example, Unsaturated carbon, such as (meth) acrylic acid (In addition, in this invention, "(meth) acryl" shall mean "acryl" and / or "methacryl.") Acids, esters of monohydroxy compounds and unsaturated carboxylic acids, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids, esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids, unsaturated carboxylic acids and polyhydric carboxylic acids, and It has a urethane skeleton which made the ester obtained by esterification of polyhydric hydroxy compounds, such as the aliphatic polyhydroxy compound and aromatic polyhydroxy compound mentioned above, the polyisocyanate compound, and the (meth) acryloyl-group containing hydroxy compound. Ethylenic compound etc. are mentioned.

Examples of esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and trimethylol ethane tri (meth). Acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta ( (Meth) acrylic acid esters, such as meth) acrylate, dipentaerythritol hexa (meth) acrylate, and glycerol (meth) acrylate, are mentioned. Moreover, the itaconic acid ester which replaced the (meth) acrylic acid part of these acrylates with the itaconic acid part, the crotonic acid ester which replaced with the crotonic acid part, or the maleic acid ester which changed into the maleic acid part etc. are mentioned. Examples of the ester of the aromatic polyhydroxy compound and the unsaturated carboxylic acid include hydroquinone di (meth) acrylate, resorcindi (meth) acrylate, pyrogallol tri (meth) acrylate, and the like. In addition, the ester obtained by esterification of an unsaturated carboxylic acid, a polyhydric carboxylic acid, and a polyhydric hydroxy compound may be a mixture, not necessarily a single substance. Representative examples include condensates of (meth) acrylic acid, phthalic acid, and ethylene glycol, condensates of (meth) acrylic acid, maleic acid, and diethylene glycol, condensates of (meth) acrylic acid, terephthalic acid, and pentaerythritol, (meth ) Condensates of acrylic acid, adipic acid, butanediol, and glycerin.

As an ethylenic compound which has a urethane skeleton which made the polyisocyanate compound and the (meth) acryloyl-group containing hydroxy compound react, Aliphatic diisocyanate, such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; Alicyclic diisocyanates such as cyclohexane diisocyanate and isophorone diisocyanate; Aromatic diisocyanates such as tolylene diisocyanate and diphenylmethane diisocyanate; 2-hydroxyethyl (meth) acrylate, 3-hydroxy [1,1,1-tri (meth) acryloyloxymethyl] propane The reactant with the (meth) acryloyl group containing hydroxy compound is mentioned.

In addition, as an example of the ethylenic compound used for this invention, (meth) acrylamide, such as ethylenebis (meth) acrylamide; Allyl esters such as diallyl phthalate; Vinyl group containing compounds, such as divinyl phthalate, etc. are mentioned.

In addition, the monomer which has an acid value may be sufficient as an ethylenic compound. The monomer having an acid value is, for example, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and has an acid group by reacting a non-aromatic carboxylic anhydride in an unreacted hydroxyl group of the aliphatic polyhydroxy compound. Functional monomers are preferred, and particularly preferably, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol in this ester. Although these monomers may be used individually by 1 type, since it is difficult to obtain a single compound in manufacture, you may mix and use 2 or more types. Moreover, you may use together the polyfunctional monomer which does not have an acidic radical as a monomer, and the polyfunctional monomer which has an acidic radical as needed.

As a preferable acid value, the polyfunctional monomer which has an acidic radical is 0.1-40 mgKOH / g, Especially preferably, it is 5-30 mgKOH / g. If the acid value of the polyfunctional monomer is too low, the development and dissolution characteristics are inferior. If the acid value of the polyfunctional monomer is too high, manufacturing and handling become difficult, resulting in poor photopolymerization performance and poor sclerosis such as surface smoothness of the pixel. Therefore, when using together 2 or more types of polyfunctional monomers of different acid groups, or when using together the polyfunctional monomer which does not have an acidic radical, it is preferable to adjust so that the acid value as a whole polyfunctional monomer may fall in the said range. In this invention, the polyfunctional monomer which has a more preferable acid value is dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentaacryl which are marketed by Toa synthesis Co., Ltd. product "T01382". It is a mixture which has a succinic acid ester of the rate as a main component. You may use combining this polyfunctional monomer and another polyfunctional monomer.

In the resin composition for liquid crystal panels of this invention, the content rate of these ethylenic compounds is total solid content [In addition, in this invention, "total solid content" is the whole component in resin compositions for liquid crystal panels other than the solvent mentioned later. Is 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 Is 50% by weight or less, particularly preferably 40% by weight or less. In addition, the ratio with respect to the color material mentioned later is 0 weight% or more normally, Preferably it is 5 weight% or more, More preferably, it is 10 weight% or more, Especially preferably, it is 20 weight% or more, Moreover, 200 weight% or less normally Preferably it is 100 weight% or less, More preferably, it is 80 weight% or less.

[1-2. Photopolymerization Initiation System]

It is preferable that the resin composition for liquid crystal panels of this invention contains a photoinitiator. The photopolymerization initiator is usually used as a mixture with a photopolymerization initiator and additives such as sensitizing dyes and polymerization accelerators added as needed, and absorbs light directly or photosensitizes to cause decomposition reactions or dehydrogenation reactions. It is a component having a function of generating polymerization active radicals.

As a photoinitiator which comprises a photoinitiator, the titanocene derivatives as described in each of Unexamined-Japanese-Patent No. 59-152396, Unexamined-Japanese-Patent No. 61-151197, etc., Unexamined-Japanese-Patent No. 10-300922, for example. Derivation of halomethylated oxadiazoles described in hexaaryl biimidazole derivatives described in Japanese Patent Application Laid-Open No. H11-174224, Japanese Patent Laid-Open No. 2000-56118, etc. Radical activators such as retention, halomethyl-s-triazine derivatives, N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acid salts, and N-aryl-α-amino acid esters; (alpha)-aminoalkyl phenone derivatives, the oxime ester system derivatives as described in each Unexamined-Japanese-Patent No. 2000-80068, etc. are mentioned.

Specifically, for example, as titanocene derivatives, dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis (2,3,4,5,6- Pentafluoropheni-1-yl), dicyclopentadienyltitaniumbis (2,3,5,6-tetrafluoropheni-1-yl), dicyclopentadienyltitaniumbis (2,4,6- Trifluoropheny-1-yl, dicyclopentadienyltitaniumdi (2,6-difluoropheny-1-yl), dicyclopentadienyltitaniumdi (2,4-difluoropheni-1- 1), di (methylcyclopentadienyl) titaniumbis (2,3,4,5,6-pentafluoropheni-1-yl), di (methylcyclopentadienyl) titaniumbis (2,6-di Fluoropheny-1-yl), dicyclopentadienyltitanium [2,6-di-fluoro-3- (pyro-1-yl) -pheny-1-yl], and the like. As derivatives, 2- (2'-chlorophenyl) -4,5-diphenylimidazole dimer and 2- (2'-chlorophenyl) -4,5-bis (3'- Methoxyphenyl) imidazole dimer, 2- (2'-fluorophenyl) -4.5-diphenylimidazole dimer, 2- (2'-methoxyphenyl) -4,5-diphenylimidazole 2 Dimers, (4'-methoxyphenyl) -4,5-diphenylimidazole dimers, and the like further include 2-trichloromethyl-5- (2'-benzofuryl as halomethylated oxadiazole derivatives. ) -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 and the like Further, as halomethylated triazine derivatives, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine and 2- (4-methoxynaphthyl) -4 , 6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycar Bonylnaphthyl) -4,6-bis (trichloromethyl) -s-triazine and the like are also used as α-aminoalkylphenone derivatives. Is 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone -1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzoate, 4-diethylamino Acetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) carcon and the like also include oxime ester derivatives such as 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, respectively. Can be.

Moreover, benzoin alkyl ether, such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, and benzoin isopropyl ether; Anthraquinone derivatives such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone and 1-chloroanthraquinone; Benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, etc. Benzophenone derivatives; 2,2-dimethoxy-2-phenylacetphenone, 2,2-diethoxyacetphenone, 1-hydroxycyclohexylphenyl ketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methyl Ethyl- (p-isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl- (4'-methylthiophenyl) -2-morpholino-1-propanone Acetophenone derivatives such as 1,1,1-trichloromethyl- (p-butylphenyl) ketone; Thioxanthone, 2-ethyl thioxanthone, 2-isopropyl thioxanthone, 2-chlorothioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, 2.4-diisopropyl Thioxanthone derivatives such as thioxanthone; benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoic acid; Acridine derivatives such as 9-phenylacridine and 9- (pmethoxyphenyl) acridine; Phenadine derivatives such as 9,10-dimethylbenzphenadine; And anthrone derivatives such as benzanthrone.

Moreover, as a polymerization accelerator used as needed, For example, N, N- dialkylamino benzoic acid alkyl esters, such as N, N- dimethylamino benzoic acid ethyl ester; Mercapto compounds, such as a mercapto compound which has heterocycles, such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, and 2-mercaptobenzoimidazole, or an aliphatic polyfunctional mercapto compound, etc. are mentioned. have. These photoinitiators and polymerization accelerators may be used individually by 1 type, respectively, and may mix and use 2 or more types.

In the resin composition for liquid crystal panel of this invention, the content rate of these photoinitiators is 0.1 weight% or more normally in total solid content, Preferably it is 0.5 weight% or more, or 40 weight% or less normally, Preferably It is 30 weight% or less. If the content ratio is significantly low, it may cause a decrease in sensitivity to the exposure light rays. On the contrary, if the content ratio is significantly high, the solubility of the unexposed portion in the developing solution may be lowered, and development defects may be induced.

Moreover, as a sensitizing dye used according to the wavelength of an image exposure light source for the purpose of improving a sensitive sensitivity as needed, the xanthene type pigment | dye of Unexamined-Japanese-Patent No. 4-221958, Unexamined-Japanese-Patent No. 4-219756, etc. is mentioned. , Coumarin pigments having heterocycles described in Japanese Unexamined Patent Publication No. Hei 3-239703, Japanese Unexamined Patent Application Publication No. Hei 5-289335, Japanese Unexamined Patent Application Publication No. Hei 5-23989 3-ketokumarin type pigment | dye described in each publication of Unexamined-Japanese-Patent No. 6-19240, a pyrromethene type pigment | dye, Unexamined-Japanese-Patent No. 47-2528, Japan Unexamined-Japanese-Patent No. 54-155292, Japanese Patent Publication No. 45-37377, Japanese Patent Application Publication No. 48-84183, Japanese Patent Application Publication No. 52-112681, Japanese Patent Application Publication No. 58-15503, Japanese Patent Application Publication No. 60-88005, Japanese Laid-Open Patent Publication No. 59-56403, Japanese Unexamined Patent Publication No. Hei 2-69, Japanese Unexamined Patent Application Publication No. 57-168088, Japanese Unexamined Patent Publication No. Hei 5-107761, Japanese Unexamined Patent Publication No. Hei 5-210240, and Japanese Unexamined Patent Application Publication No. 4-288818 The pigment | dye which has the dialkylaminobenzene frame | skeleton described in the publication etc. are mentioned.

Preferred among these sensitizing dyes are amino group-containing sensitizing dyes, and more preferably, 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'-diaminobenzo Benzophenone compounds such as phenone, 3,3'-diaminobenzophenone and 3,4-diaminobenzophenone; 2- (p-dimethylaminophenyl) benzoxazole, 2- (p-diethylaminophenyl) benzooxazole, 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-diethylaminophenyl) 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-diethylamino P-dialkylaminophenyl group-containing compounds such as phenyl) quinoline, (p-dimethylaminophenyl) pyrimidine and (p-diethylaminophenyl) pyrimidine. Most preferable among these is 4,4'- dialkylamino benzophenone. A sensitizing dye may also be used individually by 1 type, and may mix and use 2 or more types.

In the resin composition for liquid crystal panels 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, and usually in the total solids. 20 weight% or less, Preferably it is 15 weight% or less, More preferably, it is the range of 10 weight% or less.

[1-3. Color material]

The resin composition for liquid crystal panels of this invention contains a color material as needed (for example, when using for the use of a pixel, a black matrix, etc.). As a coloring material, although a pigment or dye can be used, a pigment is preferable at the point of heat resistance, light resistance, etc. As a 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. Examples of the chemical structure include organic pigments such as azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indansrene and perylene. In addition, various inorganic pigments can also be used. Hereinafter, the specific example of the pigment which can be used is shown by a pigment number. "C.I." shown below means a color index (C.I.).

As a red pigment, C.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, 1 01, 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, 179, 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. Among them, preferably, C.I. Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, more preferably C.I. Pigment Red is 177, 209, 224 and 254.

As a blue pigment, C.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. Among them, preferably C.I. Pigment blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, more preferably C.I. Pigment Blue 15: 6.

As a green pigment, C.I. Pigment green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55. Among them, preferably C.I. Pigment Green 7, 36.

As a yellow pigment, C.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, 173, 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, and 208. Among them, preferably C.I. Pigment yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, more preferably C.I. Pigment Yellow 83, 138, 139, 150, 180.

As a purple pigment, C.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. Among them, preferably C.I. Pigment violet 19, 23, more preferably C.I. Pigment Violet 23.

As an orange pigment, C.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. Among them, preferably C.I. Pigment Orange 38, 71.

Examples of the inorganic pigments include barium sulfate, lead sulfate, titanium oxide, yellow lead, bengal, chromium oxide, and the like.

Said various pigment can also use multiple types together. For example, in order to adjust chromaticity, as a pigment, a green pigment and a yellow pigment can be used together, or a blue pigment and a purple pigment can be used together. Moreover, the average particle diameter of these pigments is 1 micrometer or less normally, Preferably it is 0.5 micrometer or less, More preferably, it is 0.25 micrometer 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.

As an azo dye, it is C.I. Acid yellow (11), C.I. Acid orange (7), C.I. Acid red (37), C.I. Acid red (180), C.I. Acid blue (29), C.I. Direct Red (28), C.I. Direct Red (83), C.I. Direct Yellow (12), C.I. Direct Orange (26), C.I. Direct Green (28), C.I. Direct Green (59), C.I. Reactive Yellow (2), C.I. Reactive Red (17), C.I. Reactive Red 120, C.I. Reactive black (5), C.I. Disperse Orange (5), C.I. Disperse Red (58), C.I. Disperse Blue (165), C.I. Basic Blue (41), C.I. Basic Red (18), C.I. Modern Red (7), C.I. Modern Yellow (5), C.I. Modern blue (7) and the like.

As an anthraquinone type dye, it is C.I. Pad blue (4), C.I. Acid blue (40), C.I. Acid green (25), C.I. Reactive Blue (19), C.I. Reactive Blue (49), C.I. Disperse Red (60), C.I. Disperse Blue (56), C.I. Disperse blue 60, etc. are mentioned.

As phthalocyanine-based dyes, for example, C.I. Pad blue (5) and the like are quinoneimine-based dyes, for example, C.I. Basic Blue (3), C.I. Basic blue (9) and the like are quinoline dyes, for example, C.I. Solvent Yellow (33), C.I. Acid yellow (3), C.I. Disperse yellow 64 and the like are nitro dyes, for example, C.I. Acid yellow (1), C.I. Acid orange (3), C.I. Disperse yellow 42, etc. are mentioned.

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 black color material alone, or may be a mixture of red, green, blue, and the like. In addition, these color materials can be suitably selected from pigments or dyes of inorganic or organic. In the case of an inorganic and an organic pigment, it is preferable to disperse | distribute to 1 micrometer or less normally, Preferably it is 0.5 micrometer or less as an average particle diameter.

As a black color material which can be used independently, carbon black, acetylene black, lamp black, bone black, graphite, iron black, aniline black, cyanine black, titanium black, etc. are mentioned. Among these, carbon black and titanium black are preferable from the viewpoint of light blocking rate and image characteristics.

As an example of carbon black, it is a product made by Mitsubishi Chemical Corporation, for example, MA7, MA8, MA11, MA100, MA100R, MA220, MA230, MA600, # 5, # 10, # 20, # 25, # 30, # 32, # 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, # 10, OIL7B, OIL9B, OIL11B, OIL30B, OIL31B, etc. As a product made by Degussa, Printex3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, Printex A, Printex L, Printex G, Printex P, Printex U, Printex V Product made by cabot company, Printex G, SpecialBlack550, SpecialBlack350, SpecialBlack250, SpecialBlack 100, SpecialBlack6, SpecialBlack5, SpecialBlack4, ColorBlack FW1, ColorBlack FW2, ColorBlack FW2V, ColorBlack FW18, ColorBlack FW18, ColorBlack FW200, ColorBlack S160, ColorBlack S170 As, Monarch120, Monarch280, Monarch460, Monarch800, Mon arch880, Monarch900, Monarch1000, Monarch1100, Monarch1300, Monarch1400, Monarch4630, REGAL99, REGAL99R, REGAL415, REGAL415R, REGAL250, REGAL250R, REGAL330, REGAL400R, REGAL55R0, REGAL660R, BLACK PEARLS 480, PULLS130, ULC130, ULC As product made by carbon company, RAVEN11, RAVEN14, RAVEN15, RAVEN16, RAVEN22, RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RAVEN850, RAVEN890H, RAVEN1000, RAVEN1020, RAVEN1040, RAVEN1060U, RAVEN1080U, RAVENU1170 , RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000, and the like. In addition, it is particularly preferable to use resin coated carbon black for producing a resin black matrix having a high optical density and a high surface resistivity.

Moreover, as titanium black, the manufacturing method is the method obtained by heating the mixture of titanium dioxide and a metal titanium in a reducing atmosphere (reducing Japanese Patent Laid-Open Publication No. 49-5432), and the high temperature hydrolysis of titanium tetrachloride. A method of reducing fine titanium dioxide in a reducing atmosphere containing hydrogen (Japanese Laid-Open Patent Publication No. 57-205322), a method of high temperature reducing titanium dioxide or titanium hydroxide in the presence of ammonia (Japanese Patent Laid-Open Publication No. 60-65069). (JP-A-61-201610), a method of attaching a vanadium compound to titanium dioxide or titanium hydroxide, and high-temperature reduction in the presence of ammonia (JP-A-61-201610), and the like. It is not. As an example of the commercial item of titanium black, titanium black 10S, 12S, 13R, 13M, 13M-C etc. by Mitsubishi Material Corporation are mentioned.

As an example of another black pigment, red, green, blue three color materials can be mixed and used as a black pigment. Colorants which can be mixed to prepare a black colorant include Victoria Pure Blue (42595), Oramine O (41000), Catilon Brillient Flavine (Basic 13), Rhodamine 6GCP (45160), Roda Min B (45170), Safranin OK70: 100 (50240), eryoglausin X (42080), No.120 / Lionol Yellow (21090), Lionol Yellow GRO (21090), Simulator First Yellow 8GF ( 21105), Benzidine Yellow 4T-564D (2 1095), Simula First Red 4015 (12355), Lionol Red 7B 4401 (15850), Firstgen Blue TGR-L (74160), Lionol Blue SM (26150), Rio Knoll Blue ES (Pigment Blue 15: 6), Leonogen Red GD (Pigment Red 168), and Lionol Green 2YS (Pigment Green 36). In addition, the number in said parenthesis means color index (C.I.). Further, for pigments which can be used in other mixtures, C.I. In number, for example, C.I. Yellow pigment, 2O, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166, C.I. Orange pigments 36, 43, 51, 55, 59, 61, C.I. Red pigments 9, 97, 122, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, C.I. Violet pigments, 19, 23, 29, 30, 37, 40, 50, C.I. Blue pigment 15, 15: 1, 15: 4, 22, 60, 64, C.I. Green pigment 7, C.I. Brown pigment 23, 25, 26 etc. are mentioned.

In the resin composition for liquid crystal panels of the present invention, the content ratio of these color 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 solids. It is as follows. If the ratio of the colorant is too small, the film thickness with respect to the color concentration becomes too large, adversely affecting the gap control during liquid crystal cell formation and the like. On the other hand, if the ratio of the colorant is too large, sufficient image formability cannot be obtained.

1-4. Dispersant]

The resin composition for liquid crystal panels of this invention contains the dispersing agent used as needed. Although a dispersing agent is not specifically limited, A urethane type dispersing agent is preferable, As this urethane type dispersing agent, a polyisocyanate compound, the compound which has one or two hydroxyl groups in the same molecule, and an active hydrogen and a tertiary amino group are contained in the same molecule The urethane resin obtained by making a compound react is especially preferable.

Examples of the polyisocyanate compound include paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, tritin Aliphatic diisocyanates such as aromatic diisocyanate such as isocyanate, hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate, isophorone diisocyanate, 4,4'- Aromatic dicyclic isocyanate, such as methylenebis (cyclohexyl isocyanate), (omega), (omega) '-diisocinate, dimethyl cyclohexane, xylylene diisocyanate, (alpha), (alpha), (alpha)', (alpha) 'tetramethyl xylylene diisocyanate, etc. Aliphatic diisocyanate having a ring and lysine ester triisocyanate, 1,6,11 Undecane triisocyanate, 1,8- diisocyanate-4-isocyanate methyl octane, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, tris (isocyanate phenylmethane), tris (isocyanate phenyl) thiophosphate Triisocyanates, such as these, and trimers, water addition products, these polyol addition products, etc. are mentioned. Preferred as the polyisocyanate is a trimer of organic diisocyanate, most preferably a trimer of tolylene diisocyanate and a trimer of isophorone diisocyanate, and these may be used alone or in combination.

As a method for producing a trimer of isocyanate, the polyisocyanates may be prepared by using a suitable trimerization catalyst such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylic acid salts, and the like. After quantification and terminating the trimerization by addition of the catalyst poison, a method of obtaining the desired isocyanate group-containing polyisocyanate by removing unreacted polyisocyanate by solvent extraction and thin film distillation.

Moreover, as a compound which has one or two hydroxyl groups in the said molecule, polyether glycol, polyester glycol, polycarbonate glycol, polyolefin glycol, etc., and the alkoxylation of the alkyl group whose single terminal hydroxyl group of these compounds are C1-C25 And mixtures of two or more thereof.

Examples of the polyether glycols include polyetherdiol, polyetheresterdiol, and mixtures of two or more thereof. As polyetherdiol, what is obtained by individual or copolymerization of an alkylene oxide, for example, polyethyleneglycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol, And mixtures of two or more thereof. As polyether ester diol, what is obtained by reacting ether group containing diol or mixture with another glycol with dicarboxylic acid or its anhydride, or making alkyl glycol oxide react with polyester glycol, for example, poly (Polyoxytetramethylene) adipate etc. are mentioned. Most preferable as polyether glycol are polyethyleneglycol, polypropylene glycol, polyoxytetramethylene glycol, or the compound in which the single terminal hydroxyl group of these compounds was alkoxylated by the C1-C25 alkyl group.

As polyester glycol, For example, dicarboxylic acids, such as succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, and phthalic acid, or their anhydrides, 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 , Neopentyl glycol, 2-methyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,5- Pentanediol, 1,6-hexanediol, 2-methyl-2,4-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5 Alicyclic glycols such as -dimethyl-2,5-hexanediol, 1,8-octamethylene glycol, 2-methyl-1,8-octamethylene glycol, 1,9-nonanediol, and alicyclic glycols such as bishydroxymethylcyclohexane Such as group glycol, xylene glycol, bishydroxyethoxybenzene What is obtained by polycondensing diols, such as N-alkyl dialkanolamine, such as aromatic glycol and N-methyl diethanolamine, For example, a polyethylene adipate, a polybutylene adipate, a polyhexamethylene adipate, a polyethylene Polylactonediol or polylactone monool obtained by using a dipropylene or a monohydric alcohol having 1 to 25 carbon atoms as an initiator such as propylene adipate, for example, polycaprolactone glycol, polymethylvalerolactone, and And mixtures of two or more thereof. Most preferred as polyester glycol are polycaprolactone glycol having polycaprolactone glycol or an alcohol having 1 to 25 carbon atoms as an initiator, and more specifically, a compound obtained by ring-opening addition polymerization of ε-caprolactone to monool.

Examples of the polycarbonate glycol include poly (1,6-hexylene) carbonate, poly (3-methyl-1,5-pentylene) carbonate, and the like. Moreover, as polyolefin glycol, polybutadiene glycol, hydrogenated polybutadiene glycol, hydrogenated polyisoprene glycol, etc. are mentioned.

Among the compounds having one or two hydroxyl groups in these same molecules, polyether glycol and polyester glycol are particularly preferable. In addition, the number average molecular weight of the compound which has one or two hydroxyl groups in the same molecule is 300-10,000 normally, Preferably it is 500-6,000, More preferably, it is 1,000-4,000.

In the compound having active hydrogen and a tertiary amino group in the same molecule, active hydrogen, that is, a hydrogen atom directly bonded to an oxygen atom, a nitrogen atom, or a sulfur atom, is used in a functional group such as a hydroxyl group, an amino group, a thiol group, or the like. A hydrogen atom is mentioned, Especially, the hydrogen atom of an amino group, especially a primary amino group 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 dialkylamino group is connected to form a heterocyclic structure. Although a group, more specifically, an imidazole ring or a triazole ring is mentioned, Especially, since a dimethylamino group and an imidazole ring are excellent in dispersion stability, it is preferable.

Examples of the compound having active hydrogen and tertiary amino groups in the same molecule include N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, and 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 etc. are mentioned.

In addition, since the tertiary amino group is a nitrogen-containing hetero ring, pyrazole ring, imidazole ring, triazole ring, tetrazole ring, indole ring, carbazole ring, indazole ring, benzimidazole ring, benzotriazole ring Hetero 5-membered ring containing a nitrogen atom such as benzoxazole ring, benzothiazole ring, benzothiadiazol ring, pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, acridine ring, isoquinoline Nitrogen atom containing hetero 6-membered rings, such as a ring, are mentioned. Specific examples of the compounds having these imidazole rings and primary amino groups include 1- (3-aminopropyl) imidazole, histidine, 2-aminoimidazole, 1- (2-aminoethyl) imidazole, and the like. have. Moreover, when a compound which has a triazole ring and a primary amino group is concretely illustrated, 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-1,4-diphenyl-1,2,3-triazole, 3-amino-1-benzyl-1H-2,4-triazole and the like. Among these, N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, 1- (3-aminopropyl) imidazole, 3-amino-1,2,4 -Triazole, etc. are preferable.

The use ratio of these urethane resin dispersant raw materials is preferable that the compound which has one or two hydroxyl groups in the same molecule is 100-200 weight part normally with respect to 100 weight part of polyisocyanate compounds, Preferably it is 20-190 weight part More preferably, it is 30-180 weight part, and the compound which has active hydrogen and a tertiary amino group in the same molecule is 0.2-25 weight part normally, Preferably it is 0.3-24 weight part.

In addition, manufacture of a urethane resin dispersing agent is performed according to the well-known method of urethane resin manufacture. As a solvent at the time of manufacture, Ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, and isophorone, esters, such as ethyl acetate, butyl acetate, and a cellosolve, benzene, and toluene normally , Hydrocarbons such as xylene and hexane, some alcohols such as diacetone alcohol, isopropanol, second butanol and third butanol, halogenated hydrocarbons such as methylene chloride and chloroform, ethers such as tetrahydrofuran and diethyl ether Aprotic polar solvents such as dimethylformamide, N-methylpyrrolidone and dimethyl sulfoxide. In addition, as a catalyst at the time of manufacture, a normal urethanation reaction catalyst is used. For example, tin type, such as dibutyl tin dilaurate, dioctyl tin dilaurate, dibutyl tin dioctoate, stanas octoate, iron type, such as iron acetylacetonate and ferric chloride, triethylamine, and triethylene Tertiary amines such as diamine; and the like. Moreover, it is preferable to control the introduction amount of the compound which has active hydrogen and a tertiary amino group in the same molecule in the range of 1-100 mgKOH / g in the amine value of the dispersion resin after reaction, More preferably, it is 5-80 mgKOH It is the range of / g, More preferably, it is the range of 10-60 mgKOH / g. If the amine value is less than or equal to the above range, the dispersing ability tends to be lowered, and if it exceeds the above range, developability tends to decrease. In the case where the isocyanate group remains in the dispersion resin in the above reaction, it is preferable to further deform the isocyanate group in the alcohol or the amino compound because the elongation stability of the dispersion resin is increased.

In addition, the weight average molecular weight of polystyrene conversion measured by GPC of these urethane resin dispersing agents is 1, OO0-200, OOO normally, Preferably it is 2, OOO-100, OOO, More preferably, it is the range of 3,000-50,000. Dispersibility and dispersion stability are inferior at molecular weight 1,000 or less, and solubility falls at 200,000 or more, and when dispersibility is inferior, control of reaction becomes difficult simultaneously.

In the resin composition for liquid crystal panels of the present invention, the content ratio of these dispersants is usually 10% by weight or more, preferably 20% by weight or more, particularly preferably 30% by weight or more, with respect to the colorant component. Usually it is 300 weight% or less, Preferably it is 100 weight% or less, Especially preferably, it is 80 weight% or less. If the dispersant is too small, adsorption to the color material is insufficient, aggregation cannot be prevented, and high viscosity or gelation may occur. On the contrary, when the dispersant is too large, the film thickness becomes too thick, and the color filter is used to form a liquid crystal cell. Since the cell gap control failure in a process may come out, neither is preferable.

[1-5. Binder resin]

The resin composition for liquid crystal panels of this invention makes binder resin an essential component. The binder resin is, for example, Japanese Patent Application Laid-open No. Hei 7-207211, Japanese Patent Application Laid-open No. Hei 8-259876, Japanese Patent Application Laid-Open No. Hei 10-300922, Japanese Patent Application Laid-Open No. Hei 11-140144, and Japanese Laid-Open Patent Publication. Although the well-known high molecular compound described in Unexamined-Japanese-Patent No. 11-174224, Unexamined-Japanese-Patent No. 2000-56118, Unexamined-Japanese-Patent No. 2003-233179, etc. can be used, Among these, the high molecular compound which does not contain a nitrogen atom is preferable, Unsaturated monobasic acid is added to 10-100 mol% of the epoxy group of the copolymer of 5-90 mol% of epoxy group containing (meth) acrylates with 10-95 mol% of other radically polymerizable monomers copolymerizable with it, and furthermore, Resin obtained by adding a polybasic acid anhydride to 10-100 mol% of the hydroxyl group thus formed is especially preferable.

As the epoxy group-containing (meth) acrylate, for example, glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate Although 4-hydroxybutyl (meth) acrylate glycidyl ether etc. can be illustrated, Especially, glycidyl (meth) acrylate is preferable. These epoxy group containing (meth) acrylates may be used individually by 1 type, and may mix and use 2 or more types.

Moreover, as another radically polymerizable monomer which can be copolymerized with this epoxy group containing (meth) acrylate, using 1 type (s) or 2 or more types of mono (meth) acrylate which has a structure represented by following General formula (I) is used. desirable.

[In formula (I), R <^1> -R <^6> respectively independently represents a hydrogen atom or a C1-C3 alkyl group, R <^7> and R <^8> respectively independently represents a hydrogen atom or a C1-C3 alkyl group It may represent, or may be connected to form a ring.]

In said general formula (I), it is preferable that the ring formed by connecting R <^7> and R <^8> is an aliphatic ring, any of saturated or unsaturated may be sufficient, and it is preferable that carbon number is 5-6. Among these, as the structure of general formula (I), a structure represented by the following formula (Ia), (Ib), or (Ic) is preferable. By introducing these structures into binder resin, it is possible to increase heat resistance and strength as a resin composition for liquid crystal panels. 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 mono (meth) acrylate which has a structure represented by the said General formula (I), as long as it has a structure represented by the said General formula (I), well-known various things can be used, Especially as following general formula (II) It is preferable to be displayed.

[In formula (II), R <^9> represents a hydrogen atom or a methyl group, and R <^10> can mention the structure of the said general formula (I).]

In this invention, as a copolymer of the said epoxy group containing (meth) acrylate and the other radically polymerizable monomer copolymerizable with it, in the structural repeating unit derived from the other radically polymerizable monomer which can be copolymerized, It is preferable to contain 5-90 mol% of structural repeating units derived from the mono (meth) acrylate which has a structure represented by General formula (I), It is more preferable to contain 10-70 mol%, 15-50 It is especially preferable to contain mol%.

Moreover, as another radically polymerizable monomer copolymerizable other than the mono (meth) acrylate which has a structure represented by the said General formula (I), although it does not specifically limit, Specifically, For example, Styrene, Vinyl aromatics such as α-, o-, m-, p-alkyl, nitro, cyano, amide and ester derivatives of styrene; Dienes such as butadiene, 2,3-dimethylbutadiene, isoprene and chloroprene; Methyl (meth) acrylate, ethyl (meth) acrylate, (n) propyl (meth) acrylate, iso-propyl (meth) acrylate, -n-butyl (meth) acrylate, sec-butyl (meth) acrylate, (meth -Tert-butyl acrylate, pentyl (meth) acrylate, neopentyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, ( Dodecyl methacrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, dicyclohexyl (meth) acrylate, isoboroyl (meth) acrylate, (meth) acrylate Adamantyl acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, anthracenyl (meth) acrylate, anthraquinonyl (meth) acrylate, (meth) acrylate Piperonyl acrylate, salicylic (meth) acrylate, furyl (meth) acrylate, (meth Purfuryl acrylate, tetrahydrofuryl (meth) acrylate, pyranyl (meth) acrylate, benzyl (meth) acrylate, phenethyl (meth) acrylate, crezyl (meth) acrylate, (meth) acrylic acid-1,1,1 -Trifluoroethyl, perfluoroethyl (meth) acrylate, perfluoro-n-propyl (meth) acrylate, perfluoro-iso-propyl (meth) acrylate, triphenylmethyl (meth) acrylate, (meth) (Meth) acrylic acid esters such as acrylic acid cumyl, (meth) acrylic acid 3- (N, N-dimethylamino) propyl, (meth) acrylic acid-2-hydroxyethyl and (meth) acrylic acid-2-hydroxypropyl; (Meth) acrylic acid amide, (meth) acrylic acid N, N-dimethylamide, (meth) acrylic acid N, N-diethylamide, (meth) acrylic acid N, N-dipropylamide, (meth) acrylic acid N, N-di (meth) acrylic acid amides such as -iso-propylamide and anthracenylamide (meth) acrylate; Vinyl compounds such as (meth) acrylic acid anhydride, (meth) acryloylnitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine and vinyl acetate; Unsaturated dicarboxylic acid diesters such as diethyl citrate, diethyl maleate, diethyl fumarate and diethyl itaconic acid; Monomaleimides such as N-phenylmaleimide, N-cyclohexyl maleimide, N-lauryl maleimide, and N- (4-hydroxyphenyl) maleimide; N- (meth) acryloyl phthalimide etc. are mentioned.

Among these other radically polymerizable monomers, in order to impart excellent heat resistance and strength by the resin composition, it is effective to use at least one selected from styrene, benzyl (meth) acrylate, and monomaleimide, In the structural repeating unit derived from the other radically polymerizable monomer which can be copolymerized, the content rate of the structural repeating unit derived from at least 1 sort (s) chosen from these styrene, benzyl (meth) acrylate, and monomaleimide is 1 It is preferable that it is -70 mol%, and it is more preferable that it is 3-50 mol%.

Moreover, the well-known solution polymerization method is applied to the copolymerization reaction of the said epoxy group containing (meth) acrylate with the said other radically polymerizable monomer which can be copolymerized with it. The solvent to be used is not particularly limited as long as it is inert to radical polymerization, and an organic solvent which is usually used 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 acetate; 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 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; Dimethyl formamide, N-methylpyrrolidone, etc. are mentioned. These solvents may be used independently and may use 2 or more types together. The usage-amount of these solvents is 30-1000 weight part normally with respect to 100 weight part of copolymers obtained, Preferably it is 50-800 weight part. If the amount of the solvent used is outside this range, it is difficult to control the molecular weight of the copolymer.

In addition, the radical polymerization initiator used for copolymerization reaction will not be specifically limited if radical polymerization can be started, The organic peroxide catalyst and azo compound catalyst which are normally used can be used. Examples of the organic peroxide catalyst include those classified into known ketone peroxides, peroxy ketals, hydroperoxides, diallyl peroxides, diacyl peroxides, peroxy esters, and peroxydicarbonates. Specific examples thereof include benzoyl peroxide, dicumyl peroxide, diisopropyl peroxide, di-t-butyl peroxide, t-butyl peroxy benzoate, t-hexyl peroxy benzoate, and t-butyl peroxy-2. Ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 2,5-dimethyl-2, 5-bis (t-butylperoxy) hexyl-3,3-isopropylhydroperoxide, t-butylhydroperoxide, dicumylperoxide, dicumylhydroperoxide, acetylperoxide, bis (4-t-butyl Cyclohexyl) peroxydicarbonate, diisopropylperoxydicarbonate, isobutyl peroxide, 3,3,5-trimethylhexanoyl peroxide, lauryl peroxide, 1,1-bis (t-butylperoxy) 3, 3, 5- trimethyl cyclohexane, 1, 1-bis (t-hexyl peroxy) 3, 3, 5- trimethyl cyclohexane etc. are mentioned. Moreover, azobisisobutyronitrile, azobiscarboxyamide, etc. are mentioned as an azo compound catalyst. Among these, 1 type, or 2 or more types of radical polymerization initiator of suitable half life is selected and used according to superposition | 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 said monomers used for a copolymerization reaction, Preferably it is 1-10 weight part.

The copolymerization reaction may be performed by heating the monomer and radical polymerization initiator used in the copolymerization reaction in a solvent while stirring and dropping the monomer to which the radical polymerization initiator is added may be added dropwise into the solvent. Moreover, you may add the monomer dropwise in the middle of adding a radical polymerization initiator in a solvent and heating up. The reaction conditions can be freely changed depending on the desired molecular weight.

In this invention, as a copolymer of the said epoxy group containing (meth) acrylate with the said other radically polymerizable monomer copolymerizable with it, 5-90 mol of structural repeating units derived from an epoxy group containing (meth) acrylate. It is preferable that it consists of 10-95 mol% of structural repeating units derived from% and the other radically polymerizable monomer copolymerizable with it, It is further more preferable that it consists of 20-80 mol% of former and 80-20 mol% of the latter. And it is especially preferable that it consists of 30-70 mol% of former, and 70-30 mol% of the latter. When there are too few electronic epoxy group containing (meth) acrylates and there are too many other latter polymerizable monomers, since the addition amount of a polymeric component and an alkali-soluble component becomes inadequate, it is unpreferable, On the other hand, an electronic epoxy group containing (meth) acrylate is When there are too many and the other radically polymerizable monomers of the latter are too few, heat resistance and strength may fall.

Moreover, as an unsaturated monobasic acid added to the epoxy group of the copolymer of the said epoxy group containing (meth) acrylate with the said other radically polymerizable monomer copolymerizable with it, a well-known thing can be used and ethylenically unsaturated double The unsaturated carboxylic acid which has a bond is mentioned, As a specific example, (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, the (alpha) position haloalkyl, alkoxyl, halogen, nitro of (meth) acrylic acid And monocarboxylic acids such as cyano substituents. Especially, it is (meth) acrylic acid preferably. These 1 type may be used independently, or 2 or more types may be mixed and used.

Although these unsaturated monobasic acids are added at 10-100 mol% of the epoxy group of a copolymer, Preferably it is added at 30-100 mol%, More preferably, 50-100 mol%. When the addition ratio of this unsaturated monobasic acid is too small, the bad influence by a residual epoxy group, such as stability over time, is feared. Moreover, a well-known method can be employ | adopted as a method of adding unsaturated monobasic acid to the epoxy group of a copolymer.

Moreover, as a polybasic acid anhydride added to the hydroxyl group which arises when adding unsaturated monobasic acid to the epoxy group of a copolymer, a well-known thing can be used, A maleic anhydride, succinic anhydride, itaconic anhydride, a phthalic anhydride, tetrahydro phthalic anhydride, Dibasic acid anhydrides such as hexahydrophthalic anhydride and chloric anhydride; And polybasic acid anhydrides such as trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride and biphenyltetracarboxylic anhydride. Especially, tetrahydro phthalic anhydride and / or succinic anhydride are preferable. These polybasic acid anhydrides may be used individually by 1 type, and may mix and use 2 or more types. By adding such a component, alkali solubility can be provided to the binder resin used by this invention.

Although these polybasic acid anhydrides are added to 10-100 mol% of hydroxyl groups which arise when an unsaturated monobasic acid is added to the epoxy group of a copolymer, Preferably it is 20-90 mol%, More preferably, it is 30-80 mol% Add. When this addition ratio is too large, the residual film rate at the time of image development may fall, and when too small, solubility will become inadequate. Moreover, as a method of adding a polybasic acid anhydride to the hydroxyl group which arises when adding unsaturated monobasic acid to the epoxy group of a copolymer, a well-known method is employable.

In addition, in this invention, in order to improve the photosensitivity, after addition of the polybasic acid anhydride mentioned above, the glycidyl ether compound which has glycidyl (meth) acrylate and a polymerizable unsaturated group is added to a part of produced | generated carboxyl group. In order to improve the developability or improve the developability, a glycidyl ether compound having no polymerizable unsaturated group can be added to a part of the generated carboxyl group, and both of them may be added. As a specific example of the glycidyl ether compound which does not have a polymerizable unsaturated group, the glycidyl ether compound etc. which have a phenyl group and an alkyl group are shown, and it is a commercial item, for example, manufactured by Nagase Chemical Co., Ltd., brand name "Denacol EX- 111, Denacol EX-121, Denacol EX-141, Denacol EX-145, Denacol EX-146, Denacol EX-171, Denacol EX-192 Etc. Moreover, about these resin structures, for example, it is described in Unexamined-Japanese-Patent No. 8-297366 and Unexamined-Japanese-Patent No. 2001-89533, and it is 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 this molecular weight is less than 3000, heat resistance and film strength will fall, and if it exceeds 100000, it will not be preferable because it will lack solubility in a developing solution. Moreover, as for the ratio of the weight average molecular weight (Mw) / number average molecular weight (Mn) as a target of molecular weight distribution, 2.0-5.0 are preferable.

Moreover, as binder resin in this invention, the resin obtained by adding an epoxy group containing unsaturated compound to the carboxyl group part of carboxyl group-containing resin is also especially 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. As a carboxyl group-containing polymer monomer, it is (meth) acrylic acid, maleic acid, crotonic acid, itaconic acid, fumaric acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl adip, for example. Acid, 2- (meth) acryloyloxyethylmaleic acid, 2- (meth) acryloyloxyethylhexahydrophthalic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyloxy Propylsuccinic acid, 2- (meth) acryloyloxypropyladipic acid, 2- (meth) acryloyloxypropylmaleic acid, 2- (meth) acryloyloxypropylhydrophthalic acid, 2- (meth) acrylo Iloxypropylphthalic acid, 2- (meth) acryloyloxybutyl succinic acid, 2- (meth) acryloyloxybutyladipic acid, 2- (meth) acryloyloxybutyl maleic acid, 2- (meth) acrylic Ε-caprolactone, β-propio to vinyl monomers such as loyloxybutylhydrophthalic acid and 2- (meth) acryloyloxybutylphthalic acid, and acrylic acid Monomers obtained by adding lactones such as tonnes, γ-butyrolactone and δ-valerolactone, and acids or anhydrides such as succinic acid, maleic acid, phthalic acid, or their anhydrides to hydroxyalkyl (meth) acrylates. The monomer which added this, etc. are mentioned. Especially, (meth) acrylic acid and 2- (meth) acryloyloxyethyl succinic acid are preferable, and (meth) acrylic acid is more preferable. You may use these multiple types.

Moreover, carboxyl group-containing resin may copolymerize another polymerizable monomer which does not have a carboxyl group to said carboxyl group-containing polymerizable monomer. Although it does not specifically limit as another polymerizable monomer, 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) acrylic acid esters such as meth) acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, glycerol mono (meth) acrylate and tetrahydrofurfuryl (meth) acrylate ; Vinyl aromatics such as styrene and derivatives thereof; Vinyl compounds such as N-vinylpyrrolidone; N-substituted maleimides such as N-cyclohexyl maleimide, N-phenylmaleimide and N-benzyl maleimide; Macromonomers such as polymethyl (meth) acrylate macromonomer, polystyrene macromonomer, poly2-hydroxyethyl (meth) acrylate macromonomer, polyethylene glycol macromonomer, polypropylene glycol macromonomer, polycaprolactone macromonomer, etc. Can be mentioned. Especially preferable things are styrene, methyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, Hydroxypropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, N-cyclohexylmaleimide, N-benzylmaleimide, and N-phenylmaleide. You may use together multiple types.

Moreover, as carboxyl group-containing resin, what has a hydroxyl group is preferable from a dispersibility of a pigment, and as this hydroxyl-containing monomer, 2-hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acryl, for example. And hydroxyalkyl (meth) acrylates such as acrylate and 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, and the like.

Specifically as these carboxyl group-containing resins, (meth) acrylic acid, methyl (meth) acrylate, benzyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, Polymerizable monomer which does not contain hydroxyl groups, such as cyclohexyl (meth) acrylate and cyclohexyl maleimide, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and 4-hydroxybutyl ( Copolymers with hydroxyl group-containing monomers such as meth) acrylates; (meth) acrylic acid and methyl (meth) acrylates, benzyl (meth) acrylates, butyl (meth) acrylates and isobutyl (meth) acryl Copolymers of (meth) acrylic acid esters such as latex, 2-hydroxyethyl methacrylate, copolymers of (meth) acrylic acid and styrene, copolymers of (meth) acrylic acid, styrene and α-methylstyrene, and (meth) And the like can be mentioned methacrylic acid copolymer-cyclohexane end of raid.

The acid value of carboxyl group-containing resin in this invention is 30-500KOHmg / g normally, Preferably it is 40-350KOHmg / g, More preferably, it is 50-300KOHmg / g. In addition, the weight average molecular weight in GPC is 2000-80000, Preferably it is 4000-50000, More preferably, it is 5000-30000 in polystyrene conversion. If the weight average molecular weight is too small, the liquid stability is inferior, and if too large, the solubility of the resin composition for liquid crystal panel tends to deteriorate.

The epoxy group-containing unsaturated compound 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. For example, glycidyl (meth) acrylate and allyl glycy Dyl ether, glycidyl-α-ethyl acrylate, crotonyl glycidyl ether, (iso) crotonic acid glycidyl ether, N- (3,5-dimethyl-4-glycidyl) benzyl acrylamide, 4 Although non-cyclic epoxy group containing unsaturated compounds, such as -hydroxybutyl (meth) acrylate glycidyl ether, are mentioned, An alicyclic epoxy group containing unsaturated compound is preferable from a heat resistance and a dispersibility.

Here, as an alicyclic epoxy group containing unsaturated compound, as this alicyclic epoxy group, it is a 2, 3- epoxy cyclopentyl group, a 3, 4- epoxy cyclohexyl group, 7, 8- epoxy [tricyclo [5.2. 1.0] dec-2-yl] group, etc. Moreover, as an ethylenically unsaturated group, what originates in a (meth) acryloyl group is preferable, As a preferable alicyclic epoxy group containing unsaturated compound, it is a following general formula (IIIa) And compounds represented by (IIIm).

[In 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 is an integer of 1 to 10.]

In said general formula (IIIa)-(IIIm), as an alkylene group of R <_2> , it is preferable that carbon number is 1-10, Specifically, a methylene group, ethylene group, a propylene group, butylene group etc. can be illustrated. However, Preferably they are a methylene group, ethylene group, and a propylene group. Moreover, as a hydrocarbon group of R <^13> , a C1-C10 thing is preferable and an alkylene group, a phenylene group, etc. are mentioned.

These alicyclic epoxy group containing unsaturated compounds can be used together 2 or more types, Among these, the compound represented by the said General formula (IIIc) is preferable, and 3, 4- epoxycyclohexyl methyl (meth) acrylate is Particularly preferred.

In order to add the said epoxy group containing unsaturated compound to the carboxyl group part of the said carboxyl group-containing resin, a well-known method can be used, For example, carboxyl group-containing resin and an epoxy group containing unsaturated compound are 3, such as triethylamine and benzyl methylamine. Organic solvents in the presence of catalysts such as quaternary ammonium salts such as amine, dodecyltrimethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, benzyltriethylammonium chloride, pyridine and triphenylphosphine An epoxy group containing unsaturated compound can be introduce | transduced in the carboxyl group of resin by making it react for several hours to several ten hours at reaction temperature of 50-150 degreeC.

The acid value of the carboxyl group-containing resin into which the epoxy group-containing unsaturated compound is introduced is usually 10 to 200 KOH mg / g, preferably 20 to 150 KOH mg / g, and more preferably 30 to 150 KOH mg / g. In addition, 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 this invention, as binder resin, 1 type of binder resin mentioned above may be used independently, 2 or more types may be mixed and used, and the above-mentioned binder resin may be made especially with the urethane resin dispersing agent etc. which were mentioned above. In combination, the undissolved matter does not remain in the non-image part on a board | substrate, and the effect which can form the high density color pixel which is excellent in adhesiveness with a board | substrate is shown, and is preferable.

In the resin composition for liquid crystal panels 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 60, in the total solids. It is below weight%. When content of binder resin is less than this range, a film | membrane becomes weak and adhesiveness to a board | substrate may fall. On the contrary, when more than this range, the permeability of the developing solution to an exposure part will become high and the surface smoothness and sensitivity of a pixel may deteriorate.

1-6. Surfactants]

The resin composition for liquid crystal panels of this invention makes surfactant an essential component. As surfactant, various things, such as anionic, cationic, nonionic, and amphoteric surfactant, can be used, but it is unlikely to adversely affect various characteristics, such as voltage retention and compatibility with an organic solvent. In, it is preferable to use a nonionic surfactant.

As an anionic surfactant, For example, alkylsulphate ester salt type surfactants, such as "Emal 10" by Cao Corporation, alkylnaphthalene sulfonate type surfactants, such as "Perex NB-L" of the same company, " Homogenol L-18 "," Homogenol L-100 ", etc., special polymeric surfactant, etc. are mentioned. Of these, special polymer surfactants are preferable, and special polycarboxylic acid type surfactants are more preferable.

Moreover, as cationic surfactant, For example, alkylamine salt type surfactant, such as "Acetamine 24" by Cao Corporation, and quaternary ammonium salt type, such as "Cotamine 24P" and "Cotamine 86W" of the same company, etc. Surfactant etc. are mentioned. Among these, quaternary ammonium salt-based surfactants are preferable, and stearyl trimethylammonium salt-based surfactants are more preferable. As the nonionic surfactant, for example, silicon surfactant such as "SH8400" manufactured by Tresilicon, "KP341" manufactured by Silicon Corporation, "FC430" manufactured by Sumitomo 3M Corporation, Dainippon Ink Chemical Industries Fluorine-based surfactants such as "F470" manufactured by Neos Corporation, "DFX-18" manufactured by Neos Corporation, polyoxyethylene-based surfactants such as "Emalgen 104P" and "Emalgen A60" manufactured by Kao Corporation. . Of these, silicon-based surfactants are preferable, and so-called polyether-modified or aralkyl-modified silicon-based surfactants having a structure in which a side chain of a polyether group or an aralkyl group is added to the polydimethylsiloxane are more preferable.

The surfactant may be a combination of two or more thereof, and a combination of a silicon-based surfactant / fluorine-based surfactant, a silicon-based surfactant / special polymer-based surfactant, a fluorine-based surfactant / special-polymer surfactant, and the like can be given. Especially, a silicon type surfactant / fluorine type surfactant is preferable. Examples of the silicon-based surfactant / fluorine-based surfactant combination include polyether-modified silicon-based surfactants and oligomeric-type fluorine-based surfactants. Specifically, GE Toshiba Silicone Co., Ltd. "TSF4460" / Neos "DFX-18", Big Chemical Co., Ltd. "BYK-300" / Seimi Chemical Co., Ltd. "S-393", Shin-Etsu Silicone Co., Ltd. make `` KP340 '' / Dainippon Inks Co., Ltd. `` F-478 '', Torre Silicone Co., Ltd. `` SH7PA '', Daikin Co., Ltd. `` DS-401 '', Nippon Unicar `` L-77 '', Sumitomo 3M Co., Ltd. `` FC4430 '', etc. Can be mentioned.

In the resin composition for liquid crystal panels of the present invention, the content ratio of these surfactants is usually 0.001% by weight or more, preferably 0.005% by weight or more, more preferably 0.01% by weight or more, and particularly preferably in the total solids. 0.02% by weight or more, or 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.

1-7. Other components than solvents]

The resin composition for liquid crystal panels of the present invention may contain, in addition to the above components, a dispersing aid, an organic carboxylic acid or / and an organic carboxylic anhydride, a plasticizer, a thermal polymerization inhibitor, a storage stabilizer, a surface protector, an adhesion promoter, a development improver, and the like. You may contain it.

A dispersing aid is used for the improvement of the dispersibility of the said coloring material, the improvement of dispersion stability, etc., As this dispersing adjuvant, an azo system, a phthalocyanyl system, quinacridone system, benzimidazolone system, a quinoph Derivatives such as talon, isoindolinone, dioxazine, anthraquinone, indansrene, perylene, perinone, diketopyrrolopyrrole and dioxazine pigments. As a substituent of these pigment derivatives, a sulfonic acid group, a sulfonamide group, its quaternary salt, a phthalimide methyl group, a dialkylaminoalkyl group, a hydroxyl group, a carboxyl group, an amide group, etc. are shown, These substituents directly to a pigment skeleton, Or may be bonded via an alkyl group, an aryl group, a heterocyclic group, or the like, preferably a sulfonamide group, a quaternary salt thereof, or a sulfonic acid group, and more preferably a sulfonic acid group. In addition, these substituents may be substituted by two or more in one pigment skeleton, and the mixture of the compound from which a substituent differs may be sufficient. Specific examples of the pigment derivative 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, and diketopyrrolopyrrole compounds. Sulfonic acid derivatives of pigments, sulfonic acid derivatives of dioxazine pigments, and the like. Among them, sulfonic acid derivative of Pigment Yellow 138, sulfonic acid derivative of Pigment Yellow 139, sulfonic acid derivative of Pigment Red 254, sulfonic acid derivative of Pigment Red 255, Pigment Red ( 264 sulfonic acid derivative, pigment red 272 sulfonic acid derivative, pigment red 209 sulfonic acid derivative, pigment orange 71 sulfonic acid derivative, pigment violet 23 sulfonic acid derivative, more preferably Is a sulfonic acid derivative of Pigment Yellow 138 and a sulfonic acid derivative of Pigment Red 254.

In the resin composition for liquid crystal panels of this invention, the content rate of these dispersion adjuvant is 0.1 weight% or more with respect to the said color material component normally, Furthermore, it is 30 weight% or less normally, Preferably it is 20 weight% or less, Furthermore, Preferably it is 10 weight% or less, Especially preferably, it is 5 weight% or less. If the amount is small, the effect is not exerted. On the contrary, if the amount is excessively large, dispersibility and dispersion stability deteriorate.

In addition, the resin composition for liquid crystal panels of the present invention uses an organic carboxylic acid having an molecular weight of 1,000 or less and / or an organic carboxylic anhydride in order to further reduce the residuals of undissolved substances of the resin composition while maintaining high pattern adhesion. It may contain, It is preferable that these are contained when the dispersing agent mentioned above is a urethane resin dispersing agent. Specific examples of the organic carboxylic acid include aliphatic carboxylic acid and aromatic carboxylic acid. Examples of the aliphatic carboxylic acids include monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, capronic acid, glycolic acid, and (meth) acrylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, and adipic. Tricarboxylic acids such as dicarboxylic acids such as acid, pimelic acid, cyclohexanedicarboxylic acid, cyclohexanedicarboxylic acid, itaconic acid, citraconic acid, maleic acid and fumaric acid, tricarbaric acid and aconitic acid And acid. Moreover, as aromatic carboxylic acid, the carboxylic acid which the carboxyl group couple | bonded with phenyl groups, such as benzoic acid and phthalic acid directly, the carboxylic acid which the carboxyl group couple | bonded through the carbon bond from a phenyl group, etc. are mentioned. Among these, the molecular weight of 600 or less, especially the molecular weight of 50-500, specifically, maleic acid, malonic acid, succinic acid, itaconic acid are preferable. Moreover, as organic carboxylic anhydride, aliphatic carboxylic anhydride and aromatic carboxylic anhydride are mentioned, Specifically, acetic anhydride, trichloroacetic anhydride, trifluoroacetic anhydride, tetrahydrophthalic anhydride, succinic anhydride, Maleic anhydride, citraconic anhydride, itaconic anhydride, glutaric anhydride, 1,2-cyclohexenedicarboxylic acid anhydride, n-octadecylsuccinic anhydride, 5-norbornene-2,3-dicarboxyl anhydride Aliphatic carboxylic anhydrides, such as an acid, are mentioned. As aromatic carboxylic anhydride, phthalic anhydride, trimellitic anhydride, a pyromellitic anhydride, naphthalic anhydride etc. are mentioned. Among these, the molecular weight of 600 or less, especially the molecular weight of 50-500, specifically, maleic anhydride, succinic anhydride, citraconic anhydride, and itaconic anhydride are preferable.

In the resin composition for liquid crystal panels of the present invention, the content ratio of these organic carboxylic acids and / or organic carboxylic anhydrides is usually 0.01% by weight or more, preferably 0.03% by weight or more, more preferably in the total solids. Preferably it is 0.05 weight% or more, and is 10 weight% or less normally, Preferably it is 5 weight% or less, More preferably, it is 3 weight% or less.

Moreover, the resin composition for liquid crystal panels of this invention may contain the plasticizer, As a plasticizer, for example, a dioctyl phthalate, a dododecyl phthalate, a triethylene glycol dicaprylate, a dimethyl glycol phthalate, a tricresyl phosphate , Dioctyl adipate, dibutyl sebacate, triacetylglycerine and the like. It is preferable that the content rate of these plasticizers is 10 weight% or less in the total solid.

Moreover, the resin composition for liquid crystal panels of this invention may contain the thermal polymerization inhibitor, As this thermal polymerization inhibitor, hydroquinone, p-methoxyphenol, a pyrogallol, catechol, 2,6-, for example. t-butyl-p-cresol, β-naphthol, and the like. It is preferable that the content rate of these thermal polymerization inhibitors is the range of 3 weight% or less in all solid content.

1-8. solvent]

The resin composition for liquid crystal panels of this invention makes a solvent an essential component. A solvent has a function which melt | dissolves or disperse | distributes said each component, and adjusts a viscosity, As a solvent, for example, diisopropyl ether, mineral spirit, n-pentane, amyl ether, ethyl caprylate, n- Hexane, diethyl ether, isoprene, ethyl isobutyl ether, butyl stearate, n-octane, barsol # 2, afco # 18 solvent, diisobutylene, amyl acetate, butyl acetate, afcosine, butyl ether, Diisobutyl ketone, methylcyclohexene, methylnonyl ketone, propyl ether, dodecane, socar solvent Nos. 1 and 2, amyl formate, dihexyl ether, diisopropyl ketone, Solvetso # 150, (n 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 , Methylhexyl ketone, meth Isobutylate, benzonitrile, ethyl propionate, methyl cellosolve acetate, methyl isoamyl ketone, methyl isobutyl ketone, propyl acetate, amyl acetate, amyl formate, bicyclohexyl, diethylene glycol monoethyl ether acetate , Dipentene, methoxymethylpentanol, methyl amyl ketone, 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-ethoxypropionic acid methyl, 3-ethoxypropionic acid ethyl, 3-methoxypropionic acid methyl, 3-methoxypropionic acid propyl, 3-methoxypropionic acid propyl, 3-methoxy Butyl oxypropionate, 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, meth Methoxy butyl acetate, 3-methyl-3- methoxy butyl acetate, etc. are mentioned. Among these, propylene glycol monomethyl ether acetate, methoxy butyl acetate, and ethyl 3-ethoxy propionate are preferable. In addition, these solvents may be used individually by 1 type, or may be used in combination of 2 or more type. As a preferable solvent combination, the solvent containing a propene glycol monomethyl ether acetate and a methoxybutyl acetate, the solvent containing a propene glycol monomethyl ether acetate, ethyl 3-ethoxy propionate, etc. are mentioned, for example.

In the resin composition for liquid crystal panels of this invention, although the content rate of these solvents does not have a restriction | limiting in particular, The upper limit is 99 weight% or less normally. When the solvent exceeds 99% by weight, it is inappropriate to form a coating film if the concentration of each component excluding the solvent becomes too small. On the other hand, the lower limit of the solvent content ratio 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 and the like suitable for coating.

[2. Preparation of Resin Composition for Liquid Crystal Panel]

Next, the method of preparing the resin composition for liquid crystal panels of this invention is demonstrated.

In the present invention, when using the colorant as an optional component, first, the predetermined amount of the colorant, the dispersant, and the solvent are weighed, and the colorant is dispersed in the dispersion treatment step to form a liquid ink liquid. In this dispersion treatment step, a paint conditioner, sand grinder, ball mill, roll mill, stone mill, jet mill, homogenizer, or the like can be used. Since the color material becomes fine particles by performing this dispersion process, the coating characteristic of the resin composition for liquid crystal panels improves, and the transmittance | permeability, such as a color filter substrate of a product, improves. When disperse | distributing a color material, it is preferable to use together binder resin, a dispersion aid, etc. suitably. In addition, when performing a dispersion process using a sand grinder, it is preferable to use glass beads of 0.1 to several mm in diameter, or zirconia beads. The temperature at the time of dispersion | distribution process is 0 degreeC or more normally, Preferably it is room temperature or more, and also sets it normally in 100 degreeC or less, Preferably it is 80 degrees C or less. In addition, since the appropriate time varies depending on the composition of the ink liquid, the size of the sand grinder, and the like, the dispersion time needs to be appropriately adjusted.

A binder resin and a solvent as essential components, a surfactant, and optionally a photopolymerizable monomer and a photopolymerization initiating system as optional components, and other components are mixed with the ink liquid obtained by the dispersion treatment, and uniform. One dispersion solution is used. In addition, in each process of a dispersion process and mixing, since fine dust may mix, it is preferable to filter-process the obtained ink liquid with a filter etc.

[3. Physical Properties of Resin Composition for Liquid Crystal Panel]

As for the resin composition for liquid crystal panels of this invention, contact angle (theta) (degree) with respect to the clean glass surface of the liquid droplet of this resin composition, and surface tension (sigma) (mN / m) are following formula (1), (2), and (3 It is characterized by that). When any of following formula (1), (2), and (3) is not satisfied, it becomes difficult to solve the generation | occurrence | production of a coating nonuniformity and a dry nonuniformity simultaneously.

θ≤5 × (σ ₀ -σ) (1)

σ≤σ ₀ -1 (2)

θ≤15 (3)

[Wherein, sigma ₀ is the surface tension (mN / m) of the solvent alone used in the resin composition.]

Moreover, it is preferable that the resin composition for liquid crystal panels of this invention satisfy | fills following formula (1 '), (2), and (3), and following formula (1' '), (2' '), and ( It is more preferable to satisfy 3 ''), and it is particularly preferable to satisfy the following formulas (2 '' ') and (3' '').

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 resin composition for liquid crystal panels of this invention is surface leveling (sigma) '(mN / m) and before dilution, when it dilutes until the solvent weight doubles with the solvent used for the resin composition from a leveling property. It is preferable that surface tension (sigma) (mN / m) satisfy | fills following formula (4), It is more preferable to satisfy following formula (4 '), It is especially preferable to satisfy following formula (4 "). .

│σ-σ'│≤0.4 (4)

│σ-σ'│≤0.3 (4 ')

│σ-σ'│≤0.2 (4 '')

In addition, in this invention, the said contact angle and the said surface tension are respectively measured by the following method. In addition, the said dilution is performed by the following method.

<Contact angle>

(Iii) After washing the glass substrate for liquid crystal panels with a cleaning agent, light washing is performed by UV ozone treatment. By the above cleaning, the contact angle with pure water is 0 (zero) degrees, that is, a clean glass substrate wets while being fully diffused. In addition, the cleaning agent includes, for example, an alkali-based cleaning agent of a surfactant-containing type, and an inorganic alkali is preferable. As a specific example, "Sanwash TL-100" by a Lion company, "Semiclean KG" by a Yokohama fat and oil company are mentioned. UV ozone treatment is a low pressure mercury lamp irradiation apparatus (e.g., "VUM" manufactured by Oak Manufacturing Co., Ltd.), and the illuminance is usually 1 to 100 mW / cm 2, preferably 5 to 20 mW / cm 2 for 10 to 300 seconds, preferably 30 to It is performed on 120 second conditions.

(Ii) The contact angle with which the resin composition with respect to the glass substrate manufactured by (iii) is static is measured at 23 degreeC using the contact angle measuring apparatus by a liquid drop method. Here, "static contact angle" means the contact angle in the condition that the state change with time by a flow etc. does not generate | occur | produce. The liquid drop method is usually carried out by measuring within 1 minute after forming the liquid drop, preferably within 5 seconds to 20 seconds. As the contact angle measuring device, for example, direct reading, image processing or the like is used. As a direct reading contact angle measuring apparatus, "CA-DT" by Kyowa Interface Science, Ltd. is mentioned, for example. As an image-processing contact angle measuring apparatus, "MCA-2" by Kyowa Interface Science, "DSA100" by KRUSS, etc. are mentioned, for example.

<Surface tension>

The cleaned platinum plate whose surface was sufficiently glowing by alcohol lamp etc. is prepared, and the surface tension in which a resin composition is static is measured at 23 degreeC using the surface tension meter by a flat plate method. Here, "static surface tension" means the surface tension in the condition that the state change with time by a flow etc. does not generate | occur | produce. Examples of the surface tension meter include "CBVP-A3" manufactured by Kyowa Interface Science Co., Ltd. and "Sigma700" manufactured by KSV.

<Dilution method>

As room temperature, if it is used for the resin composition in a beaker, the same solvent is dripped and diluted little by little under stirring. Specifically, the mixture is diluted dropwise over 10 to 30 minutes while stirring with, for example, a magnetic stirrer at about 30 to 120 rpm.

Preparation of the resin composition for liquid crystal panels which satisfy | fills said Formula (1), (2) and (3) of this invention, and also (4) is the kind and quantity of the binder resin, surfactant, and solvent which were mentioned above. It is important to realize by selecting a combination, and the like, by adjusting the balance between the hydrophilicity and hydrophobicity, the lipophilic nature and the hydrophilicity, the molecular weight and the polarity of the surfactant. These adjustments are not to be inferred from the molecular structure of the specific surfactant or the like, but are specified by whether the whole composition satisfies the above formula.

[4. Application of Resin Composition for Liquid Crystal Panel]

The resin composition for liquid crystal panels of this invention is normally supplied to the board | substrate in the state melt | dissolved or dispersed in the solvent, and is used as a resist material etc. at the time of liquid crystal panel formation. As a supply method to a board | substrate, it can carry out by a conventionally well-known method, for example, the spinner method, the wire bar method, the flow coat method, the die coat method, the roll coat method, the spray coat method, etc. Especially, according to the die-coating method, it is preferable from a comprehensive viewpoint, such that the usage-amount of coating liquid is drastically reduced, and foreign matter generation which does not have the influence of the mist etc. which adhere | attach when using the spin coat method is suppressed at all is suppressed. And the resin composition for liquid crystal panels of this invention does not generate | occur | produce application | coating nonuniformity at the time of the application | coating, the drying nonuniformity in a subsequent drying process, etc., and has a very smooth surface through an exposure process, a developing process, a heat treatment process, etc. The layer which has is formed.

Hereinafter, as an application example to the liquid crystal panel of the resin composition for liquid crystal panels of this invention, the application as a black matrix of a color filter, a pixel, a photo spacer and rib material when attaching a color filter to a liquid crystal display device (liquid crystal division orientation protrusion) ) And the liquid crystal display device (panel) using the same will be described.

4-1. Black Matrix Pixel of Color Filter]

As a transparent substrate of a color filter, if there is transparency and suitable strength, the material is not specifically limited. Examples of the material include thermoplastic resins such as polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, acrylic resins such as polycarbonate resin and polymethyl methacrylate, and polysulfone resins. Thermosetting resin sheets, such as a 1st sheet, an epoxy resin, and unsaturated polyester resin, or various glass, etc. are mentioned. Among these, glass and heat resistant resin are preferable from a heat resistant viewpoint. These transparent substrates are subjected to surface treatments such as corona discharge treatment and ozone treatment, thin film formation treatment with various resins such as silane coupling agent or urethane resin, and the like, in order to improve surface properties such as adhesiveness. You may also 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 addition, when performing the thin film formation process by various resin, the film thickness is 0.01 micrometer or more normally, Preferably it is 0.05 micrometer or more, and also usually 10 micrometer or less, Preferably it is the range of 5 micrometer or less.

A color filter can be manufactured by providing a black matrix on the above-mentioned transparent substrate, and forming a pixel image of red, green, and blue normally. A black matrix is formed on a transparent substrate using the light shielding metal thin film or the resin composition for liquid crystal panels of this invention.

As the light-shielding metal material, chromium compounds such as metal chromium, chromium oxide, chromium nitride, nickel and tungsten alloys, etc. may be used, and these may be laminated on a multilayer image. These light-shielding metal thin films are generally formed by sputtering method, and form a desired pattern on a film by positive type photoresist. For chromium, an etching solution containing a mixture of dicerium ammonium nitrate and perchloric acid and / or nitric acid is used, and for other materials, etching is performed using an etching solution according to the material, and finally, the positive photoresist is peeled off using a dedicated release agent. By doing this, a black matrix can be formed. In this case, first, a thin film of these metals or metal-metal oxides is formed on the transparent substrate by vapor deposition, sputtering, or the like. Next, the coating film of the resin composition for positive photoresists is formed on this thin film. Next, using a photomask having a repeating pattern such as stripe, mosaic, triangle, etc., a coating film is exposed and developed to form a resist image. Thereafter, the coating film can be etched to form a black matrix.

When using the resin composition for liquid crystal panels of this invention, a black matrix is formed using the coloring resin composition containing a black color material. For example, black color materials such as carbon black, graphite, iron black, aniline black, cyanine black, titanium black or the like, or a mixture of red, green, blue, etc. suitably selected from inorganic or organic pigments and dyes. Using the coloring resin composition containing a black color material, it can carry out similarly to the method of forming the following red, green, and blue pixel image, and can form a black matrix. The said colored resin composition is used as at least 2 sorts of coating liquid for resist formation among these black, red, green, and blue. As for the black resist, on the transparent substrate, as for red, green and blue, on the resin black matrix forming surface formed on the transparent substrate, or on the metal black matrix forming surface formed using a chromium compound or other light shielding metal material Each process of application | coating, heat drying, image exposure, image development, and thermosetting is performed on it, and the pixel image of each color is formed.

After apply | coating and drying the coloring resin composition containing the color material of one color of red, green, and blue on the transparent substrate in which the black matrix was formed, superposing a photomask on a coating film, and interposing this photomask A pixel image is formed by image exposure, image development, and thermosetting or photocuring as needed, and a colored layer is produced. A color filter image can be formed by performing this operation with respect to the colored resin composition of three colors of red, green, and blue, respectively.

Application of the colored resin composition at that time can be performed by any of the above-mentioned methods. Especially, a diecoat method is preferable and what is necessary is just to select the application | coating conditions by a diecoat method suitably according to the composition of a resin composition, the kind of color filter to manufacture, etc. For example, it is preferable that the lip width of a nozzle tip is 50-500 micrometers, and the space | interval of a nozzle tip and a board | substrate surface shall be 30-300 micrometers. In order to adjust the thickness of a coating film, the traveling speed of a lip and the discharge amount of the liquid resin composition from a lip may be adjusted. When the thickness of the coating film becomes too large, the pattern development becomes difficult, while gap adjustment in the liquid crystal selization step may become difficult, while when the thickness of the coating film becomes too small, it becomes difficult to increase the pigment concentration, and desired color expression may become impossible. The thickness of the coating film 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 as the film thickness after drying. Is 5 micrometers or less.

It is preferable that the drying of the coating film after apply | coating a coloring resin composition to a board | substrate is a drying method using a hotplate, IR open, and a cavity oven. Usually, after preliminary drying, it heats again and dries. The conditions of predrying can be suitably selected according to the kind of the said solvent component, the performance of the dryer to be used, and the like. Drying temperature and drying time are selected according to the kind of solvent component, the performance of the dryer used, etc., Specifically, the drying temperature is usually 40 ° C or higher, preferably 50 ° C or higher, and usually 80 ° C or lower, preferably Is in the range of 70 ° C. or less, and the drying time is usually 15 seconds or more, preferably 30 seconds or more, and usually 5 minutes or less, preferably 3 minutes or less. In addition, the temperature condition of reheating drying is preferably a temperature higher than the predrying temperature, specifically, 50 ° C or higher, preferably 70 ° C or higher, and usually 200 ° C or lower, preferably 160 ° C or lower, particularly Preferably it is 130 degrees C or less. Moreover, although drying time changes also with heating temperature, it is preferable to set it as the range of 10 second or more normally, especially 15 second or more, and usually 10 minutes or less, especially 5 minutes or less. The higher the drying temperature, the better the adhesion to the transparent substrate. However, if the drying temperature is too high, the binder resin may decompose, causing thermal polymerization, and developing defects may occur. In addition, as a drying process of this coating film, you may use the pressure reduction drying method which dries in a pressure reduction chamber, without raising a temperature.

Image exposure superimposes a negative matrix pattern on the coating film of a colored resin composition, and irradiates a light source of an ultraviolet-ray or visible light through this mask pattern. At this time, as needed, in order to prevent the fall of the sensitivity of the photopolymerizable layer by oxygen, you may expose after forming an oxygen blocking layer, such as a polyvinyl alcohol layer, on a photopolymerizable layer. The light source used for the above-mentioned image exposure is not particularly limited. Examples of the light source include lamp sources such as xenon lamps, halogen lamps, tungsten lamps, high pressure mercury lamps, ultrahigh pressure mercury lamps, metal halide lamps, medium pressure mercury lamps, low pressure mercury lamps, carbon arcs, fluorescent lamps, argon ion lasers, YAG lasers, Laser light sources, such as an excimer laser, a nitrogen laser, a helium cadmium laser, and a semiconductor laser, etc. are mentioned. When irradiating and using the light of a specific wavelength, an optical filter can also be used.

A color filter can be manufactured by the following procedures, for example. That is, (i) Image exposure is performed with respect to the coating film of colored resin composition by the said light source. (ii) The image is formed on a substrate by developing using an organic solvent or an aqueous solution containing a surfactant and an alkaline compound.

This aqueous solution can further contain an organic solvent, a buffer, a complexing agent, a dye, or a pigment. Here, as an 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, sodium hydrogen phosphate, phosphoric acid Inorganic alkaline compounds such as potassium hydrogen, sodium dihydrogen phosphate, potassium dihydrogen phosphate and ammonium hydroxide, mono-di- or triethanolamine, mono-di- or tri-methylamine, mono-di- Or tri-ethylamine, mono- or di-isopropylamine, n-butylamine, mono-di- or tri-isopropanolamine, ethyleneimine, ethylenediamine, tetramethylammonium hydroxide (TMAH), choline Organic alkaline compounds, such as these, are mentioned. These alkaline compounds may be a mixture of two or more kinds. As surfactant, For example, Nonionic surfactant, such as polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene alkyl ester, sorbitan alkyl ester, monoglyceride alkyl ester, alkylbenzene Amphoteric surfactants, such as anionic surfactant, alkylbetaines, and amino acids, such as sulfonic acid salt, alkylnaphthalene sulfonic acid salt, alkylsulfonic acid salt, alkylsulfonic acid salt, and sulfosuccinic acid ester salt, are mentioned. As an organic solvent, isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol, etc. are mentioned, for example. The organic solvent can be used alone or in combination with an aqueous solution.

There is no restriction | limiting in particular in the conditions of image development processing, The image development temperature is 10 degreeC or more normally, especially 15 degreeC or more, Furthermore, 20 degreeC or more, Furthermore, 50 degrees C or less, Especially 45 degrees C or less, Furthermore, 40 degrees C or less Is preferred. The developing method can be based on any one of a deposition developing method, a spray developing method, a brush developing method, an ultrasonic developing method, and the like.

Moreover, the color filter in this invention apply | coats to the board | substrate the curable colored resin composition containing (1) solvent, a phthalocyanine-type pigment as a color material, and polyimide-type resin as a binder resin other than the said manufacturing method, and etching It can also manufacture by the method of forming a pixel image by the method. Moreover, (2) the method of forming a pixel image directly on a transparent substrate using a coloring resin composition containing a phthalocyanine pigment as a coloring ink, and (3) the coloring resin composition containing a phthalocyanine pigment. Is used as an electrodeposition liquid, the substrate is immersed in this electrodeposition liquid, and the method of depositing a colored film on the ITO electrode which became a predetermined pattern, Furthermore, the film which apply | coated the coloring resin composition containing the (4) phthalocyanine pigment, A method of forming a pixel image by an inkjet printer using a method of adhering to a transparent substrate and peeling, image exposure and development to form a pixel image, or (5) a colored resin composition containing a phthalocyanine-based pigment as a coloring ink. It can also manufacture by, etc. As a manufacturing method of a color filter, the method suitable for this is employ | adopted according to the composition of the resin composition for liquid crystal panels of this invention.

The thermosetting process is performed to the color filter after image development. The thermosetting treatment conditions at this time are usually 100 ° C. or higher, preferably 150 ° C. or higher, and usually 280 ° C. or lower, preferably 250 ° C. or lower, and the time is 5 minutes or more and 60 minutes. Choose from the following ranges. Through these series of steps, patterning image formation of one color is completed. This process is repeated sequentially, patterning black, red, green, and blue to form a color filter. In addition, the order of patterning of four colors is not limited to said order.

In addition, the color filter is used as a part of a component such as a color display and a liquid crystal display device by forming a transparent electrode such as ITO on the image in this state, but in order to increase the surface smoothness and durability, Topcoat layers, such as a polyamide and a polyimide, can also be formed on it. In addition, in some uses, such as a planar orientation type drive system (IPS mode), a transparent electrode may not be formed. In addition, in a vertically-oriented driving system (MVA mode), a rib can also be formed. In addition, a columnar structure (photo spacer) by photolithography may be formed instead of the bead distribution spacer.

4-2. Photo spacer]

The resin composition for liquid crystal panels of this invention is normally supplied on a board | substrate in the state melt | dissolved or dispersed in the solvent. As this supply method, it can implement also by the application | coating method of the shift | deviation mentioned above. Especially, the die-coat method is preferable, and application | coating amount is 0.5 micrometer or more, Preferably it is 1 micrometer or more as a dry film thickness, Moreover, it is 10 micrometers or less normally, Preferably it is 8 micrometers or less, More preferably, 5 It is the range of micrometer or less. In that case, it is important that the dry film thickness or the height of the finally formed spacer is uniform over the whole substrate. When the gap is large, nonuniform defects occur in the liquid crystal panel. Moreover, you may supply to a pattern shape by the inkjet method, the printing method, etc.

It is preferable that the drying after supplying a resin composition on a board | substrate is the drying method using a hotplate, IR open, and a cavity oven. In addition, you may combine the reduced pressure drying method which performs drying in a reduced pressure chance, without raising a temperature. The conditions for drying can be suitably selected according to the kind of solvent component, the performance of the dryer to be used, and the like. The drying time is usually selected in the range of 15 seconds to 5 minutes at a temperature of 40 to 100 ° C, preferably 30 seconds at a temperature of 40 to 90 ° C, depending on the kind of the solvent component, the performance of the dryer to be used, and the like. It is selected in the range of -3 minutes.

Exposure superimposes a negative mask pattern on the coating film of a resin composition, and irradiates a light source of an ultraviolet-ray or visible light through this mask pattern. Moreover, you may use the scanning exposure system by a laser beam. At this time, as needed, in order to prevent the fall of the sensitivity of the photopolymerizable layer by oxygen, you may expose after forming an oxygen blocking layer, such as a polyvinyl alcohol layer, on a photopolymerizable layer. As a light source used for said exposure, the same light source as mentioned above in manufacture of a color filter is used.

After performing the said exposure, an image pattern can be formed on a board | substrate by the image development using the aqueous solution containing an alkaline compound and surfactant, or an organic solvent. This aqueous solution may further contain an organic solvent, a buffer, a complexing agent, a dye, or a pigment. As an alkaline compound, surfactant, and the organic solvent used in that case, the thing similar to what was mentioned above in manufacture of a color filter is used. Moreover, it is preferable to perform a thermosetting process to the board | substrate after image development. The thermosetting treatment conditions at this time are selected in the range of 100 to 280 ° C, preferably in the range of 150 to 250 ° C, and the time is selected in the range of 5 to 60 minutes.

4-3. Rib (Liquid Crystal Orientation Projection)]

The ribs (liquid crystal division alignment projections) refer to projections formed on the transparent electrode in order to improve the viewing angle of the liquid crystal display device, and locally tilt the liquid crystal using the slope of the projections to fill the liquid crystal in one pixel. To split in the direction.

The resin composition for liquid crystal panels of this invention is apply | coated by any one of the above-mentioned application | coating methods on the color filter substrate manufactured as mentioned above and in which transparent electrodes, such as ITO, were formed on the image. The coating film thickness of a resin composition is 0.5-5 micrometers normally. After drying the coating film which consists of this composition, a photo mask is put on a dry coating film, and image exposure is performed through the photo mask. After exposure, the uncured portion of the unexposed light is removed by development to form a pixel. Usually, the image obtained after image development has a tendency for the thin line reproducibility of the thing of 5-20 micrometers to be requested | required, and the fine line reproducibility which is more precise is calculated | required from the request of a high quality display. In stabilizing and reproducing high-definition fine lines, the shape of the edge surface of the thin line image after development has a rectangular shape in which the contrast of the non-image and the image portion is clear, such as development time, developer elapsed time, and physical stimulation of the development shower. Development margin is widely preferred.

In the present invention, the image after development has an edge shape close to that of a rectangular shape. In order to obtain the shape of the arch shape necessary for the shape of the ribs, 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 Heat treatment at 280 ° C. or less, 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, and more preferably 40 minutes or less. Then, the rectangular edge surface is deformed into an arch shape, and ribs having a width of 0.5 to 20 µm and a height of 0.2 to 5 µm are formed. As the range of the deformation | transformation at the time of this heating, the thin film image after the said heat processing of the contact angle W1 formed from the side surface of the thin line image (rectangular image edge surface shape) before a heating, and a board | substrate plane is adjusted suitably. The ratio of the contact angle (W2) formed from the side surface of the substrate to the substrate plane, W1 / W2 is 1.2 or more, preferably 1.3 or more, more preferably 1.5 or more, and usually 10 or less, preferably 8 or less. . The higher the heating temperature, or the longer the heating time, the larger the strain, and conversely, the lower the heating temperature, or the shorter the heating time, the lower the strain.

4-4. Liquid crystal display (panel)]

The liquid crystal panel which concerns on this invention can comprise the said color filter board | substrate and the drive board | substrate by a thin film transistor (TFT) by the structure which opposed through the liquid crystal layer, for example. More specifically, the TFT filter substrate is attached to the color filter substrate coated with the alignment film material and subjected to the alignment treatment through the peripheral seal material, and the liquid crystal material is injected into the gap to form a liquid crystal panel. can do.

In the liquid crystal panel according to the present invention, after forming an alignment film on the color filter according to the present invention, spreading a spacer on the alignment film, the liquid crystal panel is attached to an opposing substrate to form a liquid crystal cell and formed on the formed liquid crystal cell. It manufactures by inject | pouring a liquid crystal and connecting to a counter electrode. The alignment film is preferably a resin film such as polyimide. The gravure printing method and / or the flexographic printing method are employ | adopted for formation of an orientation film normally, and the thickness of an orientation film becomes several 10 nm. After hardening an alignment film by thermosetting, it surface-processes by irradiation of an ultraviolet-ray or a rubbing gun, and is processed into the surface state which can adjust the inclination of a liquid crystal.

As for the spacer, one having a size corresponding to a gap (interval) with the opposing substrate is used, and one having a size of 2 to 8 µm is usually suitable. On the color filter substrate, the photo spacer PS of a transparent resin film can be formed by the photolithographic method, and this can be utilized instead of a spacer. As the counter substrate, an array substrate is usually used, and in particular, a TFT (thin film transistor) substrate is suitable. In addition, although the gap of adhesion with an opposing board | substrate changes with the use of a liquid crystal panel, it is normally selected in the range of 2 micrometers or more and 8 micrometers or less. After sticking with a counter substrate, parts other than a liquid crystal injection hole are sealed by real materials, such as an epoxy resin. The actual material is cured by UV irradiation and / or heating, and the periphery of the liquid crystal cell is sealed.

The liquid crystal cell sealed in the periphery is cut into a panel unit, and the pressure is reduced in the vacuum chamber, the liquid crystal injection port is immersed in the liquid crystal, and then the liquid crystal is injected into the liquid crystal cell by leaking the chamber. The decompression degree in the liquid crystal cell is usually 1 × 10 ^-2 Pa or more, preferably 1 × 10 ^-3 or more, or usually 1 × 10 ^-7 Pa or less, preferably 1 × 10 ^-6 Pa or less. . Moreover, it is preferable to heat a liquid crystal cell at the time of pressure reduction, and a heating temperature is 30 degreeC or more normally, Preferably it is 50 degreeC or more, Moreover, it is 100 degrees C or less normally, Preferably it is the range of 90 degrees C or less. The heating and holding at the time of reduced pressure 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 which injected the liquid crystal hardens and seals a liquid crystal injection port with UV curable resin, and a liquid crystal display device (panel) is completed. Moreover, there is no restriction | limiting in particular in the kind of liquid crystal, As a liquid crystal conventionally known, such as an aromatic type, an aliphatic type, and a polycyclic compound, any of lyotropic liquid crystal and a thermotropic liquid crystal may be sufficient. Although a nematic liquid crystal, a smear liquid crystal, a cholesteric liquid crystal, etc. are known for a thermotropic liquid crystal, any may be sufficient.

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 addition, in the following example and the comparative example, the measurement of a contact angle and surface tension was based on the following methods, respectively.

<Contact angle>

After cleaning the glass substrate for liquid crystal panels ("AN100" by Asahi Glass Co., Ltd.) with a washing | cleaning agent ("Sunwash TL-100" by Lion Corporation), it washes light by performing UV ozone treatment at 1000mj, and in pure water By a 0 degree, that is, a fully diffused glass substrate is prepared. Next, using the commercially available contact angle measuring device ("CA-DT" by Kyowa Interface Science) by the liquid drop method, the static contact angle with the resin composition with respect to a glass substrate is measured at 23 degreeC.

<Surface tension>

The surface of the resin composition at 23 ° C. is statically prepared by preparing a plate of platinum that has been sufficiently heated with an alcohol lamp or the like and cleaned, and using a commercially available surface tension gauge (“CBVP-A3” manufactured by Kyowa Interface Science Co., Ltd.). Measure the tension.

Example 1

Pigment Red 177 10g as a coloring material, 13.3g of "byk-161" (non-volatile content 30%) by Big Chem Corporation as a dispersing agent, and the pigment dispersion which mixed 46.7g of propylene glycol monomethyl ether acetate as a solvent were prepared. Furthermore, separately, as a binder resin, the ternary copolymer resin of styrene (55 mol%) / (alpha) -methylstyrene (15 mol%) / acrylic acid (20 mol%) / structural repeating unit (10 mol%) of the following structure ( Weight average molecular weight 12000) 5.0 g, dipentaerythritol hexaacrylate 5.0 g as a photopolymerizable monomer, 2- (2-chlorophenyl) -4,5-diphenyl imidazole dimer 0.4 g, 4 as a photoinitiator 0.2 g of 4, -bis (diethylamino) benzophenone, 0.4 g of 2-methylbenzothiazoles as a polymerization accelerator, 0.013 g of fluorine-based surfactants "F475" manufactured by Dainippon Ink, Inc. 0.05 g of surfactant "BYK-323" and a solvent were prepared as a clear resist in which 29.5 g of propreglycol monomethyl ether acetate and 36.6 g of methoxybutyl acetate were mixed. The mixture was further mixed and uniformly stirred, and then 300 g of zirconia beads having a particle diameter of 0.5 mm were added, shaken and dispersed in a paint conditioner for 5 hours, and then filtered to obtain a uniform liquid resin panel composition.

In this resin composition for liquid crystal panels, the contact angle θ of the liquid drop on the clean glass surface was 8 degrees. Moreover, surface tension (sigma) was 25.6 mN / m, and surface tension (sigma) ₀ of the solvent alone was 27.6 mN / m. Moreover, the surface tension (sigma) when diluting until the solvent weight doubled with the solvent was 25.9 mN / m.

After apply | coating this resin composition for liquid crystal panels one sheet to a glass substrate by the slit die on the conditions of application | coating speed | rate 100mm / s, application | coating gap 100 micrometers, and application | coating thickness of wet 20 micrometers, reaching pressure 1Torr with a reduced pressure drying chamber. Dried in vacuo and baked for 3 minutes with a hotplate at 80 ° C. The application | coating nonuniformity and the generation | occurrence | production nonuniformity of the application | coating nonuniformity were observed by this interference fringe test lamp (Na lamp) about this apply | coated board | substrate, and it was a result shown in Table 1.

Example 2

A resin composition for liquid crystal panels was prepared in the same manner as in Example 1 except that 0.025 g of BIC Chemi Co., Ltd.-based silicon-based surfactant "BYK-323" was used. In this resin composition for liquid crystal panels, the contact angle θ of the liquid drop on the clean glass surface was 3 degrees. In addition, surface tension (sigma) was 26.2 mN / m, and surface tension (sigma) ₀ of the solvent alone was 27.6 mN / m. In addition, the surface tension (sigma) 'when it diluted until the solvent weight doubled with the solvent was 26.5 mN / m. About this coating board | substrate, when the generation | occurrence | production situation of application | coating nonuniformity and dry nonuniformity was observed by interference fringe test etc. (Na lamp | ramp), it was a result shown in Table 1.

Example 3

As a surfactant, it is the same as that of Example 1 except having used 0.025g of fluorine-type surfactants "F470" by Dainippon Ink Corporation, and 0.049g of silicon-based surfactant "BYK-330" (51% of non volatile components) by Big Chemi Corporation. It was made to prepare the resin composition for liquid crystal panels. In this resin composition for liquid crystal panels, the contact angle θ of the liquid drop on the clean glass surface was 5 degrees. Moreover, surface tension (sigma) was 25.7 mN / m, and surface tension (sigma) ₀ of the solvent alone was 27.6 mN / m. In addition, the surface tension (sigma) 'when it diluted until the solvent weight doubled with the solvent was 25.9 mN / m. About the application | coating board | substrate, the generation | occurrence | production situation of application | coating nonuniformity and dry nonuniformity was observed by the interference fringe test lamp (Na lamp), and it was a result shown in Table 1.

Comparative Example 1

As a surfactant, the resin composition for liquid crystal panels was prepared like Example 1 except having used 0.013g of fluorine-type surfactants "S-393" by Seimi Chemical. In this resin composition for liquid crystal panels, the contact angle θ of the liquid drop on the clean glass surface was 25 degrees. Moreover, surface tension (sigma) was 23.8 mN / m, and surface tension (sigma) ₀ of the solvent alone was 27.6 mN / m. In addition, the surface tension (sigma) 'when it diluted until the solvent weight doubled with the solvent was 25.0 mN / m. About the application | coating board | substrate, the generation | occurrence | production situation of application | coating nonuniformity and dry nonuniformity was observed by the interference fringe test lamp (Na lamp), and it was a result shown in Table 1.

Comparative Example 2

As a surfactant, it carried out similarly to Example 1 except having used 0.025g of fluorine-type surfactants "DFX-18" by Neos Corporation, and prepared the resin composition for liquid crystal panels. In this resin composition for liquid crystal panels, the contact angle θ of the liquid drop on the clean glass surface was 20 degrees. Moreover, surface tension (sigma) was 26.1 mN / m and surface tension (sigma) ₀ of the solvent alone was 27.6 mN / m. In addition, the surface tension (sigma) 'when it diluted until the solvent weight doubled with the solvent was 26.5 mN / m. The application | coating nonuniformity and the generation | occurrence | production nonuniformity of the application | coating nonuniformity were observed by this interference fringe test lamp (Na lamp) about this apply | coated board | substrate, and it was a result shown in Table 1.

Comparative Example 3

A resin composition for liquid crystal panels was prepared in the same manner as in Example 1, except that 0.05 g of a silicon chemical surfactant BYK-333 manufactured by Vicchemy Co., Ltd. was used as the surfactant. In this resin composition for liquid crystal panels, the contact angle θ of the liquid drop on the clean glass surface was 15 degrees. Moreover, surface tension (sigma) was 25.6 mN / m, and surface tension (sigma) ₀ of the solvent alone was 27.6 mN / m. Further, the surface tension σ 'when diluted until the solvent weight by the solvent doubled was 26.1 mN / m. About the application | coating board | substrate, the generation | occurrence | production situation of application | coating nonuniformity and dry nonuniformity was observed by the interference fringe test lamp (Na lamp), and it was a result shown in Table 1.

Comparative Example 4

A resin composition for liquid crystal panels was prepared in the same manner as in Example 1 except that 0.025 g of silicon chemical surfactant BYK-331 manufactured by BIC Chem Corporation was used as the surfactant. In this resin composition for liquid crystal panels, the contact angle θ of the liquid drop on the clean glass surface was 6 degrees. Moreover, surface tension (sigma) was 27.3 mN / m, and surface tension (sigma) ₀ of the solvent alone was 27.6 mN / m. In addition, the surface tension (sigma) 'when it diluted until the solvent weight doubled with the solvent was 27.5 mN / m. About the application | coating board | substrate, the generation | occurrence | production situation of application | coating nonuniformity and dry nonuniformity was observed by the interference fringe test lamp (Na lamp), and it was a result shown in Table 1.

Although this invention was demonstrated in detail using the specific aspect, it is clear for those skilled in the art for various changes and modification to be possible, without leaving | separating the intent and range of this invention.

In addition, this application is based on the JP Patent application (Japanese Patent Application 2004-363686) of an application on December 15, 2004, The whole is taken in into consideration.

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

Claims (6)

A resin composition for a liquid crystal panel containing a binder resin, a surfactant, and a solvent, wherein the contact angle θ (degrees) with respect to the clean glass surface of the liquid drop of the resin composition and the surface tension σ (mN / m) of the resin composition are as follows. Formula (1), (2), and (3) are satisfied, The resin composition for liquid crystal panels characterized by the above-mentioned. θ≤5 × (σ ₀ -σ) (1) θ≤σ ₀ -1 (2) θ≤15 (3) [Wherein, sigma ₀ is the surface tension (mN / m) of the solvent alone used in the resin composition.] The surface tension σ '(mN / m) and the surface tension σ (mN before dilution) when the resin composition for liquid crystal panels of Claim 1 is diluted until the solvent weight doubles with the solvent used for the resin composition. / m) The resin composition for liquid crystal panels which satisfy | fills following formula (4). │σ-σ'│≤0.4 (4) The method according to claim 1 or 2, The resin composition for liquid crystal panels containing a silicon type surfactant as surfactant. The method according to claim 1 or 2, The resin composition for liquid crystal panels containing a fluorochemical surfactant as surfactant. The color filter formed using the resin composition for liquid crystal panels of Claim 1 or 2. The liquid crystal panel formed using the resin composition for liquid crystal panels of Claim 1 or 2.