JP4534697B2 - Colored photosensitive resin composition - Google Patents

Description

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

  A color filter in a color liquid crystal display device or an image sensor is usually manufactured by forming red, green, and blue three primary color pixels on a substrate such as glass or a silicon wafer. Further, it is usual to provide a black matrix for shielding light between these pixels. In order to form the pixels of each color, a photosensitive resin composition containing a pigment corresponding to each color is uniformly applied on a substrate on which a black matrix is formed by a spin coater, and then dried by heating (hereinafter referred to as a “black matrix”). , Pre-baking)), and exposing and developing the coating film, and further heat-curing (hereinafter sometimes referred to as post-baking) if necessary. By repeating for each required color, an image of each color is obtained. As such a photosensitive resin composition, many compositions containing a photopolymerizable compound and a photopolymerization initiator are used together with a pigment and a binder resin. Moreover, the photosensitive resin composition containing a black pigment may be used also for formation of a black matrix. In such a photosensitive coloring composition, an acrylic resin having a carboxyl group in the side chain is used because of excellent light resistance and little color change. For example, a colored resin composition is disclosed in which an acrylic resin containing a carboxyl group in the side chain contains a pigment and a polyfunctional acrylate (see, for example, Patent Document 1). In addition, in order to increase sensitivity, a reactive acrylic resin is used, in which a polybasic acid anhydride is added after adding an unsaturated carboxylic acid to a polymer composed of a monomer having an epoxy group and an unsaturated double bond. A photosensitive resin composition is disclosed (see, for example, Patent Document 2).

  However, the conventional colored layer (colored pixel) formed in a pattern is not excellent in both sensitivity and hardness. For example, when the sensitivity is low, the productivity of the color filter is inferior and the hardness is low. In the post-process such as alignment film rubbing after color filter fabrication, the colored layer is easily damaged, and when the liquid crystal panel is assembled, it is colored by the pressure from the spacer material interposed between the two substrates As a result, the layer is easily deformed, and as a result, the cell gap fluctuates locally, which causes display defects. In general, the colored layer of a color filter is composed of at least a colorant such as a pigment (organic pigment or inorganic pigment) or dye, and a resin component (dispersant, binder resin, etc.). Even if it is cross-linked, it is soft, and the pencil hardness of the surface is usually about HB to 2H.

JP-A-3-53201, page 3, left column, lines 7-20 JP-A-8-297366, page 2, left column, lines 1-6

  An object of the present invention is to provide a colored photosensitive resin composition having high sensitivity and high hardness even if it contains a coloring material. Another object of the present invention is that when a pixel is formed using the colored photosensitive resin composition, a development residue may be generated on the substrate or surface roughness may be generated on the pixel portion. Furthermore, the obtained pixel is to provide a high-quality color filter having high pencil hardness and excellent reliability.

As a result of intensive studies on new means that can solve the above-mentioned problems, the present inventors have found that a colored photosensitive resin composition containing a specific unsaturated group-containing binder resin and a specific photopolymerization initiator has the above-mentioned problems. The inventors have found that this can be solved, and have reached the present invention.
That is, the present invention provides a binder resin (A),
Photopolymerizable compound (B),
Photopolymerization initiator (C),
In the colored photosensitive resin composition containing the coloring material (D) and the solvent (E),
The binder resin (A) is an unsaturated group-containing resin obtained by further reacting (A4) with a copolymer obtained by copolymerizing the following (A1) to (A3):
The photopolymerization initiator (C) is at least one compound selected from the group consisting of a triazine compound, an acetophenone compound, a biimidazole compound, and an oxime compound, and provides a colored photosensitive resin composition.
(A1); Compound (A2) having at least one skeleton selected from the group consisting of a tricyclodecane skeleton and a dicyclopentadiene skeleton and an unsaturated bond in one molecule; and (A1) and (A3) Compound (A3) having polymerizable unsaturated bond; Unsaturated carboxylic acid (A4); Compound having unsaturated bond and epoxy group in one molecule. The present invention also includes the above colored photosensitive resin composition. The layer is applied on the substrate or the layer formed of the solid content of the colored photosensitive resin composition previously formed, the volatile component is removed from the applied colored photosensitive resin composition layer, and the layer is formed through a photomask. A pattern forming method of exposing and developing a color filter, a color filter including the pattern formed by the above method, and a liquid crystal display device using the color filter are provided.

  The colored photosensitive resin composition of the present invention is excellent in sensitivity and pencil hardness, and no development residue is generated on the substrate when pixels are formed. Therefore, when producing the color filter using the colored photosensitive resin composition of the present invention as a pigment dispersion resist, it is possible to obtain a color filter having excellent productivity and high quality. The colored photosensitive resin composition of the present invention can also be used as a colored photospacer. Further, the photosensitive resin composition excluding the coloring material can be applied to an insulating film, a photo spacer, an overcoat (planarization film), and a protrusion forming material for controlling liquid crystal alignment.

  Hereinafter, the present invention will be described in detail.

  The colored photosensitive resin composition of the present invention is mainly used as a pigment dispersion resist, and includes a coloring material (D), a binder resin (A), a photopolymerizable compound (B), and a photopolymerization initiator ( C) and optionally other additives (F) are dissolved or dispersed in the solvent (E).

The binder resin (A) generally has reactivity and alkali solubility due to the action of light and heat, and acts as a dispersion medium for the coloring material. The binder resin (A) used in the colored photosensitive resin composition of the present invention is obtained by reacting (A4) with a copolymer obtained by copolymerizing the following (A1) to (A3). It is a saturated group-containing resin.
(A1); Compound (A2) having at least one skeleton selected from the group consisting of a tricyclodecane skeleton and a dicyclopentadiene skeleton and an unsaturated bond in one molecule; and (A1) and (A3) Compound (A3) having polymerizable unsaturated bond; Unsaturated carboxylic acid (A4); Compound having unsaturated bond and epoxy group in one molecule

  Specific examples of the compound (A1) having an unsaturated bond and a tricyclodecane skeleton and / or a dicyclopentadiene skeleton in one molecule include dicyclopentanyl (meth) acrylate and dicyclopentenyl (meth). Examples include acrylate, dicyclopentanyloxyethyl (meth) acrylate, and dicyclopentenyloxyethyl (meth) acrylate. These can be used alone or in combination. Here, description of (meth) acrylate in this specification represents an acrylate and / or a methacrylate.

Specific examples of the compound (A2) having an unsaturated bond copolymerizable with (A1) and (A3) include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, Unsubstituted or substituted alkyl esters of unsaturated carboxylic acids such as 2-hydroxyethyl (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 (meta) ) Acrylate, cycloheptenyl (meth) acrylate, cyclooctenyl (meth) acrylate, mentadienyl (meth) acrylate, isobornyl (meth) acrylate, pinanyl (meth) acrylate, adamantyl (meth) acrylate, norbornenyl (meth) acrylate, pinenyl (meth) acrylate An ester compound containing an alicyclic group of an unsaturated carboxylic acid such as
Monosaturated carboxylic acid ester compounds of glycols such as oligoethylene glycol monoalkyl (meth) acrylate;
Ester compounds containing an aromatic ring of an unsaturated carboxylic acid such as benzyl (meth) acrylate and phenoxy (meth) acrylate;
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;
Examples thereof include maleimide compounds such as N-cyclohexylmaleimide and N-phenylmaleimide. These can be used alone or in combination.

  Specific examples of the unsaturated carboxylic acid (A3) include acrylic acid and methacrylic acid. Acrylic acid and methacrylic acid can be used alone or in combination. In addition to these acrylic acid and methacrylic acid, other acids can be used. Specifically, as the other acid, at least one carboxylic acid selected from other unsaturated carboxylic acids such as crotonic acid, itaconic acid, maleic acid and fumaric acid can be used in combination. A monomer containing a hydroxy group and a carboxyl group in the same molecule, such as α- (hydroxymethyl) acrylic acid, can also be used in combination.

First, in the copolymer obtained by copolymerizing (A1) to (A3) in the present invention, the ratio of the components derived from each of (A1) to (A3) constitutes the copolymer. It is preferable to be in the following range in terms of mole fraction with respect to the total number of moles of the constituent components.
Structural units derived from (A1); 2 to 30 mol%
Structural units derived from (A2); 2 to 95 mol%
Structural units derived from (A3); 2 to 70 mol%
Moreover, it is more preferable in the ratio of the said structural component being the following ranges.
Structural units derived from (A1); 5 to 25 mol%
Structural units derived from (A2); 5 to 80 mol%
Structural units derived from (A3); 5 to 60 mol%
When the composition ratio is in the above range, the balance of developability, flexibility and heat resistance is good, and a preferable trunk polymer is obtained.
Furthermore, next, (A4) can be added to the copolymer to impart photo / thermosetting properties to the binder resin.
Specific examples of the compound (A4) having an unsaturated bond and an epoxy group in one molecule include glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, and 3,4-epoxycyclohexylmethyl. (Meth) acrylate and methyl glycidyl (meth) acrylate are mentioned. Preferably, glycidyl (meth) acrylate is used. These can be used alone or in combination of two or more.
The amount of (A4) added is 5 to 90 mol%, preferably 10 to 80 mol%, based on the carboxyl group (derived from the A3 component) in the resin obtained by polymerizing (A1) to (A3). It is.
When the composition ratio of (A4) is within the above range, sufficient photocurability and thermosetting are obtained, both sensitivity and pencil hardness are achieved, and reliability is preferable.

The binder resin (A) preferably has a polystyrene-equivalent weight average molecular weight in the range of 3,000 to 100,000, and more preferably in the range of 5,000 to 50,000. When the weight average molecular weight of the binder resin (A) is in the range of 3,000 to 100,000, film loss is unlikely to occur during development, and non-pixel portion omission tends to be good during development, which is preferable. .
The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the binder resin (A) is preferably 1.5 to 6.0, more preferably 1.8 to 4.0. preferable. A molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of 1.5 to 6.0 is preferable because of excellent developability.
The binder resin (A) used in the colored photosensitive resin composition of the present invention is usually in the range of 5 to 90% by mass, preferably 10 to 70% by mass, based on the total solid content in the colored photosensitive resin composition. Contained. When the content of the binder resin (A) is 5 to 90% by mass on the basis of the above, the solubility in the developer is sufficient, and a development residue is hardly generated on the non-pixel portion of the substrate. It is sometimes preferable because the film thickness of the pixel portion of the exposed portion is less likely to occur, and the non-pixel portion tends to be easily removed.

The photopolymerizable compound (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 described later. It can be a polyfunctional monomer.
Specific examples of the monofunctional monomer include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N-vinyl pyrrolidone and the like.
Specific examples of the bifunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and bisphenol A. Bis (acryloyloxyethyl) ether, 3-methylpentanediol di (meth) acrylate, and the like.
Specific examples of other polyfunctional monomers include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa ( And (meth) acrylate. Of these, polyfunctional monomers having two or more functions are preferably used.
A photopolymerizable compound (B) is 1-60 mass parts normally with respect to a total of 100 mass parts of binder resin (A) and a photopolymerizable compound (B) in a coloring photosensitive resin composition, Preferably it is 5-5. It is contained in the range of 50 parts by mass. When the content of the photopolymerizable compound (B) is in the range of 1 to 60 parts by mass based on the above criteria, the strength and smoothness of the pixel part tend to be favorable, which is preferable.

  The photopolymerization initiator (C) contained in the colored photosensitive resin composition of the present invention is a colored photosensitive resin obtained by an initiator system comprising at least one of a triazine compound, an acetophenone compound, and a biimidazole compound. The composition has high sensitivity, and a film formed using the composition has good strength and surface smoothness of the pixel portion. Furthermore, by using the photopolymerization initiation assistant (C-1) in combination, the resulting colored photosensitive resin composition becomes more sensitive, and the productivity when forming a color filter using this is improved. preferable.

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-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-methoxy Styryl) -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, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino- 2-methylphenyl) Thenyl] -1,3,5-triazine, such as 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.
Examples of the acetophenone compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 2-hydroxy-1- [4- (2-hydroxyethoxy). Phenyl] -2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino- Examples include oligomers of 1- (4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one, and the like. Further, as acetophenone compounds, those described in JP-A-63-264560 can be used. As said acetophenone series compound, it shows by following formula (1), for example.

[In Formula (1), R ^{1 to} R ⁴ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a phenyl group optionally substituted by an alkyl group having 1 to 12 carbon atoms, or an alkyl having 1 to 12 carbon atoms. The benzyl group which may be substituted by group, or the naphthyl group which may be substituted by the C1-C12 alkyl group is represented. ]

Furthermore, 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 (see, for example, JP-A-6-75372 and JP-A-6-75373), 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) bi Dazole (for example, see JP-B-48-38403, JP-A-62-174204, etc.), an imidazole compound in which the phenyl group at the 4,4′5,5′-position is substituted with a carboalkoxy group ( For example, see JP-A-7-10913, etc.), preferably 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2 Examples include '-bis (2,3-dichlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole.
Furthermore, as the oxime compound, O-ethoxycarbonyl-α-oximino-1-phenylpropan-1-one,

Etc.

In addition, a photopolymerization initiator or the like commonly used in this field can be used in combination as long as the effect of the present invention is not impaired. For example, a benzoin compound, a benzophenone compound, a thioxanthone compound, an anthracene And photopolymerization initiators such as a series compound.
More specifically, the following compounds can be mentioned, and these can be used alone or in combination of two or more.

  Examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

  Examples of the benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3 ', 4,4'-tetra (tert-butyl). Peroxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.

  Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like.

  Examples of the anthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl-9,10-diethoxyanthracene. It is done.

  In addition, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate And titanocene compounds are exemplified as photopolymerization initiators.

Moreover, what is described in Japanese translations of PCT publication No. 2002-544205 gazette can be used as a photoinitiator which has the group which can raise | generate chain transfer.
As a photoinitiator which has the group which can raise | generate the said chain transfer, the thing of following formula (2)-(7) is mentioned, for example.

  The photopolymerization initiator having a group capable of causing the chain transfer can be used as a constituent component (A2) of a copolymer obtained by copolymerizing the above (A1) and (A3). And the obtained copolymer can be used together with the binder resin of this invention.

Moreover, a photoinitiator (C-1) can also be used in combination with a photoinitiator. As said photoinitiation adjuvant (C-1), an amine compound and the following carboxylic acid compound are preferable, and an amine compound has an aromatic amine compound more preferable.
Specific examples of the photopolymerization initiation aid include aliphatic amine compounds such as triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid. Isoamyl, 2-dimethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (common name; Michler's ketone), 4,4'- Examples include aromatic amine compounds such as bis (diethylamino) benzophenone.
Examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, Examples include aromatic heteroacetic acids such as 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 with respect to 100 parts by mass in total of the binder resin (A) and the photopolymerizable compound (B). The total amount of (3) photopolymerization initiation assistant is usually 0.1 to 50 parts by mass, preferably 1 to 40 parts by mass based on the above-mentioned criteria.
When the total amount of the photopolymerization initiator (C) is within the above range, the colored photosensitive resin composition becomes highly sensitive, and the strength of the pixel portion formed using the colored photosensitive resin composition, The smoothness on the surface of the pixel tends to be good, which is preferable. In addition to the above, when the amount of the photopolymerization initiation assistant (C-1) is in the above range, the sensitivity of the obtained colored photosensitive resin composition is further increased, and the above colored photosensitive resin composition is used. This is preferable because the productivity of the color filter to be formed tends to be improved.

  The colored photosensitive resin composition of the present invention contains a coloring material (D). The coloring material (D) is usually a pigment, and can be an organic pigment or an inorganic pigment usually used for a pigment dispersion 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, antimony and other metal compounds. Oxides or mixed metal oxides may be 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, pigments having the following color index (C.I.) numbers may be mentioned, but the invention is not limited thereto.

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, 173 and 180;
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, 254, 255, and 264;
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.), 21, 28, 60, 64 and 76;
C. I. Pigment green 7, 10, 15, 25, 36 and 47;
C. I. Pigment brown 28;
C. I. Pigment Black 1 and 7, etc.

  These coloring materials (D) can be used alone or in combination of two or more. The coloring material (D) is usually used in the range of 3 to 60% by mass, preferably 5 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% by mass based on the above criteria, the color density of the pixel is sufficient even when a thin film is formed, and the non-pixel portion omission is reduced during development. Therefore, there is a tendency that a residue is hardly generated, which is preferable.

The colored photosensitive resin composition of the present invention contains a solvent (E). The solvent (E) can be various organic solvents used in the field of colored photosensitive resin compositions. 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.
Among the above-mentioned solvents, organic solvents having a boiling point of 100 ° C. to 200 ° C. are preferable among the above solvents from the viewpoint of coating properties and drying properties, and more preferable are alkylene glycol alkyl ether acetates and ketones 3 -Esters such as ethyl ethoxypropionate and methyl 3-methoxypropionate, particularly preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate and 3-methoxy And methyl propionate.
These solvents (E) can be used alone or in admixture of two or more.
Content of the solvent (E) in the colored photosensitive resin composition of this invention is a mass fraction with respect to the quantity of the whole colored photosensitive resin composition containing it, and is 60-90 mass% normally, Preferably it is 70. It is -85 mass%. When the content of the solvent (E) is in the range of 60 to 90% by mass based on the above criteria, a roll coater, a spin coater, a slit & spin coater, a slit coater (sometimes called a die coater), an ink jet, and the like. The coating property tends to be good when applied with the above-described coating apparatus, which is preferable.

In the colored photosensitive resin composition of the present invention, if necessary, additives such as fillers, other polymer compounds, pigment dispersants, adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation materials ( F) can also be used in combination.
Specific examples of the filler include glass, silica, and alumina.
Specific examples of other polymer compounds include curable resins such as epoxy resins and maleimide resins, and thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane. Can be used.
Commercially available surfactants can be used as the pigment dispersant, and examples include silicone-based, fluorine-based, ester-based, cationic-based, anionic-based, nonionic-based, 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 polyethyleneimines. In addition, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoei Chemical Co., Ltd.), F-Top (manufactured by Tochem Products), MegaFuck (manufactured by Dainippon Ink & Chemicals, Inc.) ), FLORARD (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard, Surflon (manufactured by Asahi Glass Co., Ltd.), Solsperse (manufactured by Geneca Corporation), EFKA (manufactured by EFKA CHEMICALS), PB821 (manufactured by Ajinomoto Co., Inc.) ) And the like.
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), 2,6-di-tert-butyl-4-methylphenol, and the like.
Specific examples of the ultraviolet absorber include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole and alkoxybenzophenone.
Specific examples of the flocculant 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 preliminarily mixed with the solvent (E) and dispersed using a bead mill or the like until the average particle diameter of the coloring material is about 0.2 μm or less. At this time, a pigment dispersant is used as necessary, and a part or all of the binder resin (A) may be blended. In the obtained dispersion (hereinafter sometimes referred to as mill base), the remainder of the binder resin (A), the photopolymerizable compound (B) and the photopolymerization initiator (C), and other used as necessary Components and, if necessary, an additional solvent are added so as to have a predetermined concentration to obtain a desired colored photosensitive resin composition.

  The photosensitive resin composition thus prepared can be applied on a substrate as described below, and photocured and developed to form a black matrix or a colored image. First, this composition is applied on a substrate (usually glass) or a layer made of a solid content of a previously formed colored photosensitive resin composition, and prebaked from the applied colored photosensitive resin composition layer. Volatile components such as solvents are removed to obtain a smooth coating film. At this time, the thickness of the coating film is about 1 to 3 μm. The coating film thus obtained is irradiated with ultraviolet rays through a target black matrix or a mask for forming an image. At this time, it is preferable to use an apparatus such as a mask aligner or a stepper so that the entire exposed portion is uniformly irradiated with parallel light rays and the mask and the substrate are accurately aligned. Further, after that, the cured coating film is brought into contact with an alkaline aqueous solution to dissolve the non-exposed portion and developed to obtain the intended black matrix or image. After development, post-baking can be performed at 150 to 230 ° C. for about 10 to 60 minutes as necessary.

The developer used for development after patterning exposure is usually an aqueous solution containing an alkaline compound and a surfactant.
The alkaline compound may be either an inorganic or organic alkaline compound. 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 thereof include sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, 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. Etc. These inorganic and organic alkaline compounds can be used alone or in combination of two or more. The preferable 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 alkaline developer may be any of a nonionic surfactant, an anionic surfactant, or a cationic surfactant.
Specific examples of nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters, polyoxyethylene Examples thereof include oxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, and polyoxyethylene alkylamine.
Specific examples of anionic surfactants include higher alcohol sulfate salts such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, And alkyl aryl sulfonates such as sodium dodecyl naphthalene sulfonate.
Specific examples of the cationic surfactant include amine salts or quaternary ammonium salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride.
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.

  The pixel or black matrix corresponding to the color of the coloring material in the photosensitive resin composition is obtained through the operations such as application of the photosensitive resin liquid, drying, patterning exposure to the resulting dried coating film, and development. Further, by repeating these operations for the number of colors required for the color filter, a color filter is obtained. That is, the color filter is usually a black matrix and pixels of three primary colors of red, green and blue arranged on the substrate, but the colored photosensitive resin composition of the present invention containing a coloring material corresponding to a certain color is used. 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 the desired color for the other colors. Yes, a black matrix and three primary color pixels can be placed on the substrate. Of course, it is also possible to apply the photosensitive resin composition of the present invention to only one, two or three of the black matrix and the three primary colors. In addition, since the black matrix which is a light shielding layer may be formed, for example by a chromium layer etc., in this case, of course, it is not necessary to use the coloring photosensitive resin composition of this invention for formation of a black matrix.

  And the color filter manufactured using the colored photosensitive resin composition of the present invention has a small in-plane film thickness difference, for example, a film thickness of 1 to 3 μm and an in-plane film thickness difference of 0.15 μm or less, Furthermore, it can be 0.05 μm or less. Therefore, the color filter obtained in this way is excellent in smoothness, and an excellent quality liquid crystal display device can be manufactured with a high yield by incorporating it into the color liquid crystal display device.

  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 terms of the claims, and includes the meaning equivalent to the description of the claims and all modifications within the scope. EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by these Examples. In the examples, “%” and “part” representing the content or amount used are based on mass unless otherwise specified.

<Synthesis of Resin A>
After introducing 182 g of propylene glycol monomethyl ether acetate into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen introduction tube, and changing the atmosphere in the flask from air to nitrogen, the temperature was raised to 100 ° C., 70.5 g (0.40 mol) of benzyl methacrylate, 43.0 g (0.5 mol) of methacrylic acid, 22.0 g (0.10 mol) of monomethacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) ) And propylene glycol monomethyl ether acetate (136 g) in a solution obtained by adding 3.6 g of azobisisobutyronitrile to the flask from the dropping funnel over 2 hours, and further stirring at 100 ° C. for 5 hours. Next, the atmosphere in the flask was changed from nitrogen to air, and 35.5 g of glycidyl methacrylate [0.25 mol, (50 mol% with respect to the carboxyl group of methacrylic acid used in this reaction)], trisdimethylaminomethylphenol, 0.5%. 9 g and 0.145 g of hydroquinone were charged into the flask, and the reaction was continued at 110 ° C. for 6 hours to obtain a resin A having a solid content acid value of 79 mgKOH / g. The weight average molecular weight in terms of polystyrene measured by GPC was 13,000, and the molecular weight distribution (Mw / Mn) was 2.1.
<Synthesis of Resin B>
After introducing 333 g of propylene glycol monomethyl ether acetate into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen introducing tube, and changing the atmosphere in the flask from air to nitrogen, the temperature was raised to 100 ° C., 70.5 g (0.40 mol) of benzyl methacrylate, 71.1 g (0.50 mol) of glycidyl methacrylate, 22.0 g (0.10 mol) of monomethacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) ) And 3.6 g of azobisisobutyronitrile added to a mixture of 164 g of propylene glycol monomethyl ether acetate was added dropwise to the flask from the dropping funnel over 2 hours, and stirring was continued at 100 ° C. for 5 hours. Next, the atmosphere in the flask was changed from nitrogen to air, 43.0 g of methacrylic acid [0.5 mol, (100 mol% with respect to the glycidyl group of glycidyl methacrylate used in this reaction)], trisdimethylaminomethylphenol,. 9 g and 0.145 g of hydroquinone were charged into the flask, and the reaction was continued at 110 ° C. for 6 hours. When the solid content acid value reached 1 mgKOH / g, the reaction was terminated. Next, 60.9 g (0.40 mol) of tetrahydrophthalic anhydride and 0.8 g of triethylamine were added and reacted at 120 ° C. for 3.5 hours to obtain a resin B having a solid content acid value of 80 mgKOH / g. The weight average molecular weight in terms of polystyrene measured by GPC was 12,000, and the molecular weight distribution (Mw / Mn) was 2.1.

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the binder polymer were measured using the GPC method under the following conditions.
Equipment: HLC-8120GPC (manufactured by Tosoh Corporation)
Column; TSK-GELG4000HXL + TSK-GELG2000HXL (series connection)
Column temperature: 40 ° C
Mobile phase solvent; tetrahydrofuran flow rate; 1.0 ml / min
Injection volume: 50 μl
Detector; RI
Measurement sample concentration: 0.6% by mass (solvent: tetrahydrofuran)
Standard material for calibration; TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corporation)
The ratio of the weight average molecular weight and the number average molecular weight obtained above was defined as molecular weight distribution (Mw / Mn).

Example 1
Among the components described in Table 1 below, the total amount of the pigment as the coloring material (D) and the pigment dispersant as the additive (F) is the same as that of the pigment, the pigment dispersant, and propylene glycol monomethyl ether acetate. After mixing the mixture to 20% by mass and sufficiently dispersing the pigment using a bead mill, the bead mill is separated, and the remaining components including the remaining amount of propylene glycol monomethyl ether acetate are added. By mixing, a colored photosensitive resin composition was obtained.

A 2-inch square glass substrate (manufactured by Corning, # 1737) was sequentially washed with a neutral detergent, water and alcohol and then dried. On this glass substrate, the colored photosensitive resin composition (Table 1) is exposed at an exposure amount (365 nm) of 100 mJ / cm ² , and the film thickness after post-baking when the developing step is omitted is 1. It spin-coated so that it might become 9 micrometers, and it prebaked for 3 minutes at 100 degreeC then in clean oven. After cooling, a substrate coated with the colored photosensitive resin composition and a quartz glass photomask (having a pattern that changes the transmittance stepwise in the range of 1 to 100% and a line / space pattern from 1 μm to 50 μm )) Was set to 100 μm, and irradiation was performed using an ultrahigh pressure mercury lamp (trade name; USH-250D) manufactured by Ushio Electric Co., Ltd. in an air atmosphere at an exposure amount (365 nm) of 100 mJ / cm ² . Thereafter, the coating film is immersed in an aqueous developer containing 0.12% of a nonionic surfactant and 0.06% of potassium hydroxide at 26 ° C. for a predetermined time, developed, washed with water, and post-treated at 220 ° C. for 30 minutes. Bake was done. No surface roughness was observed in the obtained pixel portion. Further, no development residue was generated on the substrate in the non-pixel portion. And the minimum required exposure amount required in order to form a pattern without surface roughness even if it developed was 15 mJ / cm < ² >.

Example 2
In Example 1, except that Irgacure-369 was changed to the following oxime initiator, the same operation as in Example 1 was performed, and the evaluation results are shown in Table 2.

Comparative Example 1
In Example 1, the same operation as in Example 1 was performed except that the resin A was changed to the resin B. The evaluation results are shown in Table 2.

Explanation of annotations in the table * 1: Indicates the minimum necessary exposure amount necessary to form a pattern having no surface roughness even after development.
* 2: ○: No development residue on substrate, ×: Development residue on substrate * 3: The cross-sectional shape of the pixel end was observed using SEM. ○: Forward taper shape, ×: Reverse taper shape * 4: A cured coating film was prepared in the same manner as in Example except that a photomask was not used. The pencil hardness was measured according to JIS K5600-5-4.

  From Table 2, the photosensitive resin compositions of Examples 1 and 2 containing the unsaturated group-containing binder resin of the present invention have high sensitivity and little development residue, and the resulting pixels have high pencil hardness and high quality color. It can be seen that a filter is obtained, but in the colored photosensitive resin composition of Comparative Example 1 that does not contain the unsaturated group-containing binder resin of the present invention, the occurrence of development residue reduces the quality of the color filter, and the obtained pixel The pencil hardness is low and a high quality color filter cannot be obtained.

  According to the colored photosensitive resin composition of the present invention, it is possible to obtain a high-quality color filter having high sensitivity, high pixel hardness, and less development residue.

Claims (4)

Binder resin (A),
Photopolymerizable compound (B),
Photopolymerization initiator (C),
In the colored photosensitive resin composition containing the coloring material (D) and the solvent (E),
The binder resin (A) is an unsaturated group-containing resin obtained by further reacting (A4) with a copolymer obtained by copolymerizing the following (A1) to (A3), and (A1) to The ratio of the component derived from each of (A3) is a molar fraction with respect to the total number of moles of the component, and is contained in the copolymer in the following range and further in the copolymer (A3 ), A binder resin obtained by reacting 5 to 80 mol% of (A4),
And the photopolymerization initiator (C) is at least one compound selected from the group consisting of a triazine compound, an acetophenone compound, and a biimidazole compound,
And content of a solvent (E) is 60-90 mass% with respect to coloring photosensitive resin composition whole quantity,
Furthermore, it contains a photopolymerization initiation assistant (C-1),
Photopolymerization initiation aid (C-1) is methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-benzoic acid 2- Coloring characterized by being at least one selected from the group consisting of dimethylaminoethyl, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone and 4,4'-bis (diethylamino) benzophenone Photosensitive resin composition.
(A1); a compound having an unsaturated bond tricyclodecane bone skeleton in one molecule; 2-30 mole%
(A2); benzyl methacrylate; 2 to 95 mol%
(A3); unsaturated carboxylic acid; 2-70 mol%
(A4); Compound having an unsaturated bond and an epoxy group in one molecule   A pattern formed using the colored photosensitive resin composition according to claim 1.   A color filter comprising the pattern according to claim 2.   A liquid crystal display device using the color filter according to claim 3.