JP3938375B2 - Photosensitive coloring composition, color filter, and liquid crystal display device - Google Patents

Description

The present invention is sensitive light colored composition are those color filters, and a liquid crystal display device. More specifically, the photosensitive coloring composition is excellent in liquid stability and heat resistance, has little background stain during development, has good adhesion to the substrate, has a good pixel edge shape, and is suitable for the production of color filters. It is about things.

Conventionally, as a method for producing a color filter using a pigment, a dyeing method, an electrodeposition method, an ink jet method, a pigment dispersion method, and the like are known.
In the case of the pigment dispersion method, a photosensitive coloring composition obtained by adding a binder resin, a photopolymerization initiator, a photopolymerizable monomer, etc. to a coloring composition obtained by dispersing a pigment with a dispersing agent or the like is usually a glass substrate. After coating on top and drying, exposure is performed using a mask and development is performed to form a colored pattern, which is then heated to fix the pattern to form pixels. These steps are repeated for each color to form a color filter. Thus, in the image formation of the color filter using the photosensitive coloring composition, sufficient resolution, adhesion to the substrate, low development residue and the like are required. Furthermore, in recent years, a pixel having a high color density and a resin black matrix having a high optical density are required, and the content of a coloring material such as a pigment or carbon black in the photosensitive coloring composition tends to be high.

  On the other hand, in general, a photosensitive composition containing a photopolymerizable component, a photopolymerization initiator, and a binder resin, including the photosensitive coloring composition, generally includes coating, drying, exposure, and development steps. Although it is used for the photolithography process that passes, in such a process, there is no residue or soiling in the removed part in the development process, the removed part has sufficient solubility, the sharpness of the pattern edge, etc. There is always a need to improve the pixel formability.

  In particular, when a pixel is formed using a photosensitive coloring composition having a high content of the coloring material as described above, a residue or background stain is generated on the substrate in the unexposed area in the development process, and the unexposed area is well dissolved. Such as inability to obtain image quality, inferior sharpness of the edge shape of the pixel, and the phenomenon that the sensitivity of the pixel formed in the exposed area is not sufficient and the surface smoothness is notable. Met.

  Then, the photosensitive coloring composition using the novolak epoxy acrylate which has a carboxyl group as binder resin is disclosed (refer patent document 1). However, even when this binder resin is used, the balance between solubility and sensitivity is inferior, so that the developer permeates into the exposed area at the same time as the unexposed area dissolves, and the pixel edge becomes shaky. It has been found that the problem of poor adhesion occurs.

Furthermore, although the photosensitive resin composition which uses the alicyclic epoxy group containing unsaturated compound for the acrylic resin which has a carboxyl group is disclosed as binder resin (refer patent document 2), when this binder resin is used However, it has been found that since the sensitivity is not sufficient, the adhesion of the pixel to the substrate is poor and it is difficult to form a high-definition pixel.
Japanese Patent Laid-Open No. 11-84126 JP-A-1-289820

An object of the present invention is excellent in image-forming property even when the concentration of the coloring material high photosensitive coloring composition suitable for color filter applications, and color filter manufactured using the same, to provide a liquid crystal display device There is.

Therefore, as a result of intensive studies to solve the above problems, the present inventors have found that a photosensitive composition containing a specific binder resin (A) and a photopolymerization initiator (B) has an excellent balance between sensitivity and solubility. Furthermore, the inventors have found that the sharpness and adhesion of the pixel edge are very excellent, and found that the shape of the obtained light-shielding pattern (black matrix) is good, and have reached the present invention.
That is, the first gist of the present invention is a binder obtained by further reacting a reaction product of an epoxy resin (a) and an unsaturated group-containing carboxylic acid (b) with a polybasic carboxylic acid or its anhydride (c). cyclic with the resin (a), the a photosensitive composition containing the photopolymerization initiator (B), the epoxy resin in the binder resin (a) (a) is two or more unsaturated groups per molecule a polyaddition reaction product of a hydrocarbon compound and a phenol, the reaction product of an epihalohydrin, and a photopolymerization initiator (B) is an oxime-based initiator der Ru sensitive optical composition, and a coloring material ( A photosensitive coloring composition containing C) .

The second gist of the present invention is that, in the cross-sectional shape when a light-shielding pattern is formed on the transparent substrate using the photosensitive coloring composition in which the color material (C) is a black color material, The color filter is characterized in that an angle formed between the surface in contact with the substrate and the substrate surface is 50 degrees or less.

The third gist of the present invention resides in a liquid crystal display device using the color filter.

  The photosensitive composition of the present invention has good adhesion to the substrate. In addition, a photosensitive coloring composition containing a coloring material is excellent in developability, adhesion to a substrate or a light shielding layer, and surface smoothness even when containing a coloring material such as pigment or carbon black at a high concentration. High-definition pixels can be formed. Furthermore, it is possible to provide a high-quality color filter using the photosensitive coloring composition and a high-quality liquid crystal display device using the color filter.

  The photosensitive composition of the present invention is not only used for color filters, but also for solder resists for flexible printed wiring boards, plating resists, correlated insulating films for multilayer printed wiring boards, photosensitive optical waveguides, photo-curable liquid crystal sealing materials, and photo-curing. It is useful as a type EL sealing material, a photocurable adhesive, and the like.

Hereinafter, the present invention will be described in detail.
[Photosensitive composition]
The photosensitive composition of this invention contains binder resin (A) and a photoinitiator (B) as an essential component, and contains a photopolymerizable monomer etc. as needed.
<Binder resin (A)>
The binder resin (A) is obtained by further reacting a reaction product of the epoxy resin (a) and the unsaturated group-containing carboxylic acid (b) with a polybasic carboxylic acid or its anhydride (c).

Epoxy resin (a)
The epoxy resin (a) is a polyaddition reaction product of a cyclic hydrocarbon compound having two or more unsaturated groups per molecule (hereinafter simply referred to as “unsaturated cyclic hydrocarbon compound”) and a phenol, It is a reaction product with epihalohydrin.
The binder resin (A) exhibits good characteristics because the constituent epoxy resin (a) has a cyclic hydrocarbon structure, which is bulky, and has an appropriate hydrophobicity, so that the developing solution penetrates the exposed area. It is possible to prevent erosion caused by

The number of unsaturated groups contained in the unsaturated cyclic hydrocarbon compound is usually 4 or less per molecule, but preferably 2 groups.
The unsaturated cyclic hydrocarbon compound is not particularly limited, but usually has 5 to 20 carbon atoms, preferably 6 to 12 carbon atoms. Specifically, unsaturated aliphatic hydrocarbon compounds such as dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, 5-vinylnorborna-2-ene, α-pinene, β-pinene and limonene, and divinylbenzene and the like. A saturated aromatic hydrocarbon compound is mentioned. Of these, dicyclopentadiene is particularly preferred. Since dicyclopentadiene is contained in petroleum fractions, industrial dicyclopentadiene may contain other aliphatic or aromatic dienes as impurities. Considering the above, it is desirable that dicyclopentadiene is 90% by weight or more. Particularly preferred are those having a purity of 95% by weight or more.

  Next, the phenol to be polyadded with the unsaturated cyclic hydrocarbon compound is not particularly limited as long as it is a compound having at least one aromatic hydroxyl group in one molecule, specifically, an unsubstituted phenol, And substituted phenols to which an alkyl group, alkenyl group, allyl group, aryl group, aralkyl group or halogen group is bonded. The latter substituted phenols include cresol, xylenol, ethylphenol, isopropylphenol, butylphenol, octylphenol, nonylphenol, vinylphenol, isopropylphenol, allylphenol, phenylphenol, benzylphenol, chlorophenol, bromophenol (each with different substitution positions) Monosubstituted phenols such as isomers), disubstituted phenols such as dimethylphenol and t-butyl-methylphenol (including isomers having different substitution positions), or trimethylphenol (isomers having different substitution positions). 1-naphthol, 2-naphthol, dihydroxynaphthalene (1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7) -, 1, -, 2,3-, 2,6-, 2,7-isomers), bisphenol A, bisphenol F, bisphenol S, bisphenol Z, bisphenol P, bisphenol M, dihydroxynaphthalenebenzophenone, biphenyl, And dihydric phenols such as hydroquinone and resorcin. Of these, phenol and cresol are preferred from the viewpoint of curability.

Epichlorohydrin, epiiodohydrin, epibromohydrin, β-methylepichlorohydrin, and the like can be used as the epihalohydrin used in the reaction of the unsaturated cyclic hydrocarbon compound with the polyaddition reaction product of phenols, but epichlorohydrin can be used. Is most preferred.
Therefore, the epoxy resin (a) is most preferably a reaction product of a polyaddition reaction product of dicyclopentadiene and phenol or cresol and an epihalohydrin.

As long as the said raw material is used for the epoxy resin (a) used by this invention, the manufacturing method in particular is not limited, For example, the method as described in Unexamined-Japanese-Patent No. 11-209584 is mentioned.
As the above-mentioned epoxy resin (a), for example, a dicyclopentadiene type epoxy resin Epicron HP7200 series manufactured by Dainippon Ink Co., Ltd. and an epoxy resin XD1000 series manufactured by Nippon Kayaku Co., Ltd. are commercially available and preferably used.

Unsaturated group-containing carboxylic acid compound (b)
Examples of the unsaturated group-containing carboxylic acid compound (b) include unsaturated carboxylic acids having an ethylenically unsaturated double bond. Specific examples thereof include (meth) acrylic acid (in this specification, “( “(Meth) acrylic”, “(meth) acrylate” and the like mean “acrylic or methacrylic”, “acrylate or methacrylate” and the like, for example, “(meth) acrylic acid” means “acrylic acid or methacrylic acid”. Monocarboxylic acids such as crotonic acid, o-, m-, p-vinylbenzoic acid, α-haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, cyano substituents, -(Meth) acryloyloxyethyl succinic acid, 2-acryloyloxyethyl adipic acid, 2- (meth) acryloyloxyethyl phthalate 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl maleic acid, 2- (meth) acryloyloxypropyl succinic acid, 2- (meth) acryloyloxypropyl adipic acid 2- (meth) acryloyloxypropyltetrahydrophthalic acid, 2- (meth) acryloyloxypropylphthalic acid, 2- (meth) acryloyloxypropylmaleic acid, 2- (meth) acryloyloxybutyl succinic acid, 2- (meth) acryloyloxybutyl adipic acid, 2- (meth) acryloyloxybutyl hydrophthalic acid, 2- (meth) acryloyloxybutyl phthalic acid, 2- (meth) acryloyloxybutyl maleic acid (meta ), Ε-caprolactone, β-propiolactone, γ-butyrolactone, δ- Monomers to which lactones such as rolactone are added, or hydroxyalkyl (meth) acrylate, pentaerythritol tri (meth) acrylate, (anhydrous) succinic acid, (anhydrous) phthalic acid, (anhydrous) maleic acid, etc. And a monomer to which an acid (anhydride) is added, (meth) acrylic acid dimer, and the like.

Particularly preferred is (meth) acrylic acid. A plurality of these may be used.
Reaction of Epoxy Resin (a) and Unsaturated Group-Containing Carboxylic Acid (b) As a method for reacting the epoxy group in the epoxy resin with the unsaturated group-containing carboxylic acid, a known method can be used. For example, the epoxy resin and unsaturated group-containing carboxylic acid are tertiary amines such as triethylamine and benzylmethylamine, quaternary ammonium salts such as dodecyltrimethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, benzyltriethylammonium chloride, Carboxylic acid can be added to the epoxy resin by reacting in an organic solvent at a reaction temperature of 50 to 150 ° C. for several to several tens of hours using pyridine, triphenylphosphine or the like as a catalyst. The amount of the catalyst used is preferably 0.01 to 10% by weight, particularly preferably 0.3 to 5% by weight, based on the reaction raw material mixture. In order to prevent polymerization during the reaction, it is preferable to use a polymerization inhibitor (for example, methoquinone, hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine, etc.). Preferably it is 0.01 to 10 weight% with respect to a raw material mixture, Most preferably, it is 0.1 to 5 weight%. The ratio of adding the unsaturated group-containing carboxylic acid to the epoxy group of the epoxy resin is usually 90 to 100 mol%. Since the remaining epoxy group adversely affects storage stability, the reaction is usually carried out at a ratio of 0.8 to 1.5 equivalents, more preferably 0.9 to 1.1 equivalents per 1 equivalent of epoxy group.

Polybasic carboxylic acid or anhydride (c)
As the polybasic carboxylic acid to be added to the hydroxyl group produced when the epoxy resin (a) is reacted with the unsaturated group-containing carboxylic acid (b) or its anhydride (c), known ones can be used. Maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, 5-norbornene-2,3-dicarboxylic acid, methyl-5 A dibasic carboxylic acid such as norbornene-2,3-dicarboxylic acid or an anhydride thereof; a polybasic carboxylic acid such as trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, biphenyltetracarboxylic acid, or an anhydride thereof. Can be mentioned. Among these, tetrahydrophthalic anhydride or succinic anhydride is preferable.

The addition rate of the polybasic carboxylic acid or its anhydride (c) is usually 10 to 100 mol%, preferably 20 to 100 mol%, more preferably the hydroxyl group produced when the component (b) is added. Is added to 30 to 100 mol%. If the amount is too large, the remaining film ratio at the time of development may be lowered. If the amount is too small, the solubility may be insufficient or the adhesion to the substrate may be insufficient.
As a method of adding the unsaturated group-containing carboxylic acid (b) to the epoxy resin (a) and then adding the polybasic carboxylic acid or its anhydride (c), a known method may be used. I can do it.

  Moreover, in this invention, you may use the binder resin obtained by adding an epoxy-group containing compound (d) to a part of produced | generated carboxyl group after adding polybasic acid carboxylic acid or its anhydride (c). . For example, as a component (d), in order to improve photosensitivity, glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, and epoxy group-containing compounds having a polymerizable unsaturated group In order to add an unsaturated compound or improve developability, a glycidyl ether compound having no polymerizable unsaturated group may be added, or both of them may be used in combination. Specific examples of the glycidyl ether compound having no polymerizable unsaturated group include a glycidyl ether compound having a phenyl group or an alkyl group (manufactured by Nagase Chemical Industries, Ltd., trade names: Denacol EX-111, Denacol EX-121, Denacol) EX-141, Denacol EX-145, Denacol EX-146, Denacol EX-171, Denacol EX-192) and the like. In the binder resin (A) of the present invention, the reaction product of the epoxy resin (a) and the unsaturated group-containing carboxylic acid (b) as described above is further reacted with a polybasic carboxylic acid or its anhydride (c). Also included is a binder resin obtained by adding the epoxy group-containing compound (d) to a part of the carboxyl groups of the resin obtained.

The weight average molecular weight (Mw) in terms of polystyrene measured by GPC of the binder resin (A) of the present invention is usually 700 or more, preferably 1000 or more, and usually 50000 or less, preferably 30000 or less. If the weight average molecular weight is too small, the heat resistance and film strength are inferior, and if too large, the solubility in the developer is insufficient, which is not preferable.
The acid value (mgKOH / g) of the binder resin (A) of the present invention is usually 10 or more, preferably 50 or more, and usually 200 or less, preferably 150 or less. If the acid value is too low, sufficient solubility cannot be obtained, and if the acid value is too high, curability is insufficient and surface properties deteriorate.

These binder resins (A) are usually 10% by weight or more, preferably 20% by weight or more based on the total solid content of the photosensitive composition of the present invention. When content of binder resin (A) is remarkably low, the solubility with respect to the developing solution of an unexposed part will fall and it will become easy to induce a development defect. In the present invention, “total solid content” means all components other than the solvent. The total solid content in the photosensitive composition of the present invention is usually 10% by weight or more and 90% by weight or less.
<Photoinitiator (B)>
The photopolymerization initiator used in the present invention is not particularly limited as long as it is a compound that polymerizes an ethylenically unsaturated group by actinic rays, but the photosensitive composition of the present invention is ethylenic as a compound having a polymerizable group. When the compound is contained, it is preferable to use a photopolymerization initiator that has a function of directly absorbing light or photosensitizing to cause a decomposition reaction or a hydrogen abstraction reaction to generate a polymerization active radical.

Specific examples of the polymerization initiator that can be used in the present invention are listed below. 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4 Halomethylated triazine derivatives such as -ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -s-triazine; 2 -Trichloromethyl-5- (2'-benzofuryl) -1,3,4-oxadiazole, 2-trichloromer-5- [β- (2'-benzofuryl) vinyl] -1,3,4-oxadi Azole, -Trichloromethyl-5-[[beta]-(2 '-(6 "-benzofuryl) vinyl)]
Halomethylated oxadiazole derivatives such as -1,3,4-oxadiazole, 2-trichloromethyl-5-furyl-1,3,4-oxadiazole; 2- (2′-chlorophenyl) -4,5 -Diphenylimidazole dimer, 2- (2'-chlorophenyl) -4,5-bis (3'-methoxyphenyl) imidazole dimer, 2- (2'-fluorophenyl) -4,5-diphenyl Imidazole derivatives such as imidazole dimer, 2- (2'-methoxyphenyl) -4,5-diphenylimidazole dimer, (4'-methoxyphenyl) -4,5-diphenylimidazole dimer; benzoin Benzoin alkyl ethers such as methyl ether, benzoin phenyl ether, benzoin isobutyl ether, benzoin isopropyl ether; 2-methylanthraquinone, 2-ethylanthralkyl Down, 2-t-butyl anthraquinone, anthraquinone derivatives such as 1-chloro anthraquinone; benzophenone, Michler's ketone, 2-
Benzophenone derivatives such as methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone; 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl- (p-isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) Ketone, 2-methyl- (4 '-(
Acetophenone derivatives such as methylthio) phenyl) -2-morpholino-1-propanone, 1,1,1-trichloromethyl- (p-butylphenyl) ketone; thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone Thioxanthone derivatives such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone; benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate; 9-phenyl Acridine derivatives such as acridine and 9- (p-methoxyphenyl) acridine; phenazine derivatives such as 9,10-dimethylbenzphenazine; anthrone derivatives such as benzanthrone; di-cyclopentadienyl-Ti-di-chloride, di- Cyclopentage Ru-Ti-bis-phenyl, di-cyclopentagenyl-Ti-bis-2,3,4,5,6-pentafluorophenyl-1 monoyl, di-cyclopentaenyl-Ti-bis-2, 3,5,6-tetrafluorophenyl-1-yl, di-cyclopentaenyl-Ti-bis-2,4,6-trifluorophen-1-yl, di-cyclopentagenyl-Ti-2, 6-dipuruolophen-1-yl, di-cyclopentagenyl-Ti-2,4-di-fluorophenyl-1-yl, di-methylcyclopentagenyl-Ti-bis-2,3,4 5,6-pentafluorophen-1-yl, di-methylcyclopentaenyl-Ti-bis-2,6-di-fluorophen-1-yl, di-cyclopentaenyl-Ti-2,6- G
Titanocene derivatives such as fluoro-3- (pyr-1-yl) -phen-1-yl. Moreover,
An oxime initiator described in JP-A No. 2000-80068 can also be used particularly suitably.

In addition, photopolymerization initiators that can be used in the present invention are described in Fine Chemical, March 1, 1991, Vol. 20, no. 4, P. 16-P26, JP-A-59-152396, JP-A-61-151197, JP-B-45-37377, JP-A-58-40302, JP-A-10-39503 Has been.
The content of the photopolymerization initiator is usually 0.01% by weight or more, preferably 0.1% by weight or more, more preferably 0.5% by weight or more based on the total solid content of the photosensitive composition of the present invention. The amount is usually 30% by weight or less, preferably 10% by weight or less. If the content is too low, the sensitivity may be lowered. On the other hand, if the content is too high, the solubility of the unexposed portion in the developer is lowered, and development failure is likely to be induced.
<Photopolymerizable monomer>
In the present invention, in addition to the binder resin (A) and the photopolymerization initiator (B), it is preferable to use a photopolymerizable monomer (photopolymerizable compound) in terms of sensitivity and the like. Examples of the photopolymerizable monomer used in the present invention include compounds having at least one ethylenically unsaturated group. Specific examples of the compound having an ethylenically unsaturated group in the molecule include (meth) acrylic acid, alkyl ester of (meth) acrylic acid, acrylonitrile, styrene, carboxylic acid having one ethylenically unsaturated bond and many ( And monoesters of monohydric alcohols.

  In the present invention, it is desirable to use a polyfunctional ethylenic monomer having two or more ethylenically unsaturated groups in one molecule. Examples of such polyfunctional ethylenic monomers include, for example, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; aliphatic polyhydroxy compounds, aromatics Examples thereof include esters obtained by an esterification reaction of a polyvalent hydroxy compound such as a polyhydroxy compound with an unsaturated carboxylic acid and a polybasic carboxylic acid.

  Examples of the ester of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, Acrylic esters of aliphatic polyhydroxy compounds such as pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerol acrylate, etc. In the same way, itaconic acid ester instead of itaconate, Maleic acid esters in which instead of the crotonic acid ester or maleate was changed to and the like.

Examples of the ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include acrylic acid esters and methacrylic acid esters of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, pyrogallol triacrylate and the like. Etc.
The ester obtained by the esterification reaction of a polybasic carboxylic acid and an unsaturated carboxylic acid and a polyvalent hydroxy compound is not necessarily a single substance, but typical examples include acrylic acid, phthalic acid, and ethylene. Condensates of glycols, condensates of acrylic acid, maleic acid and diethylene glycol, condensates of methacrylic acid, terephthalic acid and pentaerythritol, condensates of acrylic acid, adipic acid, butanediol and glycerin.

  In addition, as an example of the polyfunctional ethylenic monomer used in the present invention, a polyisocyanate compound and a hydroxyl group-containing (meth) acrylate ester or a polyisocyanate compound and a polyol and a hydroxyl group-containing (meth) acrylate ester are reacted. Urethane (meth) acrylates as obtained; epoxy acrylates such as addition reaction product of polyvalent epoxy compound and hydroxy (meth) acrylate or (meth) acrylic acid; acrylamides such as ethylenebisacrylamide; diallyl phthalate Allyl esters such as: vinyl group-containing compounds such as divinyl phthalate are useful.

The content of the photopolymerizable monomer in the photosensitive composition is usually 90% by weight or less, preferably 80% by weight or less, based on the total solid content. When the content of the photopolymerizable monomer is too high, the permeability of the developing solution to the exposed portion becomes high, and it becomes difficult to obtain a good image.
[Photosensitive coloring composition]
When using the photosensitive composition of this invention for a color filter use etc., a coloring material is mix | blended with a photosensitive composition and a photosensitive coloring composition is prepared.
<Coloring material (C)>
A coloring material means what colors the photosensitive composition which concerns on this invention. As the coloring material, dyes and pigments can be used, but pigments are preferable from the viewpoint of heat resistance, light resistance and the like. As the pigment, pigments of various colors such as a blue pigment, a green pigment, a red pigment, a yellow pigment, a purple pigment, an orange pigment, a brown pigment, and a black pigment can be used. In addition to organic pigments such as azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, and perylene, various inorganic pigments can be used. It is. Hereinafter, specific examples of usable pigments are indicated by pigment numbers. Terms such as “CI Pigment Red 2” mentioned below mean the color index (CI).

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

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

Examples of green pigments include C.I. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55. Of these, C.I. I. And CI Pigment Green 7 and 36.
Examples of yellow pigments include C.I. I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 6
2, 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, 20 , Mention may be made of 205, 206, 207, and 208. Of these, C.I. I. Pigment yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, more preferably C.I. I. Pigment yellow 83, 138, 139, 150, 180.

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

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

  Moreover, when forming the resin black matrix of a color filter using a photosensitive coloring composition, a black coloring material can be used. The black color material may be a single black color material or a mixture of red, green, blue and the like. These color materials can be appropriately selected from inorganic or organic pigments and dyes. In the case of inorganic and organic pigments, it is preferable to use the pigment dispersed in an average particle size of 1 μm or less, preferably 0.5 μm or less.

  Color materials that can be mixed for preparing a black color material include Victoria Pure Blue (42595), Auramin O (41000), Catillon Brilliant Flavin (Basic 13), Rhodamine 6GCP (45160), Rhodamine B (45170). Safranin OK 70: 100 (50240), Erioglaucine X (42080), No. 120 / Lionol Yellow (21090), Lionol Yellow GRO (21090), Shimla First Yellow 8GF (21105), Benzidine Yellow 4T-564D (21095), Shimler First Red 4015 (12355), Lionol Red 7B4401 (15850), Fast Gen Blue TGR-L (74160), Lionol Blue SM (26150), Lionol Blue ES (Pigment Blue 15: 6), Lionogen Red GD (Pigment Red 168), Lionol Green 2YS (Pigment Green 36), etc. (The numbers in parentheses above mean the color index (CI)).

In addition, other pigments that can be used in combination are C.I. I. For example, C.I. I. Yellow pigments 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166, C.I. I. Orange pigments 36, 43, 51, 55, 59, 61, C.I. I. Red pigments 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, C.I. I. Violet pigments 19, 23, 29, 30, 37,
40, 50, C.I. I. Blue pigment 15, 15: 1, 15: 4, 22, 60, 64, C.I. I. Green pigment 7, C.I. I. Examples thereof include brown pigments 23, 25, and 26.

Examples of the black color material that can be used alone include carbon black, acetylene black, lamp black, bone black, graphite, iron black, aniline black, cyanine black, and titanium black.
Among these, carbon black is preferable from the viewpoints of light shielding rate and image characteristics. Examples of carbon black include the following carbon black.

Mitsubishi Chemical Corporation: 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, # 4010, OIL7B, OIL9B, OIL11B, OIL30B, OIL31B Made by Degussa: Printex3, Printex3OP, Printex30, Printex30OP Printex40, Printex45, Pri tex55, Printex60, Printex75, Printex80, Printex85, Printex90, Printex A, Printex L, Printex G, Printex P, Printex U, Printex V, PrintexG, SpecialBlack550, SpecialBlack350, SpecialBlack250, SpecialBlack100, SpecialBlack6, SpecialBlack5, SpecialBlack4, Color Black FW1, Color
Black FW2, Color Black FW2V, Color Black FW18, Color Black FW18, Color Black FW200, Color Black S160, Color Black
S170 manufactured by Cabot Corporation: Monarch120, Monarch280, Monarch460, Monarch800, Monarch880, Monarch900, Monarch1000, Monarch1100, Monarch1300, Monarch1400, Monarch4630, REGAL99, REGAL99R, REGAL415, REGAL415R, REGAL250, REGAL250R, REGAL330, REGAL400R, REGAL55R0, REGAL660R, BLACK PEARLS480, PEARLS130, VULCAN XC72R, ELFTEX-8 Colombian Carbon Corporation: RAVEN11, RAVEN14, RAVEN15, RAVEN16, RAVEN22RAV N30, Raven35, Raven40, Raven410, Raven420, Raven450, Raven450, Raven500, Raven780, Raven850, Raven890H, Raven1000, Raven1020, Raven1040, Raven1060U, Raven1080U, Raven1170, Raven1190U, Raven1170, Raven1170U RAVEN7000
As examples of other black pigments, titanium black, aniline black, iron oxide black pigments, and organic pigments of three colors of red, green, and blue can be mixed and used as black pigments.

In addition, barium sulfate, lead sulfate, titanium oxide, yellow lead, bengara, chromium oxide, and the like can also be used as the pigment.
These various pigments can be used in combination. For example, in order to adjust the chromaticity, a green pigment and a yellow pigment can be used in combination, or a blue pigment and a violet pigment can be used in combination.

The average particle size of these pigments is usually 1 μm, preferably 0.5 μm or less, more preferably 0.25 μm or less. Examples of dyes that can be used as the colorant include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.
Examples of the azo dye include C.I. I. Acid Yellow 11, C.I. I. Acid Orange 7, C.I. I. Acid Red 37, C.I. I. Acid Red 180, C.I. I. Acid Blue 29, C.I. I. Direct Red 28, C.I. I. Direct Red 83, C.I. I. Direct Yellow 12, C.I. I. Direct Orange 26, C.I. I. Direct Green 28, C.I. I. Direct Green 59, C.I. I. Reactive Yellow 2, C.I. I. Reactive Red 17, C.I. I. Reactive Red 120, C.I. I. Reactive Black 5, C.I. I. Disperse Orange 5, C.I. I. Disperse thread 58, C.I. I. Disperse Blue 165, C.I. I. Basic Blue 41, C.I. I. Basic Red 18, C.I. I. Molded Red 7, C.I. I. Moldant Yellow 5, C.I. I. Examples thereof include Moldant Black 7.

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

  The ratio of the coloring material (C) in the total solid content in the photosensitive coloring composition can be usually selected in the range of 1 to 70% by weight with respect to the total solid content in the photosensitive composition. In this range, 10 to 70% by weight is more preferable, and 20 to 60% by weight is particularly preferable. When the ratio of the color material is too small, the film thickness with respect to the color density becomes too large, which adversely affects the gap control when the liquid crystal cell is formed. On the other hand, if the ratio of the color material is too large, sufficient image formability may not be obtained. In addition, the total solid content in the photosensitive coloring composition of the present invention is usually 10% by weight or more and 80% by weight or less.

  A pigment derivative or the like may be added to improve the dispersibility of the pigment and improve the dispersion stability. As pigment derivatives, azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, dioxazine, anthraquinone, indanthrene, perylene, perinone, diketopyrrolopyrrole, dioxazine Derivatives such as quinophthalone are preferable. As substituents of pigment derivatives, sulfonic acid groups, sulfonamide groups and their quaternary salts, phthalimidomethyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxyl groups, amide groups, etc. can be directly in the pigment skeleton or alkyl groups, aryl groups, complex groups. Examples thereof include those bonded via a ring group or the like, and a sulfonic acid group is preferable. Further, a plurality of these substituents may be substituted on one pigment skeleton. Specific examples of the pigment derivative include phthalocyanine sulfonic acid derivatives, quinophthalone sulfonic acid derivatives, anthraquinone sulfonic acid derivatives, quinacridone sulfonic acid derivatives, diketopyrrolopyrrole sulfonic acid derivatives, and dioxazine sulfonic acid derivatives. The addition amount of the pigment derivative is usually 0.1 to 30% by weight, preferably 0.1 to 20% by weight or less, more preferably 0.1 to 10% by weight, still more preferably 0.1 to 5% by weight based on the pigment. % Or less.

The photosensitive composition and photosensitive coloring composition of the present invention include an organic solvent, a pigment dispersant, an adhesion improver, a coating improver, a development improver, an ultraviolet absorber, an antioxidant, and a silane coupling agent. Etc. can be suitably blended.
<Organic solvent>
Although there is no restriction | limiting in particular as an organic 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, Apco # 18 solvent, diisobutylene, amyl acetate, butyl butyrate, apcocinner, butyl ether, diisobutyl ketone, methylcyclohexene, methyl nonyl ketone, propyl ether, dodecane, social solvent
No. 1 and no. 2, amyl formate, dihexyl ether, diisopropyl ketone, Solvesso # 150, butyl acetate (n, sec, t), hexene, shell TS28 solvent, butyl chloride, ethyl amyl ketone, ethyl benzoate, amyl chloride, ethylene glycol diethyl ether , Ethyl orthoformate, methoxymethylpentanone, methyl butyl ketone, methyl hexyl ketone, methyl isobutyrate, benzonitrile, ethyl propionate, methyl cellosolve acetate, methyl isoamyl ketone, methyl isobutyl ketone, propyl acetate, amyl acetate, Amylformate, bicyclohexyl, diethylene glycol monoethyl ether acetate, dipentene, methoxymethylpentanol, methylamino 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, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxypropionic acid, 3- Ethoxypropionic acid , Ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, dipropylene glycol monomethyl ether, ethylene glycol acetate, ethyl carb Specific organic solvents such as Tol, butyl carbitol, ethylene glycol monobutyl ether, propylene glycol-t-butyl ether, 3-methyl-3-methoxybutanol, tripropylene glycol methyl ether, 3-methyl-3-methoxybutyl acetate Can be mentioned.

The solvent is capable of dissolving or dispersing each component, and it is preferable to select a solvent having a boiling point in the range of 100 to 250 ° C. More preferably, it has a boiling point of 120-170 ° C. These solvents can be used alone or in combination.
<Pigment dispersant>
In the dispersion treatment, it is particularly preferable to use a polymer dispersant as the pigment dispersant because the dispersion stability over time is excellent. Examples of the polymer dispersant include a urethane dispersant, a polyethyleneimine dispersant, a polyoxyethylene alkyl ether dispersant, a polyoxyethylene glycol diester dispersant, a sorbitan aliphatic ester dispersant, and an aliphatic modified polyester. And the like, and the like. Specific examples of such a dispersant include trade names of EFKA (manufactured by EFKA Chemicals Beebuy (EFKA)), Disperbik (manufactured by BYK Chemie), Disparon (manufactured by Enomoto Kasei Co., Ltd.), and SOLPERSE (manufactured by GENECA). ), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), polyflow (manufactured by Kyoeisha Chemical Co., Ltd.) and the like. These dispersants can be used alone or in admixture of two or more. The content of the pigment dispersant is usually 50% by weight or less, preferably 30% by weight or less in the solid content of the photosensitive coloring composition.

<Silane coupling agent>
In addition, a silane coupling agent can be added to improve the adhesion to the substrate. Various types of silane coupling agents such as epoxy, methacrylic, amino and the like can be used, and epoxy silane coupling agents are particularly preferable.
[Production method of photosensitive coloring composition]
The photosensitive coloring composition of this invention is manufactured in accordance with a conventional method. For example, first, a predetermined amount of each of the coloring material, the solvent, and the dispersing agent is weighed, and in the dispersion treatment step, the coloring material is dispersed to obtain a liquid colored composition (ink-like liquid). In this dispersion treatment step, a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, or the like can be used. By performing this dispersion treatment, the coloring material is made fine particles, so that the coating characteristics of the photosensitive coloring composition are improved, and the transmittance of the product color filter substrate is improved.

  When the color material is subjected to a dispersion treatment, it is preferable to appropriately use the binder resin or the dispersion aid. For example, when the dispersion treatment is performed using a sand grinder, it is preferable to use glass beads or zirconia beads having a diameter of 0.1 to several mm. The temperature for the dispersion treatment is usually set in the range of 0 ° C to 100 ° C, preferably in the range of room temperature to 80 ° C. The dispersion time varies depending on the composition of the ink-like liquid {coloring material, solvent, dispersant}, the size of the sand grinder apparatus, and the like, and therefore needs to be adjusted as appropriate.

  The ink-like liquid obtained by the above dispersion treatment is mixed with a solvent, a binder resin, and in some cases, a predetermined amount of a photopolymerizable monomer, a photopolymerization initiator system component, and components other than those described above to obtain a uniform dispersion solution And In addition, in each process of a dispersion | distribution process and mixing, since fine refuse may mix, it is preferable to filter the obtained ink-like liquid with a filter etc.

The content of the binder resin (A) in the prepared photosensitive coloring composition is usually 5% by weight or more, preferably 10% by weight or more, and usually 95% by weight or less, based on the total solid content. Preferably it is 80 weight% or less.
The content of the photopolymerizable monomer in the photosensitive coloring composition is usually 90% by weight or less, preferably 80% by weight or less, based on the total solid content. When the content is too high, the permeability of the developing solution to the exposed portion is increased, and the sharpness and adhesion of the pixel are deteriorated.

  Moreover, as a ratio with respect to a coloring material of binder resin (A) in a photosensitive coloring composition, it is 20 to 500 weight% normally, Preferably it is 30 to 300 weight%, More preferably, it is the range of 50 to 200 weight%. . If the content of the binder resin (A) is too low, the solubility of the unexposed portion in the developing solution is lowered and development failure is likely to be induced. If the content is extremely high, it is difficult to obtain a desired pixel film thickness.

The content of the photopolymerization initiator in the photosensitive coloring composition is usually 0.1% by weight or more, preferably 0.5% by weight or more, more preferably 0.7% by weight or more, based on the total solid content. Usually, it is 30% by weight or less, preferably 10% by weight or less.
[3] Manufacture of color filter substrate [3-1] Transparent substrate (support)
Next, a color filter substrate and a method for manufacturing the color filter will be described. The transparent substrate of the color filter is not particularly limited as long as it is transparent and has an appropriate strength. Examples of materials include polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, polycarbonate, polymethyl methacrylate, polysulfone thermoplastic resin sheets, epoxy resins, unsaturated polyester resins, and poly (meth) acrylic. Examples thereof include thermosetting resin sheets such as a resin, and various glasses. Among these, glass and heat resistant resin are preferable from the viewpoint of heat resistance.

  For transparent substrates and black matrix forming substrates, to improve surface properties such as adhesion, corona discharge treatment, ozone treatment, silane coupling agents, and thin film formation treatment of various resins such as urethane resins May be performed. The thickness of the transparent substrate is usually 0.05 to 10 mm, preferably 0.1 to 7 mm. Moreover, when performing the thin film formation process of various resin, the film thickness is 0.01-10 micrometers normally, Preferably it is the range of 0.05-5 micrometers.

[3-2] Black matrix The color filter of the present invention can be manufactured by providing a black matrix on a transparent substrate and usually forming red, green, and blue pixel images. The photosensitive coloring composition is used as at least one resist forming coating solution of black, red, green, and blue. For black resist, on the transparent glass substrate glass surface, for red, green, and blue, on the resin black matrix forming surface formed on the transparent substrate, or metal black formed using a chromium compound or other light shielding metal material A pixel image of each color is formed on the matrix forming surface by performing coating, heat drying, image exposure, development and thermosetting.

The black matrix is formed on a transparent substrate using a light shielding metal thin film or a photosensitive coloring composition for black matrix. As the light-shielding metal material, chromium compounds such as metal chromium, chromium oxide, and chromium nitride, nickel and tungsten alloys, and the like may be used, and these may be laminated in a plurality of layers.
These metal light shielding films are generally formed by a sputtering method, and after forming a desired pattern in a film shape with a positive photoresist, ceric ammonium nitrate and perchloric acid and / or nitric acid are added to chromium. Other materials are etched using an etchant according to the material, and finally a positive photoresist is stripped with a dedicated stripper to form a black matrix. be able to.

  In this case, first, a thin film of these metals or metal / metal oxide is formed on the transparent substrate by vapor deposition or sputtering. Next, after forming a coating film of the photosensitive coloring composition on the thin film, the coating film is exposed and developed using a photomask having a repetitive pattern such as a stripe, a mosaic, and a triangle to form a resist image. Thereafter, this coating film can be etched to form a black matrix.

  When using the photosensitive coloring composition for black matrix, a black matrix is formed using the photosensitive coloring composition containing a black coloring material. For example, black color material such as carbon black, graphite, iron black, aniline black, cyanine black, titanium black or the like, or red, green, blue or the like appropriately selected from inorganic or organic pigments and dyes A black matrix can be formed in the same manner as described below for forming a red, green, and blue pixel image using a photosensitive coloring composition containing a black color material by mixing.

  In the black matrix pattern formed in this way, the angle formed between the surface of the light-shielding pattern in contact with the substrate and the substrate surface (hereinafter referred to as the taper angle) is usually 50 in the cross-sectional shape when the image is formed. Degrees or less, preferably 40 degrees or less, more preferably 30 degrees or less, and usually 5 degrees or more, preferably 10 degrees or more. If the taper angle is too large, the step in the pixel, which will be described later, becomes large.

Here, the taper angle means the angle between the substrate and the straight line connecting the end of the pattern and the height of the pattern at a position 2 μm from the end in the cross section of the black matrix pattern (FIG. 1). In addition, it is preferable that the taper angle is in the above range, and that a forward taper shape is used.
[3-3] Formation of Pixels A photosensitive coloring composition containing a coloring material of one color of red, green, and blue is applied on a transparent substrate provided with a black matrix, dried, and then applied onto the coating film. A photomask is overlapped, and a pixel image is formed through image exposure, development, and thermosetting or photocuring as necessary through this photomask to form a colored layer. A color filter image can be formed by performing this operation for each of the three color photosensitive coloring compositions of red, green, and blue.

  The photosensitive coloring composition for the color filter can be applied by a spinner method, a wire bar method, a flow coating method, a die coating method, a roll coating method, a spray coating method, or the like. Above all, according to the die coating method, the amount of coating solution used is greatly reduced, there is no influence of mist adhering to the spin coating method, and the generation of foreign matter is suppressed. To preferred.

  If the thickness of the coating film is too large, pattern development will be difficult, and it may be difficult to adjust the gap in the liquid crystal cell forming process. If it is too small, it will be difficult to increase the pigment concentration and the desired color will be exhibited. May become impossible. The thickness of the coating film is usually preferably in the range of 0.2 to 20 μm as the film thickness after drying, more preferably in the range of 0.5 to 10 μm, and still more preferably in the range of 0.8 to 5 μm. It is a range.

[3-4] Drying of coating film The coating film after the photosensitive coloring composition is applied to the substrate is preferably dried by a drying method using a hot plate, an IR oven, or a convection oven. Usually, after preliminary drying, it is heated again and dried. The conditions for the preliminary drying can be appropriately selected according to the type of the solvent component, the performance of the dryer 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 80 ° C., preferably 50 to 70 ° C., depending on the type of the solvent component and the performance of the dryer used. It is selected in the range of 30 seconds to 3 minutes.

  The reheat drying temperature condition is 50 to 200 ° C higher than the predrying temperature, preferably 70 to 160 ° C, particularly preferably 70 to 130 ° C. The drying time is preferably 10 seconds to 10 minutes, and more preferably 15 seconds to 5 minutes, depending on the heating temperature. The higher the drying temperature, the better the adhesion to the transparent substrate. However, if the drying temperature is too high, the binder resin is decomposed, and thermal polymerization may be induced to cause development failure. The thickness of the photosensitive coloring composition coating film after drying is in the range of 0.5 to 3 μm, preferably 1 to 2 μm. The drying process of the coating film may be a vacuum drying method in which drying is performed in a vacuum chamber without increasing the temperature.

[3-5] Exposure Step Image exposure is performed by overlaying a negative matrix pattern on the coating film of the photosensitive coloring composition, and irradiating with an ultraviolet or visible light source through this mask pattern. At this time, if necessary, exposure may be performed after an oxygen blocking layer such as a polyvinyl alcohol layer is formed on the photopolymerizable layer in order to prevent a decrease in sensitivity of the photopolymerizable layer due to oxygen. The light source used for said image exposure is not specifically limited. Examples of the light source include a xenon lamp, a halogen lamp, a tungsten lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a medium-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc, and a fluorescent lamp, an argon ion laser, a YAG laser, Examples include an excimer laser, a nitrogen laser, a helium cadmium laser, and a laser light source such as a semiconductor laser. An optical filter can also be used when used by irradiating light of a specific wavelength.

[3-6] Development Step The color filter according to the present invention contains an organic solvent or a surfactant and an alkaline compound after image-exposing the coating film of the photosensitive coloring composition with the above-mentioned light source. An image can be formed on a substrate by development using an aqueous solution. This aqueous solution may further contain an organic solvent, a buffering agent, a complexing agent, a dye or a pigment.

  Examples of alkaline compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate , Inorganic alkaline compounds such as sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide, mono-di- or triethanolamine, mono-di- or trimethyl Ami, mono-di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), coli And organic alkaline compounds such as. These alkaline compounds may be a mixture of two or more.

  Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters, and alkylbenzene sulfonic acids. Examples include anionic surfactants such as salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, and sulfosuccinate esters, and amphoteric surfactants such as alkylbetaines and amino acids.

Examples of the organic solvent include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol and the like. The organic solvent can be used alone or in combination with an aqueous solution.
The development processing conditions are not particularly limited, and the development temperature is usually in the range of 10 to 50 ° C., particularly 15 to 45 ° C., particularly preferably 20 to 40 ° C. The development methods are immersion development, spray development, brush Any of a developing method, an ultrasonic developing method and the like can be used.

In addition to the manufacturing method described above, the color filter of the present invention is obtained by applying (1) a curable coloring composition containing a solvent, a phthalocyanine pigment as a coloring material, and a polyimide resin as a binder resin to a substrate. It can also be manufactured by a method of forming a pixel image by an etching method. Further, (2) a method for forming a pixel image directly on a transparent substrate by using a photosensitive coloring composition containing a phthalocyanine pigment as a coloring ink, and (3) a photosensitive coloring composition containing a phthalocyanine pigment. A method of depositing a colored film on an ITO electrode having a predetermined pattern by immersing the substrate as an electrodeposition solution and immersing the substrate in the electrodeposition solution may be used. Further, (4) a method in which a film coated with a photosensitive coloring composition containing a phthalocyanine pigment is attached to a transparent substrate and peeled off, image exposure and development to form a pixel image, and (5) a phthalocyanine pigment. The method of forming a pixel image with an inkjet printer using the photosensitive coloring composition containing as a coloring ink, etc. are mentioned. The manufacturing method of a color filter employ | adopts the method suitable for this according to the composition of the photosensitive coloring composition for color filters.

[3-7] Thermosetting treatment The color filter substrate after development is subjected to thermosetting treatment. The thermosetting treatment conditions at this time are selected such that the temperature is in the range of 100 to 280 ° C, preferably 150 to 250 ° C, and the time is in the range of 5 to 60 minutes. Through these series of steps, the patterning image formation for one color is completed. This process is sequentially repeated to pattern black, red, green, and blue to form a color filter. Note that the order of patterning the four colors is not limited to the order described above.

The color filter thus obtained has a light-shielding pattern on a transparent substrate, and the angle formed between the surface of the light-shielding pattern in contact with the substrate and the substrate surface is 50 degrees or less, but 40 degrees or less. Is preferably 30 ° or less.
Further, when the pixel image of the colored pattern is formed in this way, if the taper angle is small, the thickness of the overlapping portion between the light shielding pattern and the red, green, and blue pixel images is reduced. The difference between the highest point and the lowest point on the surface in each pixel image (hereinafter referred to as an in-pixel step) is usually 0.7 μm or less, preferably 0.5 μm or less, more preferably 0 for any pixel image. .4 μm or less. If the step in the pixel is too large, the ITO film may be disconnected due to the raised portion, and a high-quality color filter cannot be obtained.

[3-8] Formation of transparent electrode The color filter is used as a part of components such as color displays and liquid crystal displays by forming transparent electrodes such as ITO on the image as it is. In order to enhance the property and durability, a top coat layer such as polyamide or polyimide can be provided on the image as necessary. Further, in some applications such as a planar alignment type drive system (IPS mode), the transparent electrode may not be formed.

[4] Liquid crystal display device (panel)
Next, a method for manufacturing a liquid crystal display device (panel) will be described. A liquid crystal display device usually forms an alignment film on a color filter, spreads spacers on the alignment film, and then bonds to a counter substrate to form a liquid crystal cell, injects liquid crystal into the formed liquid crystal cell, Complete by connecting to the counter electrode. The alignment film is preferably a resin film such as polyimide. For the formation of the alignment film, a gravure printing method and / or a flexographic printing method is usually employed, and the thickness of the alignment film is several tens of nm. After the alignment film is cured by thermal baking, it is surface-treated by irradiation with ultraviolet rays or a rubbing cloth to be processed into a surface state in which the tilt of the liquid crystal can be adjusted.

  A spacer having a size corresponding to a gap (gap) with the counter substrate is used, and a spacer of 2 to 8 μm is usually preferable. A photo spacer (PS) of a transparent resin film can be formed on the color filter substrate by photolithography, and this can be used instead of the spacer. As the counter substrate, an array substrate is usually used, and a TFT (thin film transistor) substrate is particularly preferable.

The gap for bonding to the counter substrate varies depending on the use of the liquid crystal display device, but is usually selected in the range of 2 to 8 μm. After bonding to the counter substrate, the portion other than the liquid crystal injection port is sealed with a sealing material such as an epoxy resin. The sealing material is cured by UV irradiation and / or heating, and the periphery of the liquid crystal cell is sealed.
The liquid crystal cell whose periphery is sealed is cut into panel units, then decompressed in a vacuum chamber, the liquid crystal injection port is immersed in liquid crystal, and then the liquid crystal is injected into the liquid crystal cell by leaking in the chamber. . The degree of decompression in the liquid crystal cell is usually 1 × 10 ⁻² to 1 × 10 ⁻⁷ Pa, preferably 1 × 10 ⁻³ to 1 × 10 ⁻⁶ Pa. Moreover, it is preferable to heat a liquid crystal cell at the time of pressure reduction, and heating temperature is 30-100 degreeC normally, More preferably, it is 50-90 degreeC. The warming hold during decompression is usually in the range of 10 to 60 minutes, and then immersed in the liquid crystal. In the liquid crystal cell into which liquid crystal is injected, the liquid crystal display device (panel) is completed by sealing the liquid crystal injection port by curing the UV curable resin.

The type of liquid crystal is not particularly limited, and is a conventionally known liquid crystal such as an aromatic, aliphatic, or polycyclic compound, and may be any of lyotropic liquid crystal, thermotropic liquid crystal, and the like. As the thermotropic liquid crystal, nematic liquid crystal, smectic liquid crystal, cholesteric liquid crystal, and the like are known, but any of them may be used.

Next, although a manufacture example, an Example, and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to a following example, unless the summary is exceeded. In the following examples, “part” represents “part by weight”.
[1] Comparison of adhesion and pixel sharpness <Synthesis Example 1>
XD1000 manufactured by Nippon Kayaku Co., Ltd. (polyglycidyl ether of dicyclopentadiene / phenol polymer, weight average molecular weight 700, epoxy equivalent 252) 300 parts, 87 parts acrylic acid, 0.2 parts p-methoxyphenol, triphenylphosphine 5 parts and 255 parts of propylene glycol monomethyl ether acetate were charged into a reaction vessel and stirred at 100 ° C. until the acid value became 3.0 mgKOH / g. It took 9 hours for the acid value to reach the target (acid value 2.5). Next, 145 parts of tetrahydrophthalic anhydride was further added and reacted at 120 ° C. for 4 hours to obtain a binder resin I solution having an acid value of 100 and a weight average molecular weight of 2600 in terms of polystyrene measured by GPC.

<Synthesis Example 2>
Daikoku Ink Co., Ltd. Epiklon HP7200HH (polyglycidyl ether of dicyclopentadiene / phenol polymer, weight average molecular weight 1000, epoxy equivalent 270) 155 parts, acrylic acid 41 parts, p-methoxyphenol 0.1 part, triphenyl A reaction vessel was charged with 2.5 parts of phosphine and 130 parts of propylene glycol monomethyl ether acetate, and the mixture was heated and stirred at 100 ° C. until the acid value was 3.0 mgKOH / g or less. It took 9 hours for the acid value to reach the target (acid value 2.9). Subsequently, 74 g of tetrahydrophthalic anhydride was further added and reacted at 120 ° C. for 4 hours to obtain a binder resin II solution having an acid value of 98 and a weight average molecular weight of 3,500.

<Example 1>
52 parts by weight of binder resin I solution obtained in Synthesis Example 1 (35 parts by weight in terms of solid content), 5 parts by weight of dipentaerythritol hexaacrylate, 4 parts by weight of CGI-124 (manufactured by Ciba Geigy), and carbon black dispersion 56 parts by weight of a body (carbon concentration: 25%) was mixed with propylene glycol monomethyl ether acetate to obtain a photosensitive black composition.

  The photosensitive black composition thus obtained was spin-coated on a 10 cm square glass substrate and dried at 90 ° C. for 150 seconds on a hot plate. The film thickness after drying was 1 μm. Next, this sample was image-exposed with a high-pressure mercury lamp through a mask. A black pixel (black matrix) was formed by spray development using an aqueous solution of KOH having a temperature of 23 ° C. and a concentration of 0.1%.

<Example 2>
A black pixel was formed by performing the same treatment as in Example 1 except that the binder resin I in Example 1 was changed to the binder resin II.
<Comparative Example 1>
A black pixel was obtained by performing the same treatment as in Example 1 except that the binder resin I of Example 1 was changed to EA4805 (manufactured by Mitsubishi Chemical Corporation, tetrahydrophthalic anhydride adduct of cresol novolac type epoxy acrylate. Acid value 100). Formed.

<Comparative example 2>
A black color was obtained by performing the same treatment as in Example 1 except that the binder resin I of Example 1 was changed to ZAR (Nippon Kayaku Co., Ltd., tetrahydrophthalic anhydride adduct of bisphenol A type epoxy acrylate. Acid value 100). Pixels were formed.
<Comparative Example 3>
The same treatment as in Example 1 except that the binder resin I of Example 1 was changed to ACA200M (manufactured by Daicel Chemical Industries, Ltd., 3,4-epoxycyclohexyl acrylate adduct of acrylic resin having carboxylic acid. Acid value 115). To form a black pixel.

Evaluation of Pixels The obtained pixels were evaluated by the following items, and the results are shown in Table-1.
<Adhesion>
The minimum pattern size of a resist that can be resolved at an exposure amount that faithfully reproduces a 20 μm mask pattern was observed with a microscope at a magnification of 200 times. When the minimum pattern dimension was 10 μm or less, the adhesion was good, and the case where the adhesion exceeded 10 μm was evaluated as x, and the results shown in Table 1 were obtained.

<Pixel sharpness>
The shape of the fine black pixel at an exposure amount that faithfully reproduces a 20 μm mask pattern was observed with a microscope at a magnification of 1000 times. The linearity was good for those having good linearity, and the resist pattern having protrusions and irregularities was crossed, and the results shown in Table 1 were obtained.

[2] Comparison of taper angle and in-pixel step <Example 3>
Carbon black (“MA-220” manufactured by Mitsubishi Chemical Corporation) 19.7 g, “Disperbyk-182” 7.7 g manufactured by Bykchemie as a dispersing agent, and 72.6 g PGMEA are mixed together to give a zirconia bead 100 having a particle size of 0.5 mm. cc was added and shaken with a paint conditioner for 10 hours to obtain a carbon black dispersion. 50.7 g of this dispersion was taken, 10.79 g of binder resin I solution (solid content: 7.26 g), 1.82 g of dipentaerythritol hexaacrylate (“DPHA” manufactured by Nippon Kayaku Co., Ltd.), Ciba Specialty Chemicals as photopolymerization initiator A black resist was prepared by adding 2.0 g of CGI-242, 0.025 g of Megafac F475 manufactured by Dainippon Ink Co., Ltd., and 38.2 g of PGMEA as an organic solvent.

The resist prepared as described above was applied on a glass substrate (AN100 manufactured by Asahi Glass Co., Ltd.) with a die coater so as to have a film thickness of 1.0 μm, and a mercury lamp using a photomask for black matrix (pattern line width 20 μm). Was exposed for 3 seconds (60 mJ / cm ² ) with an illuminance of 20 mW / cm ² (i-line conversion). The gap between the photomask and the resist surface was 150 μm. The exposed substrate was developed using a 0.1% KOH aqueous solution and then heat-treated in an oven at 230 ° C. for 30 minutes to obtain a black matrix pattern.

<Comparative example 4>
63.4 g of the carbon black dispersion prepared in Example 3 was collected, and EA 4805 (manufactured by Mitsubishi Chemical Corporation, cresol novolac type epoxy acrylate tetrahydrophthalic anhydride adduct. Acid value 100) 4.98 g, dipentaerythritol as a binder resin. 1.25 g of hexaacrylate (“DPHA” manufactured by Nippon Kayaku Co., Ltd.), 1.37 g of CGI-242 manufactured by Ciba Specialty Chemicals as a photopolymerization initiator, 0.025 g of MegaFac F475 manufactured by Dainippon Ink Co., Ltd. as a surfactant, and 29.0 PGMEA as an organic solvent g was added to prepare a black resist.
The black resist thus obtained was exposed, developed and heat treated in the same manner as in Example 3 to obtain a black matrix pattern.

Evaluation of pixels The obtained pixels were evaluated according to the following items, and the results are shown in Table-2.
<Taper angle>
The cross-sectional shape of the black pixel obtained as described above was observed with an SEM (Hitachi S-4500), and the taper angle was measured.
<Step in pixel>
7.4g of PGMEA is mixed with 7.7g of red pigment ("Cromophtal Red A2B" manufactured by Ciba Geigy and "Paliotol Yellow K1841D" manufactured by BASF) and 3.1g of polyester dispersant, and 10cc of 0.5mm zirconia beads is mixed. In addition, a red pigment dispersion was obtained by shaking for 5 hours in a paint conditioner. 7.48 g of this dispersion was taken, 1.0 g of the acrylic resin of Chemical 1 as the binder, 0.5 g of dipentaerythritol hexaacrylate (Nippon Kayaku Co., Ltd. “DPHA”) as the ethylenic compound, and photopolymerization started 0.075 g of biimidazole as a system, 0.045 g of Michler's ketone, 0.0004 g of a fluorosurfactant (Sumitomo 3M Co., Ltd. “FC-430”), and 1.51 g of PGMEA as an organic solvent were added to prepare a red color resist. .

The obtained red color resist was applied using a spin coating method so that the overlap width with the black matrix was 5 μm and the dry film thickness was 1.3 μm, and dried on a hot plate at 70 ° C. for 1 minute, After exposure to 150 mj / cm ^{2 of} ultraviolet rays using a mask for a red filter, development was performed using a 0.5 wt% diethanolamine aqueous solution, thereby obtaining a red pixel pattern between the black matrix patterns. Next, the sample was irradiated with 15000 mj / cm ² ultraviolet rays using a high-pressure mercury lamp, and further subjected to heat treatment in an oven at 200 ° C. for 10 minutes to form a red pixel image.

Regarding the surface shape of the red pixel image of the obtained sample, the step in the pixel was measured using “alpha-step” manufactured by TENCOR INSTRUMENTS.
In addition, a green pixel image was formed in the same manner as described above except that a green pigment ("Lionol Green 6Y501" manufactured by Toyo Ink Co., Ltd. and "Paliotol Yellow K1841D" manufactured by BASF) was used instead of the red pigment. The step in the pixel was measured.

A blue pixel image is obtained in the same manner as described above except that a blue pigment (“Lionol Blue ES” manufactured by Toyo Ink Co., Ltd. and “IRGAZIN BLUE A3RN” manufactured by Ciba Geigy Co., Ltd.) is used instead of the red pigment. Then, the step inside the pixel was measured.

The schematic diagram explaining the taper angle in a black matrix pattern.

Explanation of symbols

1 Black matrix pattern 2 Substrate surface 3 Taper angle

Claims (8)

A binder resin (A) obtained by further reacting a reaction product of an epoxy resin (a) and an unsaturated group-containing carboxylic acid (b) with a polybasic carboxylic acid or its anhydride (c), a photopolymerization initiator ( a photosensitive composition containing a B), an epoxy resin in the binder resin (a) (a) is, polyaddition reaction between a cyclic hydrocarbon compound and a phenol having two or more unsaturated groups per molecule and goods, the reaction product of an epihalohydrin, and a photopolymerization initiator (B) is an oxime-based initiator der Ru sensitive optical composition, and photosensitive characterized by containing a colorant (C) Coloring composition. The photosensitive coloring composition according to claim 1, wherein the epoxy resin (a) is a reaction product of a polyaddition reaction product of dicyclopentadiene and phenol or cresol and an epihalohydrin. Colorant (C) is, photosensitive coloring composition according to claim 1 or 2 is a black colorant. In the cross-sectional shape when a light-shielding pattern is image-formed using the photosensitive coloring composition of Claim 3 on a transparent substrate, the angle formed between the surface of the light-shielding pattern in contact with the substrate and the substrate surface is 50. A color filter characterized by being less than or equal to degrees. The color filter of Claim 4 which has a pixel formed using the photosensitive coloring composition of Claim 1 or 2 on a transparent substrate. Having a pixel image of two or more different colored patterns on a substrate on which a light-shielding pattern is formed, and using the substrate as a reference plane, the difference between the highest point and the lowest point on the surface of each pixel image is any pixel image The color filter according to claim 5 , which is 0.7 μm or less. The color filter according to claim 5 or 6 , wherein the film thickness of the pixel image is in the range of 0.5 to 10 µm. A liquid crystal display device using the color filter according to any one of claims 5 to 7 .

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