JP2004163917A - Colored photosensitive resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a colored photosensitive resin composition which exhibits high sensitivity even if the composition contains coloring materials at a high concentration, the colored photosensitive resin composition which is made into forward tapered shapes at the ends of colored pixels formed by using the colored photosensitive resin composition and prevents ITO (Indium Tin Oxide) films from being disconnected even if the ITO films are formed without via over-coatings on the pixels and a color filter of high quality using the colored photosensitive resin composition. <P>SOLUTION: The colored photosensitive resin composition contains a binder resin (A), a photopolymerizable monomer (B), a photopolymerization initiator (C), the coloring materials (D), and a solvent (E), in which the photopolymerizable monomer (B) includes at least one monomer (b10) selected from the group consisting of a (metha)acrylic monomer (b11) having two (metha)acrylic groups within the same molecule and a vinyl ether monomer (b12) having two vinyl ether groups within the same molecule, and a (metha)acrylic monomer (b20) having ≥5 (metha)acrylic groups within the same molecule. <P>COPYRIGHT: (C)2004,JPO

Description

  The present invention relates to a photosensitive resin composition widely used for ultraviolet-curable inks, photoresists, and the like, and particularly to a colored image (hereinafter, referred to as a pixel) used for a color liquid crystal display device, an imaging device, and the like. The present invention relates to a colored photosensitive resin composition suitable for a resist for forming the photosensitive resin composition.

  2. Description of the Related Art A color filter in a color liquid crystal display device, an imaging device, or the like is usually manufactured by forming three primary color pixels of red, green, and blue on a substrate such as glass or a silicon wafer. Usually, a black matrix for shielding light between these pixels is provided. Then, in order to form pixels of these colors, a resist solution containing a pigment corresponding to each color is uniformly applied by a spin coater on a substrate on which a black matrix is formed, and then heated and dried (prebaked). A method of exposing and developing a coating film is adopted, and an image of each color is obtained by repeating these operations for each color required for a color filter. As such a resist, a photosensitive resin composition containing a photopolymerizable monomer and a photopolymerization initiator together with a pigment and a binder resin is often used. Also, a photosensitive resin composition containing a black pigment may be used for forming a black matrix.

  Since the photopolymerizable monomer used in such a resist determines the properties and quality required for producing a color filter, the photopolymerizable monomer having excellent sensitivity, developability, resolution and adhesion is used for a color filter. As the polymerizable composition, the polymerizable monomer has 3 to 4 (meth) acrylic groups in the same molecule and a (meth) acrylic monomer having 5 or more (meth) acrylic groups in the same molecule (meth) A mixture with an acrylic monomer has been proposed (for example, see Patent Document 1).

  When forming the color filter, an ITO film is usually deposited on the pixel via an overcoat (for example, refer to Patent Documents 3 to 5, Non-Patent Document 1 and the like). However, in recent years, it has been desired to omit the overcoat in order to increase the productivity of the color filter. However, if the overcoat is omitted and the ITO film is formed on the pixel, there is a problem that the pixel is wrinkled or the ITO film is disconnected (for example, see Patent Documents 6 and 2).

Japanese Patent Application Laid-Open No. H10-319583, page 2, left column, second line-page 2, left column, eighth line JP-A-2002-236210, page 49, left column, line 49-right column, second line JP-A-7-5319, page 8, left column, lines 17-47 JP-A-7-128519, page 6, left column, lines 21-35 JP-A-2002-129307, page 4, left column, line 45-page 6, right column, line 14 JP-A-9-292514, page 2, left column, line 11-25, page 3, right column, line 38-46 Japan Patent Office "Standard Technology Collection, Electro-Organic EL, ITO Electrode Manufacturing Method Using Sputter Deposition Method", [online], [update date 2002.6.28], [searched October 2, 2003], Internet <URL: http: // www.jpo.go.jp/shiryou/s_sonota/hyoujun_gijutsu/yuuki_el/body_htm/d008.htm>

  An object of the present invention is to provide a colored photosensitive resin composition exhibiting high sensitivity even when a colored material is contained at a high concentration, and the shape of the end portion of a colored pixel formed using the colored photosensitive resin composition is in order. A colored photosensitive resin composition which has a tapered shape and does not break the ITO film even if an ITO film is formed on the pixel without an overcoat, and a high quality color filter using the colored photosensitive resin composition Is to provide.

As a result of intensive studies, the present inventors have found that a colored photosensitive resin composition containing a specific photopolymerization initiator can solve the above-mentioned problems, and have accomplished the present invention.
That is, the present invention provides a colored photosensitive resin composition containing a binder resin (A), a photopolymerizable monomer (B), a photopolymerization initiator (C), a coloring material (D) and a solvent (E). The functional monomer (B) is selected from the group consisting of a (meth) acrylic monomer (b11) having two (meth) acrylic groups in the same molecule and a vinyl ether monomer (b12) having two vinylether groups in the same molecule A colored (meth) acrylic monomer (b20) having at least one selected monomer (b10) and five or more (meth) acrylic groups in the same molecule; The colored photosensitive resin composition is applied on a substrate or a layer formed of the solid content of the previously formed colored photosensitive resin composition, and the applied colored photosensitive resin composition layer A volatile component is removed, the layer is exposed through a photomask, and a method for forming a pattern to be developed, a color filter including the pattern formed by the method, and a liquid crystal display device using the color filter are provided. provide.

  The colored pixel obtained by the colored photosensitive resin composition of the present invention has a forward tapered shape, which is preferable. Therefore, even if an ITO film is formed directly on the forward-tapered pixel without using an overcoat, the ITO film does not break. Therefore, when the colored photosensitive resin composition of the present invention is used as a pigment-dispersed resist to produce a color filter, a high-quality color filter with excellent productivity can be obtained.

  Hereinafter, the present invention will be described in detail.

  The colored photosensitive resin composition of the present invention is mainly used as a pigment-dispersed resist, and is usually a pigmented coloring material (D), a binder resin (A), a photopolymerization initiator (C) and As the photopolymerizable monomer (B), at least one selected from the group consisting of a (meth) acryl monomer having two (meth) acryl groups in the same molecule and a vinyl ether monomer having two vinyl ether groups in the same molecule. A mixture of a kind monomer and a (meth) acrylic monomer having 5 or more (meth) acrylic groups in the same molecule, optionally (F) and other additives are dissolved or dispersed in the solvent (E). .

  The binder resin (A) has alkali solubility and acts as a dispersion medium for the coloring material. As the binder resin used in the present invention, a polymer containing a structural unit derived from an unsaturated carboxylic acid is preferable. As the binder resin, a resin obtained by copolymerizing an unsaturated carboxylic acid and another monomer copolymerizable therewith is more preferable.

  Specific examples of the structural unit derived from the unsaturated carboxylic acid include a structural unit derived from acrylic acid and a structural unit derived from methacrylic acid. Acrylic acid and methacrylic acid can be used alone or in combination of both. Further, in addition to these acrylic acid and methacrylic acid, at least one carboxylic acid selected from the group consisting of other unsaturated carboxylic acids and unsaturated carboxylic anhydrides such as crotonic acid, itaconic acid, maleic acid and fumaric acid. An acid can be used in combination. Further, a monomer containing a hydroxy group and a carboxyl group in the same molecule, such as α- (hydroxymethyl) acrylic acid, can be used in combination.

  The binder resin used in the present invention is preferably a resin obtained from a structural unit derived from an unsaturated carboxylic acid as described above and a structural unit copolymerizable with the structural unit derived from the unsaturated carboxylic acid. A structure copolymerizable with the structural unit derived from the unsaturated carboxylic acid

The constituent unit preferably includes a constituent unit derived from an acrylate ester.

Examples of the structural unit derived from an acrylate ester include an acrylate compound. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, benzyl (meth) acrylate, and 2-hydroxyethyl Unsubstituted or substituted alkyl esters of unsaturated carboxylic acids such as (meth) acrylate and aminoethyl (meth) acrylate;
Cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cycloheptyl (meth) acrylate, cyclooctyl (meth) acrylate, menthyl (meth) acrylate, cyclopentenyl (meth) acrylate, cyclohexenyl (meth) ) Acrylate, cycloheptenyl (meth) acrylate, cyclooctenyl (meth) acrylate, mentadienyl (meth) acrylate, isobornyl (meth) acrylate, pinanyl (meth) acrylate, tricyclodecyl (meth) acrylate, tricyclodecyloxyethyl (meth) acrylate , Adamantyl (meth) acrylate, norbornenyl (meth) acrylate, pinenyl (meth) acrylate, dicyclope Esters including thenyl (meth) acrylate and alicyclic group of unsaturated carboxylic acids such as dicyclopentenyl oxyethyl (meth) acrylate;
Unsaturated carboxylic acid glycidyl esters such as glycidyl (meth) acrylate;
Unsaturated carboxylic acid oxetane esters such as oxetane (meth) acrylate;
Examples include monosaturated carboxylic esters of glycols such as oligoethylene glycol monoalkyl (meth) acrylate, and preferred examples include methyl (meth) acrylate and benzyl (meth) acrylate.

More preferably, in the above copolymer, another monomer copolymerizable with the unsaturated carboxylic acid and the acrylate ester can be used. Structural units derived from the other monomers include aromatic vinyl compounds such as styrene, α-methylstyrene and vinyltoluene;
Carboxylic acid vinyl esters such as vinyl acetate and vinyl propionate;
Vinyl cyanide compounds such as (meth) acrylonitrile and α-chloroacrylonitrile;
And maleimide compounds such as N-phenylmaleimide.
These may be used alone or in combination of two or more in producing the binder resin (A).
Further, if necessary, an unsaturated compound other than the acrylate ester may be used in combination.

  Among these other structural units, (meth) acrylic acid esters, in particular, unsubstituted or substituted alkyl esters of (meth) acrylic acid and esters containing alicyclic groups of (meth) acrylic acid are advantageously used.

  In the binder resin (A), the constitutional unit derived from the unsaturated carboxylic acid is usually present in the range of 10 to 50% by mass, preferably 15 to 40% by mass of all the constitutional units of the copolymer. preferable. When the structural unit derived from the unsaturated carboxylic acid is from 10 to 50% by mass based on the above criteria, the solubility in the developing solution is sufficient, so that no residue is generated on the unexposed portion of the substrate. This is preferable because there is no tendency for the pixel portion of the exposed portion to be reduced in film thickness at the time of development and the whole pixel does not peel off.

The binder resin (A) preferably has a weight average molecular weight in terms of polystyrene of 10,000 to 100,000, more preferably 15,000 to 50,000. When the weight average molecular weight of the binder resin (A) is in the range of 10,000 to 100,000, it is difficult to reduce the film thickness during development, and the non-pixel portion tends to have good removability during development. .
The binder resin (A) is contained in an amount of usually 5 to 90% by mass, preferably 10 to 70% by mass, based on the total solid content in the resist composition. When the amount of the binder resin (A) is 5 to 90% by mass on the basis of the above, the solubility in a developing solution is sufficient, and a development residue is hardly generated on a substrate in a non-pixel portion. This is preferable because film reduction of the pixel portion hardly occurs and the non-pixel portion tends to have good removability.

  The photopolymerizable monomer (B) contained in the colored photosensitive resin composition of the present invention is a compound that can be polymerized by the action of light and a photopolymerization initiator (C) described below. At least one monomer (b10) selected from the group consisting of a (meth) acrylic monomer (b11) having a (meth) acrylic group and a vinylether monomer (b12) having two vinylether groups in the same molecule; In combination with a (meth) acrylic monomer (b20) having five or more (meth) acrylic groups.

  Examples of (meth) acrylic monomers having two (meth) acrylic groups in the same molecule include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and polyethylene glycol di ( (Meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, propylene Glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 2-hydroxy-1,3-diacrylo Cipropane, 2,2-bis [4- (acryloxyethoxy) phenyl] propane, 2,2-bis [4- (acryloxydiethoxy) phenyl] propane, bis (acryloyloxyethyl) ether of bisphenol A, bisphenol Modified (meth) acrylic acid of A-type epoxy resin, 3-methylpentanediol di (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, dimethylol-tricyclodecanedi (meth) acrylate, and the like. Preferred are dimethylol-tricyclodecane di (meth) acrylate, neopentyl glycol di (meth) acrylate, and (meth) acrylic acid-modified bisphenol A type epoxy resin, and more preferably dimethylol-tricyclodecane diacrylate. Les DOO, neopentyl glycol diacrylate, acrylic acid-modified product of bisphenol A type epoxy resins.

  Vinyl ether monomers having two vinyl ether groups in the same molecule include ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, polyethylene glycol divinyl ether, 1,3-butylene glycol divinyl ether, and 1,4-butane. Diol divinyl ether, 1,6-hexanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, neopentyl glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, tripropylene glycol divinyl ether, polypropylene glycol divinyl ether, 2-hydroxy-1,3-divinyloxypropane, 2,2-bis [ -(Vinyloxyethoxy) phenyl] propane, 2,2-bis [4- (vinyloxydiethoxy) phenyl] propane, 3-methylpentanediol divinyl ether, dimethylol-tricyclodecane divinyl ether, divinyl etherified hydroquinone, Examples thereof include a divinyl etherified product of bisphenol A, and preferably, and more preferably.

  Examples of the (meth) acrylic monomer having five or more (meth) acrylic groups in the same molecule include dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and UA- manufactured by Kyoeisha Chemical Co., Ltd. Examples thereof include urethane acrylates such as 306H, UA-306T, and UA-306I, and preferably include dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate.

  At least one monomer selected from the group consisting of the (meth) acrylic monomer having two (meth) acrylic groups in the same molecule and the vinyl ether monomer having two vinylether groups in the same molecule; The molecular weight or polystyrene equivalent weight average molecular weight of a (meth) acrylic monomer having five or more (meth) acryl groups is preferably less than 1,000, and more preferably less than 800. It is preferred that the molecular weight of each of the monomer components be in the above range in terms of polystyrene, since a uniform coating film can be obtained. However, even when the molecular weight of each monomer component or the weight average molecular weight in terms of polystyrene exceeds 1,000, it may be used as long as a uniform coating film can be obtained.

In addition, other monofunctional monomers and other polyfunctional monomers can be used to the extent that the effects of the present invention are not impaired. Specific examples of other monofunctional monomers include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone, and the like.
Specific examples of other polyfunctional monomers include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and pentaerythritol tetra (meth) acrylate.

The photopolymerizable monomer (B) is usually 1 to 60 parts by mass, preferably 5 to 5 parts by mass, based on a total of 100 parts by mass of the binder resin (A) and the photopolymerizable monomer (B) in the colored photosensitive resin composition. It is contained in the range of 50 parts by mass. When the content of the photopolymerizable monomer (B) is in the range of 1 to 60 parts by mass based on the above criteria, the strength, pattern shape and smoothness of the pixel portion tend to be good, which is preferable.
Further, at least one monomer selected from the group consisting of a (meth) acryl monomer having two (meth) acryl groups in the same molecule and a vinyl ether monomer having two vinyl ether groups in the same molecule, The ratio of the (meth) acrylic monomer having 5 or more (meth) acrylic groups in the same molecule has two (meth) acrylic groups in the same molecule when the total of these monomers is 100 parts by mass. The use ratio of at least one monomer selected from the group consisting of a (meth) acrylic monomer and a vinyl ether monomer having two vinyl ether groups in the same molecule is preferably in the range of 10 to 90 parts by mass, more preferably 15 to 80 parts by mass. The range is more preferable. When the use ratio is within the above range, a forward tapered shape is obtained, which is preferable.

Next, the photopolymerization initiator (C) contained in the colored photosensitive resin composition of the present invention is obtained when it is a photopolymerization initiator containing at least one of a biimidazole compound, a triazine compound and an acetophenone compound. The colored photosensitive resin composition is preferable because it has higher sensitivity.
Furthermore, in addition to a photopolymerization initiator containing at least one of a triazine compound, an acetophenone compound and a biimidazole compound, a colored photosensitive resin composition obtained by using a photopolymerization initiation auxiliary agent (C-1) in combination Is more preferable because the sensitivity is further improved and the productivity when forming a color filter using this is improved.

  The triazine compound contained in the photopolymerization initiator (C) used in the colored photosensitive resin composition of the present invention includes 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,3 5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5 -Triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran -2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, , 4-bis (trichlorometh L) -6- [2- (4-Diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxy Phenyl) ethenyl] -1,3,5-triazine and the like, and examples of the acetophenone compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, and 2-hydroxy -1- [4- (2-hydroxyethoxy) phenyl] -2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1 -One, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-hi Oligomers of roxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one; and the like, and as the biimidazole compound, 2,2′-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole (for example, Patent Document 7 and 8 etc.), 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5 , 5'-Tetra (alkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (dialkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole (for example, Patent Documents 9 and 10 and the like). ) And imidazole compounds in which the phenyl group at the 4,4'5,5'-position is substituted by a carboalkoxy group (Patent Document 11), and the like, and preferably 2,2'-bis (2-chlorophenyl)- 4,4 ′, 5,5′-tetraphenylbiimidazole and 2,2′-bis (2,3-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole are exemplified.

JP-A-6-75372, page 27, left column, lines 27-41 JP-A-6-75373, page 3, left column, line 49-right column, line 13 JP-B-48-38403, page 2, left column, line 40-right column, line 44 JP-A-62-174204, page 2, right column, line 13-3 page, left column, line 9 Japanese Patent Laid-Open Publication No. 7-10913, page 23, left column, lines 23-37

  Further, as long as the effect of the present invention is not impaired, a photopolymerization initiator or the like usually used in this field can be used in combination, for example, benzoin-based, benzophenone-based, thioxanthone-based, anthracene-based, and other Of the initiator. More specifically, the following compounds can be mentioned, and these can be used alone or in combination of two or more.

(A) benzoin benzoin,
Benzoin methyl ether,
Benzoin ethyl ether,
Benzoin isopropyl ether,
Benzoin isobutyl ether and the like.
(B) benzophenone benzophenone,
methyl o-benzoylbenzoate,
4-phenylbenzophenone,
4-benzoyl-4'-methyldiphenyl sulfide,
3,3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone,
2,4,6-trimethylbenzophenone and the like.

(C) thioxanthone 2-isopropylthioxanthone,
4-isopropylthioxanthone,
2,4-diethylthioxanthone,
2,4-dichlorothioxanthone,
1-chloro-4-propoxythioxanthone and the like.

(D) anthracene 9,10-dimethoxyanthracene,
2-ethyl-9,10-dimethoxyanthracene,
9,10-diethoxyanthracene,
2-ethyl-9,10-diethoxyanthracene and the like.

(E) other 2,4,6-trimethylbenzoyldiphenylphosphine oxide,
10-butyl-2-chloroacridone,
2-ethylanthraquinone,
Benzyl,
9,10-phenanthrenequinone,
Camphor quinone,
Methyl phenylglyoxylate,
Titanocene compounds and the like.

  Further, the photopolymerization initiator may be used in combination with the photopolymerization initiation assistant (C-1). As the photopolymerization initiation aid, an amine compound, a thiol group-containing compound and a specific carboxylic acid compound are preferable, and the amine compound is more preferably an aromatic amine compound. Specific examples of the photopolymerization initiation aid include aliphatic amine compounds such as triethanolamine, methyldiethanolamine, and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and 4-dimethylaminobenzoic acid. Isoamyl, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'-bis An aromatic amine compound such as (diethylamino) benzophenone is exemplified, and the thiol group-containing compound is a compound having a thiol group in a molecule. As a thiol compound having one thiol group, 2-mercaptobenzothiazole, 2-mercapto Benzo Examples of aliphatic polyfunctional thiol compounds having a plurality of thiol groups in an aliphatic group such as oxazole include hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol bisthiopropionate, and butanediol bis. Thioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, butanediol bisthiopropionate, trimethylolpropane tristhiopropionate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthio Propionate, pentaerythritol tetrakisthioglycolate, trishydroxyethyltristhiopropionate, and, in addition to these, thioglycolate, Pioneto and the like, preferably trimethylolpropane tris thiopropionate, trimethylolpropane tris thioglycolate and pentaerythritol tetrakis thio propionate. Specific carboxylic acid compounds include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, Examples include N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

In the photopolymerization initiator (C), the total amount of the photopolymerization initiator (C) is usually 0.1 to 40 parts by mass based on 100 parts by mass of the total of the binder resin (A) and the photopolymerizable monomer (B). , Preferably 1 to 30 parts by mass. The total amount of (3) the photopolymerization initiation auxiliary is usually 0.1 to 50 parts by mass, preferably 1 to 40 parts by mass, based on 100 parts by mass of the total of the binder resin (A) and the photopolymerizable monomer (B). Parts.
When the total amount of the photopolymerization initiator (C) is in the above range, the colored photosensitive resin composition has high sensitivity, and the strength of the pixel portion formed using the colored photosensitive resin composition, This is preferable because the smoothness on the surface of the pixel tends to be good.
Further, when the amount of the photopolymerization initiation aid (C-1) in addition to the photopolymerization initiator (C) is within the above range, the sensitivity of the obtained colored photosensitive resin composition is further increased, and The productivity of the color filter formed using the photosensitive resin composition tends to improve, which is preferable.

  The coloring material (D) is usually a pigment, and can be an organic pigment or an inorganic pigment usually used for a pigment-dispersed resist. Examples of inorganic pigments include metal compounds such as metal oxides and metal complex salts.Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony metals Oxides or composite metal oxides are mentioned. Specific examples of organic pigments and inorganic pigments include compounds classified as Pigment in the Color Index (published by The Society of Dyers and Colorists). More specifically, examples include, but are not limited to, compounds having the following color index (CI) numbers.

C. I. Pigment Yellow 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 153, 154, 166 and 173;
C. I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65 and 71;
C. I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 215, 216, 224, 242 and 254;
C. I. Pigment Violet 14, 19, 23, 29, 32, 33, 36, 37 and 38;
C. I. Pigment Blue 15 (15: 3, 15: 4, 15: 6, etc.), 2122, 28, 60 and 64;
C. I. Pigment Green 7, 10, 15, 25, 36 and 47;
C. I. Pigment brown 28;
C. I. Pigment Black 1 and 7, and the like.

  These coloring materials (D) can be used alone or in combination of two or more. The coloring material (D) is used in an amount of usually 5 to 60% by mass, preferably 10 to 55% by mass, based on the total solid content in the colored photosensitive resin composition. When the content of the coloring material (D) is in the range of 5 to 60 parts by mass based on the above-described standard, the color density of the pixel is sufficient even if the film is formed as a thin film, and the removability of the non-pixel portion decreases during development. Therefore, there is a tendency that a residue hardly occurs, which is preferable.

The solvent (E) can be various ones used in this field. Specific examples thereof include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether and ethylene glycol monobutyl ether;
Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether;
Ethylene glycol alkyl ether acetates, such as methyl cellosolve acetate and ethyl cellosolve acetate;
Alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxypentyl acetate;
Aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene;
Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone;
Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin;
Esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate;
and cyclic esters such as γ-butyrolactone.
These solvents (E) can be used alone or in combination of two or more.
The amount of the solvent (E) to be used is 60 to 90% by mass, preferably 70 to 85% by mass, based on the total amount of the colored photosensitive resin composition containing the solvent. When the content of the solvent (E) is in the range of 60 to 90 parts by mass on the basis of the above, the coating properties tend to be good, which is preferable.

  In the colored photosensitive resin composition of the present invention, if necessary, additives such as a filler, another polymer compound, a pigment dispersant, an adhesion promoter, an antioxidant, an ultraviolet absorber, and an anti-aggregation material ( F) may be used as a mixture.

  Specific examples of the filler include glass, silica, and alumina, and specific examples of the other polymer compound include polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylate. .

  As the pigment dispersant, a commercially available pigment dispersant can be used, and examples thereof include silicone-based, fluorine-based, ester-based, cationic, anionic, nonionic, and amphoteric surfactants. Or a combination of two or more. Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, and polyethylene imines In addition to the above, KP (made by Shin-Etsu Chemical Co., Ltd.), Polyflow (made by Kyoei Chemical Co., Ltd.), F-top (made by Tochem Products Co., Ltd.), Megafax (made by Dainippon Ink and Chemicals, Inc.) ), Florard (manufactured by Sumitomo 3M Limited), Asahi Guard, Surflon (all manufactured by Asahi Glass Co., Ltd.), Solsperse (manufactured by Zeneca Corporation), EFKA (manufactured by EFKA CHEMICALS), PB821 (manufactured by Ajinomoto Co., Ltd.) ).

  Specific examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2- Aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) Examples include ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane.

  Specific examples of the antioxidant include 2,2'-thiobis (4-methyl-6-tert-butylphenol) and 2,6-di-tert-butyl-4-methylphenol.

  Specific examples of the ultraviolet absorber include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole, alkoxybenzophenone, and the like.

  Specific examples of the other polymer compound include a thermosetting resin such as an epoxy resin and a thermoplastic resin such as polyester and polyurethane.

  Specific examples of the coagulant include sodium polyacrylate.

  The colored photosensitive resin composition of the present invention can be prepared, for example, as follows. That is, the coloring material (D) is previously mixed with the solvent (E) and dispersed using a bead mill or the like until the coloring material has an average particle diameter of about 0.2 μm or less. At this time, a pigment dispersant is used as needed, and a part or all of the binder resin (A) may be blended. To the resulting dispersion (mill base), the remainder of the binder resin (A), the photopolymerizable monomer (B) and the photopolymerization initiator (C), other components used as needed, and further added as necessary To obtain a desired colored photosensitive resin composition.

  The photosensitive resin composition thus prepared can be applied to a base material as described below, and subjected to photocuring and development to form a black matrix or a colored image. First, the composition is spin-coated on a substrate (usually glass) and dried by heating (prebaking) to remove the solvent, thereby obtaining a smooth coating film. The thickness of the coating film at this time is about 1 to 3 μm. The coating film thus obtained is irradiated with ultraviolet rays through a target black matrix or a negative mask for forming an image. At this time, it is preferable to use a device such as a mask aligner so that the entire exposed portion is uniformly irradiated with parallel light beams and accurate alignment between the mask and the substrate is performed. Thereafter, the cured coating film is brought into contact with a dilute aqueous alkaline solution to dissolve and develop the non-exposed portions, thereby obtaining a desired black matrix or image. After development, post-curing (post-baking) at 150 to 230 [deg.] C. for about 10 to 60 minutes can be performed as necessary.

The developer used for the development after the patterning exposure is usually an aqueous solution containing an alkaline compound and a surfactant.
The alkaline compound may be any of inorganic and organic alkaline compounds. Specific examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, Examples include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium borate, potassium borate, and ammonia.
Specific examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, and ethanolamine. And the like. These inorganic and organic alkaline compounds can be used alone or in combination of two or more. The preferred concentration of the alkaline compound in the alkaline developer is in the range of 0.01 to 10% by mass, more preferably 0.03 to 5% by mass.

The surfactant in the alkali developer may be any of a nonionic surfactant, an anionic surfactant and a cationic surfactant.
Specific examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymer, sorbitan fatty acid ester, polyoxyethylene Oxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine and the like can be mentioned.
Specific examples of anionic surfactants include higher alcohol sulfates such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, sodium dodecylbenzene sulfonate, Alkyl aryl sulfonates such as sodium dodecylnaphthalene sulfonate, and the like.
Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride, and quaternary ammonium salts.
These surfactants can be used alone or in combination of two or more.
The concentration of the surfactant in the alkali developer is usually in the range of 0.01 to 10% by mass, preferably 0.05 to 8% by mass, and more preferably 0.1 to 5% by mass.

  Through the steps of applying the photosensitive resin liquid as described above, drying, patterning exposure to the obtained dried coating film, and developing, a pixel or a black matrix corresponding to the color of the coloring material in the photosensitive resin composition is formed. The color filter is obtained by repeating these operations by the number of colors required for the color filter. That is, the color filter is usually a black matrix, and three primary color pixels of red, green and blue are arranged on the substrate, but using the colored photosensitive resin composition of the present invention containing a coloring material corresponding to a certain color. By performing the above operation, a black matrix or pixel of that color is obtained, and the same operation is performed using the colored photosensitive resin composition of the present invention containing a coloring material corresponding to a desired color also for other colors. To arrange the black matrix and the three primary color pixels on the substrate. Of course, the photosensitive resin composition of the present invention can be applied to only one, two, or three of the black matrix and the three primary colors. In addition, since the black matrix which is the light-shielding layer may be formed of, for example, a chromium layer, it is not necessary to use the colored photosensitive resin composition of the present invention for forming the black matrix in this case.

The color filter produced using the photosensitive solution of the present invention has a small in-plane film thickness difference, for example, a film thickness of 1 to 3 μm, an in-plane film thickness difference of 0.15 μm or less, and more preferably 0.1 μm or less. It can be not more than 05 μm.
Further, an ITO film can be formed on the obtained pixels without an overcoat. The ITO film can be formed by appropriately examining the conditions described in Non-Patent Document 1, for example.
Accordingly, the color filter thus obtained has a forward tapered pixel pattern, and by incorporating this into a color liquid crystal display device, a liquid crystal panel of excellent quality can be manufactured with a high yield.

  Although the embodiments of the present invention have been described above, the embodiments of the present invention disclosed above are merely examples, and the scope of the present invention is not limited to these embodiments. The scope of the present invention is defined by the appended claims, and includes all modifications within the meaning and scope equivalent to the description of the claims. Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In the examples, percentages and parts representing the content or the used amount are based on mass unless otherwise specified.

Example 1
Among the components described in Table 1, the pigment and the pigment dispersant were previously mixed so that the total amount of the pigment and the pigment dispersant was 20% by mass with respect to the mixture of the pigment, the pigment dispersant, and propylene glycol monomethyl ether acetate. The pigment was sufficiently dispersed using the mixture, and the remaining components including the remaining amount of propylene glycol monomethyl ether acetate were added thereto and mixed to obtain a colored photosensitive resin composition.

A 2-inch square # 7059 glass substrate manufactured by Corning Incorporated was washed sequentially with a neutral detergent, water and alcohol, and then dried. The photosensitive resin solution prepared above (Table 1) was spin-coated on this glass substrate, and then prebaked at 100 ° C. for 3 minutes in a clean oven. After cooling, the distance between this resist-coated substrate and a quartz glass photomask (having a pattern in which the transmittance changes stepwise in the range of 1 to 100% and a line / space pattern from 1 to 50 μm) is set to 100 μm. Then, light irradiation was performed using an ultrahigh pressure mercury lamp (model number: USH-250D) manufactured by Ushio Inc. at an exposure amount of 100 mJ / cm ^{2 in} an air atmosphere. Thereafter, the coating film is immersed in a water-based developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at room temperature for a predetermined time to be developed, washed with water, and post-baked at 220 ° C. for 30 minutes. Was performed to obtain a pixel. Table 2 shows the obtained results. An ITO film was formed on the obtained pixel without an overcoat. The ITO film was formed by using a vapor deposition device (model number: SPF-530H) manufactured by Anelva Co., Ltd. at a sputtering temperature of 120 ° C. and a vapor deposition rate of 50 nm / min for 3 minutes, and then 230 in a clean oven at normal pressure. Annealing was performed at 40 ° C. for 40 minutes to form an ITO film. Observation of the cross section of the pixel with a scanning electron microscope confirmed that the ITO film was not disconnected.

Example 2
The same operation as in Example 1 was performed, except that dimethylol-tricyclodecane diacrylate was changed to neopentyl glycol diacrylate (molecular weight: 212) in Example 1. Table 2 shows the obtained results. The ITO film formed on the obtained pixel without an overcoat was not disconnected.

Example 3
Example 1 was the same as Example 1 except that dimethylol-tricyclodecane diacrylate was changed to an acrylic acid-modified product of diglycidyl etherified bisphenol A (Kyoeisha Chemical Co., Ltd. epoxy ester 3000A; molecular weight 484). A similar operation was performed. Table 2 shows the obtained results. The ITO film formed on the obtained pixel without any overcoat was not disconnected.

Comparative Example 1
The same operation as in Example 1 was performed, except that dimethylol-tricyclodecane diacrylate was changed to dipentaerythritol hexaacrylate (KAYARAD DPHA). Table 2 shows the obtained results. When an ITO film was formed on the obtained pixel without overcoating, the ITO film was not formed in the reverse tapered portion and the ITO film was broken by observation of the cross section of the pixel with a scanning electron microscope. .

Comparative Example 2
In the same manner as in Example 1, except that dimethylol-tricyclodecane diacrylate was changed to pentaerythritol tetraacrylate. Table 2 shows the obtained results. When an ITO film was formed on the obtained pixel without overcoating, the ITO film was not formed in the reverse tapered portion and the ITO film was broken by observation of the cross section of the pixel with a scanning electron microscope. .

Comparative Example 3
In Example 1, the same operation as in Example 1 was performed except that dimethylol-tricyclodecane diacrylate was changed to trimethylolpropane triacrylate. Table 2 shows the obtained results. When an ITO film was formed on the obtained pixel without overcoating, the ITO film was not formed in the reverse tapered portion and the ITO film was broken by observation of the cross section of the pixel with a scanning electron microscope. .

Example 4
In Example 1, the same operation as in Example 1 was performed except that dimethylol-tricyclodecane diacrylate was changed to divinyl etherified product of bisphenol A (BPA-DEV manufactured by Nisso Maruzen Chemical Co., Ltd .; molecular weight: 368). went. Table 3 shows the obtained results. The ITO film formed on the obtained pixel without any overcoat was not disconnected.

Example 5
In Example 4, the same operation as in Example 4 was performed, except that the divinyl ether compound of bisphenol A was changed to a divinyl ether compound of hydroquinone (HQ-DEV manufactured by Nisso Maruzen Chemical Co., Ltd.). Table 3 shows the obtained results. The ITO film formed on the obtained pixel without any overcoat was not disconnected.

Example 6
In Example 4, the same operation as in Example 4 was performed except that the divinyl etherified product of bisphenol A was changed to a divinyl etherified product of 1,4-butanediol (Butandiol-1,4-Divinyl ether manufactured by BASF). went. Table 3 shows the obtained results. The ITO film formed on the obtained pixel without any overcoat was not disconnected.

Explanation of annotations in the table
* 1: Indicates the minimum exposure required to form a pattern without surface roughness even when developed.
* 2: Exposure was performed at an exposure amount of 30 mJ / cm ² , and the cross section of the pixel after development and post-baking (220 ° C. × 20 minutes) was observed with a scanning electron microscope. (Shape without reverse taper shape; ○, reverse taper shape; ×)

From Table 2 and the obtained results, in the colored photosensitive resin compositions of Examples 1 to 3 containing the photopolymerization initiator of the present invention, high sensitivity, a forward tapered pattern was obtained, and after the post-baking, Although it is understood that the surface smoothness is good, the colored photosensitive resin compositions of Comparative Examples 1 to 4 of the present invention which do not contain the (meth) acrylic monomer having two (meth) acrylic groups in the same molecule are not included. It can be seen that the sensitivity is good but a forward tapered shape cannot be obtained.
Table 3 and the obtained results show that the colored photosensitive resin compositions of Examples 4 to 6 containing the photopolymerization initiator of the present invention obtained a forward tapered pattern.

The colored photosensitive resin composition of the present invention is a colored photosensitive resin composition suitable for a resist for forming a colored image used in a color liquid crystal display device, an imaging device, and the like.

Claims (10)

Binder resin (A),
Photopolymerizable monomer (B),
Photopolymerization initiator (C),
In a colored photosensitive resin composition containing a coloring material (D) and a solvent (E),
The photopolymerizable monomer (B) comprises a (meth) acrylic monomer (b11) having two (meth) acryl groups in the same molecule and a vinyl ether monomer (b12) having two vinyl ether groups in the same molecule. A colored photosensitive resin composition comprising at least one monomer (b10) selected from the group and a (meth) acrylic monomer (b20) having 5 or more (meth) acrylic groups in the same molecule.   At least one monomer selected from the group consisting of a (meth) acrylic monomer (b11) having two (meth) acryl groups in the same molecule and a vinyl ether monomer (b12) having two vinyl ether groups in the same molecule 2. The coloring according to claim 1, wherein the molecular weight of the (b10) and the (meth) acrylic monomer (b20) having 5 or more (meth) acrylic groups in the same molecule is smaller than 1,000, respectively. Photosensitive resin composition.   At least one monomer selected from the group consisting of a (meth) acrylic monomer (b11) having two (meth) acryl groups in the same molecule and a vinyl ether monomer (b12) having two vinyl ether groups in the same molecule When the total of (b10) and (meth) acrylic monomer (b20) having 5 or more (meth) acrylic groups in the same molecule is 100 parts by mass, two (meth) acrylic groups in the same molecule The use ratio of at least one monomer (b10) selected from the group consisting of a (meth) acrylic monomer (b11) having the formula (I) and a vinyl ether monomer (b12) having two vinyl ether groups in the same molecule is 10 to 90 parts by mass. The colored photosensitive resin composition according to claim 1 or 2, wherein   The colored photosensitive material according to any one of claims 1 to 3, wherein the photopolymerization initiator (C) comprises at least one selected from the group consisting of a triazine compound, an acetophenone compound, and a biimidazole compound. Resin composition.   The colored photosensitive resin composition according to any one of claims 1 to 4, wherein the binder resin (A) is a polymer containing a structural unit derived from an unsaturated carboxylic acid.   The colored photosensitive resin composition according to any one of claims 1 to 5, wherein the binder resin (A) is a copolymer containing a structural unit derived from an unsaturated carboxylic acid and a structural unit derived from a (meth) acrylate compound. object.   The colored photosensitive resin composition according to any one of claims 1 to 6, further comprising a photopolymerization initiation aid (C-1).   The colored photosensitive resin composition according to any one of claims 1 to 7, which is applied on a substrate or a layer formed of the solid content of the previously formed colored photosensitive resin composition, and volatilized from the applied colored photosensitive resin composition layer. A method for forming a pattern in which components are removed, the layer is exposed through a photomask, and developed.   A color filter comprising a pattern formed by the method according to claim 8. A liquid crystal display device using the color filter according to claim 9.