KR19990014161A - Radiation-sensitive coloring composition - Google Patents

Abstract

To provide a radiation-sensitive colored composition that is sufficiently cured at the exposure material concentration and develops well. A radiation-sensitive coloring composition containing an s-triazine-based photopolymerization initiator having a specific structure.

Description

Radiation-sensitive coloring composition

The present invention relates to a radiation-sensitive coloring composition suitable for producing a radiation-sensitive coloring composition, specifically a color filter for use in liquid crystal devices or solid-state imaging devices.

As a method of manufacturing the color filter used for a liquid crystal display element or a solid-state image sensor, the dyeing method, the printing method, the electrodeposition method, and the pigment dispersion method are known.

Among these, the pigment dispersion method is a method of manufacturing a color filter by the ore plate printing method using the radiation sensitive coloring composition which disperse | distributed the pigment to various radiation sensitive components. Since this method uses a pigment, it is relatively stable to light, heat, and the like, and is produced by the Portrin method. Therefore, this method is suitable for manufacturing a screen with a sufficiently large position and color filters for high-precision color display.

On the other hand, various are proposed as a photoinitiator as a radiation sensitive component of the radiation sensitive composition for resists. Among these, photopolymerization initiators commonly used in radiation-sensitive coloring compositions for creating color filters include (4-morpholinophenyl) benzylbutanol (see Japanese Patent Application Laid-Open No. 4-340965) and 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -S-triazine (Japanese Patent Application Laid-Open No. Hei 6-201913), diethyl thioxanthone (see Japanese Patent Application Laid-Open No. Hei 6-51499), Ilgacua-369, -651, Benzoyl compounds, such as -907 (above brand name, the Ciba-Geigy company make), etc. are mentioned.

In order to secure high color purity, development of a color filter having a high pigment concentration is required in recent years, and therefore, the appearance of a radiation-sensitive coloring composition which imparts a sufficiently cured resist even when the pigment concentration is high is required. However, it was a reality that the photoinitiator widely used for color filter creation could not be sufficiently met by the above requirements, and it was difficult to know what kind of photoinitiator should be used.

Furthermore, in order to shorten a color filter manufacturing process, the radiation sensitive coloring composition which fully hardens | cures even without an oxygen barrier film, and the radiation sensitive coloring composition which fully hardens with low exposure amount is calculated | required.

Furthermore, there is a need for a radiation-sensitive coloring composition that provides a color filter produced by the pigment dispersion method, which is relatively excellent in heat resistance and light resistance, and which gives a color filter that has less thermal discoloration and less light fading even after long-term use. .

An object of the present invention is to provide a radiation-sensitive coloring composition which is preferably used for the production of color filters.

Specifically, it is an object of the present invention to provide a radiation-sensitive colored composition in which the exposed portion is sufficiently cured even at a high concentration of a design material and has good developability.

Another object of the present invention is to provide a radiation-sensitive colored composition obtained by sufficiently curing at a low exposure amount.

A further object of the present invention is to provide a radiation-sensitive colored composition obtained by curing sufficiently without an oxygen barrier film.

A further object of the present invention is to provide a radiation-sensitive coloring composition which can give a color filter which is less than ten times life and has little light fading even after long-term use.

The present inventors have studied to achieve the above object and found that the above object is achieved by using a specific photopolymerization initiator which is not used in the radiation-sensitive coloring composition, especially the radiation-sensitive coloring composition for the production of color filters. lost.

According to this invention, it turns out that the said objective of this invention is achieved by the following structures.

(1) A radiation sensitive colored composition containing a radiation sensitive component, a binder resin, a pigment, and a solvent,

A radiation-sensitive colored composition, wherein the radiation-sensitive component contains at least one photopolymerization initiator selected from the group consisting of compounds represented by the following formulas (I) to (IV).

[In the formula, each R ₁ independently represent a hydrogen atom, a hydroxy group, a carbon atom of 1 to 3 alkyl group or an alkoxy group, R ₂ and R ₃ each independently represent a hydrogen atom or a carbon atom of 1 to Three alkoxy groups, one of R ₂ and R ₃ is an alkoxy group; R ₄ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or an alkoxy group, and R ₅ and R ₆ each independently represent an alkyl group having 1 to 3 carbon atoms; R ₇ represents a hydrogen atom, a hydroxy group, an alkyl group of 1 to 3 carbon atoms or an alkoxy group; T represents a group represented by the following formula: m is an integer of 1-3 and n is an integer of 1-4.]

(2) The radiation sensitive colored composition as described in said (1) whose average particle diameter of a pigment is 0.01 micrometer-0.1 micrometer, and a pigment concentration is 30 weight% or more in conversion of solid content.

(3) The radiation sensitive colored composition according to the above (1) or (2), wherein the binder resin has a carboxyl group and has an acid value of 30 to 200.

The s-triazine-based photopolymerization initiator having a specific structure represented by the above (I) to (IV) is not used in a radiation-sensitive coloring composition, in particular, a radiation-sensitive coloring composition for producing a color filter. By using the same, the radiation sensitive colored composition of the present invention is sufficiently cured by exposure even at the above-mentioned object of the present invention, for example, the design material concentration, and developability is sufficient. Sufficient curing without or at low exposure doses was surprising.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

The radiation sensitive coloring composition of this invention consists of a radiation sensitive component, a binder resin, a pigment, and a formulation. Thus, the radiation sensitive component contains a photoinitiator and a radiation sensitive polymerization component.

First, the photoinitiator which is a radiation sensitive component is demonstrated.

In the present invention, at least one of the compounds represented by the above formulas (I) to (IV) is used as the photopolymerization initiator.

In general formula (I)-(IV), a methyl group, an ethyl group, n- or i-propyl group, etc. are mentioned as an alkyl group. As an alkoxy group, a methoxy group, an ethoxy group, n- or i-propoxy group, etc. are mentioned.

As R ₁ , a hydrogen atom is preferable. As R <_2> and R <_{3>, an} ethoxy group is preferable. As R _{4, a} methyl group is preferable. As R ₅ and R _{6, an} ethyl group is preferable. As R <_{7>, a} hydroxyl group is preferable.

As a preferable specific example of the said photoinitiator, what is represented by following General formula (1)-(6) is mentioned.

Especially, the photoinitiator represented by general formula (I)-(IV) is preferable.

These can be used individually by 1 type or in combination of 2 or more types.

In addition, although the compound represented by the said general formula (I)-(IV) is a compound known by itself, the example used for a radiation sensitive coloring composition, especially the radiation sensitive coloring composition for color filter preparation is not so far.

In the present invention, it is essential to use at least one of the compounds represented by the above formulas (I) to (IV) as the photopolymerization initiator. However, a photopolymerization initiator other than the above (hereinafter referred to as "other photopolymerization initiator") may be used in combination. Can be.

The following are mentioned as another photoinitiator which may be used together.

(1) at least one active halogen compound selected from a halomethyloxadiazole compound and a halomethyl-s-triazine compound (excluding the compounds represented by formulas (I) to (IV)), and 3-aryl substitution Coumarin compound.

(2) at least one ropin dimer.

As a photoinitiator of a halomethyl-s-triazine type compound, a vinyl halomethyl-s-triazine compound represented by following formula (i) described in Unexamined-Japanese-Patent No. 59-1281, and the following formula described in Unexamined-Japanese-Patent No. 53-133428 2- (naphtho-1-yl) -4,6-bis-halomethyl-s-triazine compound represented by (iii) and 4- (p-aminophenyl) -2,6 represented by the following formula (iii) -Di-halomethyl-s-triazine compound.

In formula (VII), Q ₃ is Br, Cl, P is -CQ ₃ , -NH ₂ , -NHR, -N (R) ₂ , -OR (where R is a petyl or alkyl group), W is optionally substituted It is represented by an aromatic, heterocyclic nucleus, or general formula (VIIA) in which Z is -O- or -S- and R is synonymous with the above. Or n is an integer of 0 to 3;

Formula (Ⅸ), X is represents -Br, -Cl, m, n is an integer of 0~3, R 'is represented by the formula (ⅨA) to, R ₁ is H or ORc (Rc is alkyl, cycloalkyl Alkyl, alkenyl, aryl group), R ₂ represents —Cl, Br or an alkyl, alkenyl, aryl, alkoxy group.

R <_1> , R <_2> in general formula (i) is represented by -H, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, or the following general formula (VII), (XB). R <_3> , R <_4> represents -H, a halogen atom, an alkyl group, and an alkoxy group. X, Y represents -Cl, -Br, and m, n represents 0, 1 or 2.

R <_5> , R <_6> , R <_7> represents an alkyl group, a substituted alkyl group, an aryl group, and a substituted aryl group in the following general formula (XA) and (XB). Examples of the substituent in the substituted alkyl group and the substituted aryl group include aryl groups such as phenyl groups, halogen atoms, alkoxy groups, carboalkoxy groups, carboaryloxy groups, acyl groups, nitro groups, dialkylamino groups, sulfonyl derivatives, and the like. have.

In general formula (VIII), R <_1> and R <_2> may form the bicyclic ring which consists of a nonmetallic atom with the nitrogen atom couple | bonded with it, As a result, what is shown below as a bicyclic ring is mentioned.

Specific examples of the formula (VII) include 2,4-bis (trichloromethyl) -6-p-methoxystyryl-s-triazine and 2,4-bis (trichloromethyl) -6- (1-p- Dimethylaminophenyl-1,3-butadienyl) -s-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyryl-s-triazine, and the like.

Specific examples of the formula (VII) include 2- (naphtho-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-methoxy-naphtho-1-yl) -4 , 6-bis-trichloromethyl-s-triazine, 2- (4-ethoxy-naphtho-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4- Butoxy-naphtho-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2-methoxyethyl) -naphtho-1-yl] -4,6 -Bis-trichloromethyl-s-triazine, 2- [4- (2-ethoxyethyl) -naphtho-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2-Butoxyethyl) -naphtho-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- (2-methoxy-naphtho-1-yl)- 4,6-bis-trichloromethyl-s-triazine, 2- (6-methoxy-5-methyl-naphtho-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-methoxy-naphtho-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (5-methoxy-naphtho-1-yl) -4,6 -Bis-trichloromethyl-s-triazine, 2- (4,7-dimethoxy-naphtho-1-yl) -4 , 6-bis-trichloromethyl-s-triazine, 2- (6-ethoxy-naphtho-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4, 5-dimethoxy-naphtho-1-yl) -4,6-bis-trichloromethyl-s-triazine, etc. are mentioned.

Specific examples of formula (VII) include 4- [pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [pN, N-di (Chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-methyl-pN, N-di (chloroethyl) aminophenyl] -2,6-di ( Trichloromethyl) -s-triazine, 4- (pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (pN-ethoxycarbonylaminophenyl)- 2,6-di (trichloromethyl) -s-triazine, 4- (pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- [pN , N-di (phenyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (pN-chloroethylcarbonylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- [pN- (p-methoxyphenyl) carbonylaminophenyl] 2,6-di (trichloromethyl) -s-triazine, 4- [mN, N-di (e) Oxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4 -[o-fluoro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-bromo-pN, N-di ( Chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-chloro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloro Rhomethyl) -s-triazine, 4- [o-fluoro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [ m-bromo-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-chloro-pN, N-di (chloroethyl) Aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-fluoro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl ) -s-triazine, 4- (m-bromo-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-chloro-pN-chloroethyl Aminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-fluoro-pN-chloroethylaminophenyl) -2,6-di (trickle Romethyl) -s-triazine, 4- (o-bromo-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-chloro-pN- Chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-fluoro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s -Triazine and the like.

The following sensitizers can be used together in these initiators.

Specific examples thereof include benzoyl, benzoin methyl ether, benzoin, 9-fluorenone, 2-chloro-9-fluorenone, 2-methyl-9-fluorenone, 9-anthrone, 2-bromo-9-an Tron, 2-ethyl-9-anthrone, 9,10-anthraquinone, 2-ethyl-9,10-anthraquinone, 2-t-butyl-9,10-anthraquinone, 2,6-dichloro-9, 10-anthraquinone, xanthone, 2-methylxanthone, 2-methoxyxanthone, thioxanthone, benzyl, benzalacetone, p- (dimethylamino) phenylstyrene ketone, p- (dimethylamino) phenyl-p- Methyl styryl ketone, benzophenone, p- (dimethylamino) benzophenone (or Michler's ketone), p- (diethylamino) benzophenone, benzoanthrone and the benzothiazole system described in Japanese Unexamined Patent Publication No. 51-48516. The compound can be mentioned.

The 3-aryl substituted coumarin compound refers to a compound represented by the following general formula (XI). R ₈ is a hydrogen atom, an alkyl group of 1 to 8 carbon atoms, 6 to 10 aryl groups (preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group), R ₉ is a hydrogen atom, carbon An alkyl group having 1 to 8 atoms, an aryl group having 6 to 10 carbon atoms, and a group represented by the following general formula (VIIA) (preferably methyl group, ethyl group, propyl group, butyl group, particularly preferably as general formula (VIII)) Appearing groups).

R _10, R ₁₁ are each a hydrogen atom, the carbon atoms 1 to ₈ alkyl group (e.g., methyl group, ethyl group, propyl group, butyl group, octyl group), the carbon atoms 1 to 8 haloalkyl group (for example, For example, a chloromethyl group, a fluoromethyl group, a trifluoromethyl group, etc., 1-8 carbon atoms (eg, methoxy group, ethoxy group, butoxy group), and 6-10 carbon atoms which may be substituted Aryl groups (e.g., phenyl groups), amino groups, N (R ₁₆ ) (R ₁₇ ), halogens (e.g., -Cl, -Br, -F). Preferably a hydrogen atom, a methyl group, an ethyl group, a methoxy group, a phenyl _{group, -N (R 16) (R} 17), -Cl. R ₁₂ represents a 6 to 16 aryl group (eg, phenyl group, naphthyl group, toryl group, cumyl group) which may be substituted. Examples of the substituent include amino group, -N (R ₁₆ ) (R ₁₇ ), alkyl group having 1 to 8 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, octyl group), and halogen atom having 1 to 8 carbon atoms. Alkyl groups (e.g., chloromethyl groups, fluoromethyl groups, trifluoromethyl groups, etc.), 1-8 carbon atoms (e.g., methoxy groups, ethoxy groups, butoxy groups), hydroxy groups, cyano groups, halogens ( For example, -Cl, -Br, -F) can be mentioned. R ₁₃ , R ₁₄ , R ₁₆ and R ₁₇ each represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, octyl group). R ₁₃ and R ₁₄ and R ₁₆ and R ₁₇ are also bonded to each other to form a heterocyclic ring with a nitrogen atom (e.g. piperidine ring, piperazine ring, morpholin ring, pyrazole ring, diazol ring, triazole). Ring, benzotriazole ring, etc.) may be formed. R ₁₅ represents a hydrogen atom, a carbon atom, 1 to 8 alkyl groups (eg, methyl, ethyl, propyl, butyl, octyl), or 1 to 8 alkoxy groups (eg, methoxy) , Ethoxy group, butoxy group), 6-10 carbon atoms which may be substituted (eg phenyl group), amino group, N (R ₁₆ ) (R ₁₇ ), halogen (eg -Cl, Br, -F). Zb represents = O, = S or = C (R ₁₈ ) (R ₁₉ ). Preferably it is = O, = S, = C (CN) ₂ , Especially preferably, it is = O. R ₁₈ and R ₁₉ represent a cyano group, -COOR ₂₀ and -COR ₂₁ , respectively. R ₂₀ and R ₂₁ each represent one to eight alkyl groups (eg, methyl, ethyl, propyl, butyl, octyl groups), one to eight haloalkyl groups (eg, chloromethyl groups, A fluoro group, a trifluoromethyl group, etc.) and 6-10 aryl groups (for example, a phenyl group) which may be substituted.

Particularly preferred 3-arylsubstituted coumarin compounds are {(s-triazin-2-yl) amino} -3-arylcoumarin compounds represented by the general formula (XII).

(3) Ropin dimer means a 2,4,5-triphenylimidazolyl dimer consisting of two lopin residues and the basic structure thereof is shown below.

Specific examples thereof include 2- (o-crophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazolyl dimer, and 2- (o -Methoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-dimethoxyphenyl)- 4,5-diphenylimidazolyl dimer, 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-mercaptophenyl) -4,5- Diphenyl imidazolyl dimer is mentioned.

In this invention, the other well-known thing of the above initiator can also be used.

Bisinal polyketolaldonyl compounds disclosed in US Pat. No. 2,367,660, α-carbonyl compounds disclosed in US Pat. Nos. 2,367,661 and 2,367,670, asyroinethers disclosed in US Pat. No. 2,448,828, US Pat. Aromatic acyloin compounds substituted with α-hydrocarbons disclosed in US Pat. Nos. 2,722,512, polynuclear quinone compounds disclosed in US Pat. Nos. 3,046,127 and 2,951,758, toriarylimidazoles disclosed in US Pat. No. 3,549,367. A benzothiazole compound / trihalomethyl-s-triazine-based compound disclosed in Japanese Unexamined Patent Publication No. 51-48516, a combination of an imer / p-aminophenyl ketone.

In the radiation-sensitive coloring composition of the present invention, the amount of the photopolymerization initiator represented by the above formulas (I) to (VI) as essential components is 5 to 10% by weight, particularly 20 to 100% by weight, based on the total amount of the photopolymerization initiator. desirable.

The total amount of photopolymerization initiator used is preferably 1 to 30% by weight, more preferably 3 to 15% by weight, based on the radiation sensitive polymerizability. The use of excess photopolymerization initiator is not preferable because the molecular weight of the polymer formed by photopolymerization is low and the film strength is weakened, and the initiator remaining in the film because it does not decompose in exposure deteriorates light resistance.

Next, the radiation sensitive polymerization component used as a radiation sensitive coloring composition of this invention is demonstrated.

As said radiation sensitive polymerization component, the compound which has at least 1 addition-polymerizable ethylenically unsaturated group, melting | fusing point is 100 degreeC or more at normal pressure, and a tetrafunctional or more functional acrylate compound is especially preferable.

Compounds having at least one addition-polymerizable ethylenically unsaturated group and having a melting point of 100 ° C. or higher at normal pressure include monofunctional groups such as polyethylene glycol mono (meth) acrylate, polypropylene glycol monoacrylate, and phenoxyethylene (meth) acrylate. Acrylates and methacrylates; Polyethylene glycol di (meth) acrylate, trimethylol ethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol (meth) acrylate, dipenta Erythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyano (Meth) acrylated, poly (meth) acrylated of pentaerythritol or dipentaerythritol after addition of ethylene oxide or propylene oxide to polyfunctional alcohols such as latex, glycerin, trimetholethane and dipentaerythritol Urethane acrylate described in Japanese Unexamined Patent Publications No. 48-41708, Japanese Unexamined Publications, Japanese Unexamined Publications 50-6034, and Japanese Unexamined Patent Publications No. 51-37193 Polyester acrylates described in JP-A-48-64183, JP-A-49-43191, JP-A-52-30490, and epoxy acrylates that are reaction products of epoxy resins and (meth) acrylic acid. What contained polyfunctional acrylate and methacrylate was performed. Moreover, the Japan Adhesion Society Vol. 20, Nos. 7,300 to 308, which are introduced as photocurable units and oligomers, can also be used.

Especially, the structure in which dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and these acryloyl groups sandwiched ethylene glycol and a propylene glycol residue is preferable.

These radiation sensitive polymerization components can be used individually by 1 type or in combination of 2 or more types.

The usage-amount of these radiation sensitive polymerization components is 5 to 90 weight% with respect to the total solid of a radiation sensitive coloring composition, More preferably, it is 10 to 50 weight%.

It is preferable that the radiation sensitive component, including a photoinitiator, a radiation sensitive polymerization component, and a sensitizer used as desired, is 10 to 90 weight%, especially 30 to 80 weight% with respect to solid content in the whole composition.

Next, the binder resin mix | blended with the radiation sensitive coloring composition of this invention is demonstrated.

The binder resin usable in the present invention is a linear organic polymer, soluble in an organic solvent, and preferably developed in a weak alkaline aqueous solution. As such a linear organic polymer polymer, a polymer having carboxylic acid in the side chain, for example, Japanese Patent Application Laid-Open No. 59-44615, Japanese Patent Application Laid-Open No. 54-34327, Japanese Patent Application Laid-Open No. 58-12577, Japanese Patent Application Publication No. 54-25957, Methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers and the like described in Japanese Patent Application Laid-Open Nos. 59-53836 and 59-71048 And acidic cellulose derivatives having carboxylic acid in the side chain in the same shape. In addition, what added the acid anhydride to the polymer which has a hydroxyl group is also useful. Especially among these, the benzyl (meth) acrylate / (meth) acrylic acid copolymer, the benzyl (meth) acrylate / (meth) acrylic acid /, and the multicomponent copolymer of another unit are suitable. In addition, 2-hydroxyethyl methacrylate, polyvinylpyrrolidone, polyethylene oxide, polyvinyl alcohol, etc. are also useful as a water-soluble polymer. In addition, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, etc. are also useful in order to raise the strength of a cured coating film. These polymers can be mixed in any amount.

Moreover, the copolymer, copolymer, copolymer, etc. of Unexamined-Japanese-Patent No. 7-140654 are mentioned.

Moreover, as a binder resin which can be used, the polyvinyl acetal resin or modified polyvinyl acetal resin represented by following General formula (XIII) of Unexamined-Japanese-Patent No. 9-258445 is mentioned.

In the formula (XIII), R ₁ is an alkyl group or hydrogen atom which may have a substituent, R ₂ is an alkyl group which may have a substituent, R ₃ is an aliphatic or aromatic hydrocarbon group having a carboxylic acid group, and R ₄ is at least The aliphatic or aromatic hydrocarbon group which has one hydroxyl group or a nitrile group and may have another substituent is shown, n1, n2, n3, n4, n5 represent the mol% of each repeating unit, and are respectively the following ranges. n1 = 5 to 85, n2 = 1 to 60, n3 = 1 to 20, n4 = 0 to 60, n5 = 0 to 10.

Preferable binder resin in this invention has a carboxyl group in a side chain especially, and the benzyl methacrylate-methacrylic acid copolymer is especially preferable. And from an viewpoint of maintaining developability and applicability | paintability after exposure favorable, it is preferable that it is 30-200, and 50-150 are more preferable.

The total amount of the binder resin of the present invention is 5 to 80% by weight based on the total solids of the radiation-sensitive coloring composition. Preferably it is 20-60 weight%. If the total amount of the binder resin is less than 5% by weight and the film strength is lowered, and more than 80% by weight, the acid component is increased, so that the solubility is difficult to control and the pigment is relatively low, so that sufficient image concentration is not obtained.

Next, the pigment mix | blended with the radiation sensitive coloring composition of this invention is demonstrated.

As a pigment which can be used for this invention, various conventionally well-known inorganic pigments or organic pigments can be used.

In addition, if the pigment is considered to have a high transmittance, preferably inorganic pigments or organic pigments, fine ones are used if possible, but considering the handleability, the average diameter particles are preferably 0.01 μm to 0.1 μm, more preferably 0.01 μm. Pigment of -0.08 micrometer is used.

Inorganic pigments are metal compounds represented by metal oxides, metal complex salts, and the like, specifically, metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony, and composite oxides of the metals. Can be mentioned.

As organic pigment

Etc. can be mentioned.

Especially in this invention, what has basic N atom can be used preferably in the structural formula of a pigment. Pigments having these basic N atoms exhibit good dispersibility in the compositions of the present invention. Although it is not elucidated sufficiently in this cause, it is presumed that the radiation-sensitive polymerization component and the goodness of the pigment affinity are affected.

Although these pigments are mentioned as these pigments, It is not limited to these.

These organic pigments are used alone or in various combinations to increase color purity. Specific examples are shown below.

As the red pigment, an anthraquinone pigment, a perylene pigment alone or a mixture of at least one of them and a disazo yellow pigment or isoisodrin yellow pigment is used. For example, as an anthraquinone pigment, C.I. Pigment Red 177, a perylene pigment, C.I. Pigment Red 155, C.I. Pigment red 224, and C.I. Pigment Yellow-83 or C.I. The mixing of Pigment Yellow-139 is good. The weight ratio of red pigment and yellow pigment is preferably 100: 5 to 100: 50. At 100: 4 or less, suppressing the light transmittance of 400 nm to 500 nm increases the color purity which is not completed. In addition, at 100: 51 or more, the dominant wavelength does not fit the NTSC target color more than the short wavelength. In particular, the range of 100: 10 to 10:30 is optimal.

As the red pigment, halogenated phthalocyanine-based pigments alone or a mixture of disazo-based yellow pigments or isoisodrin-based yellow pigments are used. For example, C.I. Pigment Green 7,36, 37 and C.I. Pigment Yellow-83 or C.I.Pigment Yellow-139 are preferred. The weight ratio of green pigment to yellow pigment is from 100: 5 to 100: 40. At 100: 4 or less, the light transmittance of 400 nm to 450 nm cannot be suppressed and chromaticity cannot be increased. Further, at 100: 41 or more, the dominant wavelength does not fit from the NISC target color more than the long wavelength. In particular, the range of 100: 5 to 100: 20 is optimal.

As the blue pigment, a phthalocyanine-based pigment alone or a mixture of dioxadine-based purple pigments is used. For example, C.I. Pigment Blue-15: 6 and C.I.Pigment Violet 23 are mixed. The weight ratio of the blue pigment to the purple pigment is preferably 100: 5 to 100: 50. In 100: 4 or less, the light transmittance of 400 nm to 420 nm cannot be suppressed, and color purity cannot be improved. Above 100: 51, the deviation from the NTSC target color increases due to the dominant wavelength. In particular, the range from 100: 5 to 100: 20 is optimal.

Furthermore, by using a powdered processing pigment obtained by finely dispersing the pigment with an acrylic resin, maleic acid resin, vinyl chloride acetate copolymer, ethyl cellulose resin, or the like, a photosensitive resin containing a good pigment having good dispersibility and dispersion stability can be obtained. have. As the pigment for the black matrix, carbon, titanium carbon, iron oxide alone or a mixture is used, and carbon and titanium carbon are preferable. The weight ratio is preferably in the range of 100: 5 to 100: 40. Below 100: 4, the light transmittance of long wavelength increases. Below 100: 41, dispersion stability becomes a problem.

The processing method of a pigment is demonstrated below.

In general, these pigments are supplied after drying by various methods. Usually, it is dried from an aqueous medium and supplied as a powder, but since a large latent heat of evaporation is required for water to dry, great energy is imparted to make it dry and powdered.

For this reason, pigments generally form aggregates (secondary particles) in which primary particles are aggregated.

It is not easy to disperse | distribute the pigment which forms this shape aggregate into microparticles | fine-particles. For this purpose, it is preferable to treat the pigment with various resins in advance.

These binders include the above-mentioned binder resins.

As a treatment method, there is a kneading method using a flushing treatment, a kneader, an extender, a ball mill, a two or three roll mill, or the like. Among these, a kneading method using a flushing treatment or a two or three roll mill or the like is suitable for atomization.

In general, the flushing treatment is a method of mixing a water dispersion of a pigment and a resin solution dissolved in a solvent which is not mixed with water, extracting a pigment from an aqueous medium into an organic medium, and treating the pigment in a resin. According to this method, since the pigment is not dried, aggregation of the pigment can be prevented and dispersion is easy.

In kneading with a two- or two-piece roll mill, the pigment is coated on the surface of the pigment by mixing the pigment with the resin or the resin solution, and then kneading the pigment with the resin by applying a high shear (shear force). That's how to handle it. Pigment particles aggregated in this process are dispersed from the lower dimension of aggregates to the primary particles.

In the present invention, processed pigments previously treated with acrylic resins, vinyl chloride vinyl acetate resins, maleic acid resins, ethyl cellulose resins, nitrocellulose resins and the like can also be preferably used.

In the present invention, as the form of the various processed pigments, powders, pastes, and pellets in which resins and pigments are uniformly dispersed are preferable. Moreover, the thing of the non-uniform lump shape in which resin gelatinized is not preferable.

The colored dispersion obtained in this form is mixed with the radiation-sensitive component and provided as a radiation-sensitive coloring composition.

In addition, although the pigment concentration in the total solid of the radiation-sensitive coloring composition of a pigment is not specifically limited, Generally, it is 5 to 80 weight%. In the case of the radioactive colored composition of the present invention, even when the pigment concentration is 30% by weight or more, sufficient curing is achieved by exposure, and the above effect is further enhanced when the pigment concentration is 35% by weight or more. However, the use of more than 80% by weight causes other problems such as bottom contamination of the non-image part and film residue.

In the present invention, a conventionally known pigment dispersant and a surfactant can be added for the purpose of improving the dispersibility of the pigment.

Although many kinds of compounds are used as these dispersing agents, For example, Phthalocyanine derivative | guide_body (commercially available EFA-745 (made by Efca Co.)) and Sol spas 5000 (made by Seneca); Organosiloxane Polymer-KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid-based (co) polymer polypro-No. 75, no. 90, no. Cationic surfactants such as 95 (manufactured by Kyoeisha Oil Chemical Co., Ltd.) and W001 (manufactured by Yusho); Polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid Nonionic surfactants such as esters; F top EF301, EF303, EF352 (made in Shinshu Uto Kasei), mega pop F171, F172, F173 (made in Dainippon ink), flora FFC430, FC431 (product made in Sumitomo M), Asahi guide AG710, Saffron S382, SC-101 Fluorine-based surfactants such as SC-102, SC-103, SC-104, SC-105, and SC-1068 (manufactured by Asahi Glass); Anionic surfactant, such as W004, W005, W017 (made by Yusho); EFKA-46, EFKA-47, EFKA-47EA, EFKA Polymer 100, EFKA Polymer 400, EFKA Polymer 401, EFKA Polymer-450 (from Morishita Industries), Dispersade 6, Dispersade 8, Disperside 15, Polymer dispersants such as dispasade 9100 (manufactured by Sanofoko); Various kinds of Sol-Spas dispersants (manufactured by Seneca Corporation) such as Sol-Spas 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000; Adekaplanic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P123 (Asahi Denkaze) and Isonex S-20 ( San-Yo-ka-Jase) is mentioned.

In the radiation-sensitive coloring composition of the present invention, various additives such as fillers, polymer compounds other than the binder resin, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, anti-agglomerating agents and the like can be blended as necessary.

Specific examples of these additives include fillers such as glass and alumina; Polymer compounds other than binder polymer (A) such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylate; Surfactants such as nonionic, cationic and anionic systems; 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-epoxycyclo Adhesion promoters such as hexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane : Antioxidants, such as 2, 2- thiobis (4-methyl-6- t-butyl phenol) and 2, 6- di-t- butyl phenol: 2- (3-t- butyl- 5-methyl- 2-) Ultraviolet absorbers such as hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenone; and anti-aggregation agents such as sodium polyacrylate.

In addition, when promoting the alkali solubility of the non-irradiated portion and further improving the developability of the composition of the present invention, it is possible to add an organic carbonic acid, preferably a low molecular weight organic carboxylic acid having a molecular weight of 1000 or less, to the composition of the present invention. have. Specifically, For example, aliphatic monocarboxylic acids, such as a pseudo acid, an acetic acid, a propyl acid, a lactic acid, a gil acetic acid, a pivalic acid, a capronic acid, a diethyl acetate, an enanthic acid, a caprylic acid; Fisheries, malonic acid, succinic acid, glutaric acid, adipic acid, pimeric acid, suberic acid, azeline acid, sebacic acid, bracinic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, sheet Aliphatic dicarboxylic acids such as laconic acid; Aliphatic tricarboxylic acids such as tricarbaric acid, aconitic acid and camphoronic acid; Aromatic monocarboxylic acids such as benzoic acid, toluic acid, cuminic acid, hemeric acid, and mesitylene acid; Aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, telephthalic acid, trimellitic acid, trimesic acid, meropanic acid and pyromellitic acid; And other carboxylic acids such as phenylacetic acid, hydroatroic acid, hydrokepaic acid, mandelic acid, phenylsuccinic acid, atroic acid, methyl cinnamic acid, cinnamic acid benzyl, cinnamilidene acetic acid, coumalic acid and unbelic acid.

To the radiation-sensitive colored composition of the present invention, it is preferable to add the above-mentioned other, further thermal polymerization inhibitors, for example, hydrokinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrrogalol, t Butylcatechol, benzokinone, 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2- Mercaptobenzoimidazole and the like are used.

As a solvent used when preparing the radiation-sensitive coloring composition of this invention, ester, For example, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl ammonium acetate, isoamyl acetate, isobutyl acetate, propionic acid Butyl, isopropyl lactate, ethyl lactate, butyl lactate, alkyl esters, methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, methoxyethyl acetate, methoxy butyl acetate, 3-oxypropionic acid alkyl esters such as methyl ethoxy acetate, ethyl ethoxy acetate, methyl 3-oxypropionate and ethyl 3-oxypropionate; Methyl 3-methoxy propionate, 3-methoxy ethylpropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, 2-methoxy Methyl propionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate , 2-methoxy-2-methylpropionate, 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2-oxo part Methyl carbonate, ethyl 2-oxobutyrate and the like; Ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethyl glycol monomethyl ether, diethylene glycol Monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate and the like; Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and the like; Aromatic hydrocarbons, for example, toluene, xylene and the like can be mentioned.

Among them, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol diether ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexa Paddy fields, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether acetate and the like are preferably used.

You may use these solvent individually or in combination of 2 or more types.

The radiation-sensitive colored composition of the present invention can be prepared by mixing and dispersing the above main components and other additives to be used as necessary, by mixing with a solvent and using various mixers and dispersers.

The radiation-sensitive coloring composition of the present invention is coated on the substrate by a coating method such as rotary coating, oil coating, roll coating, etc. to form a radiation-sensitive composition layer, exposed through a desired mask pattern, and developed with a developing solution, thereby coloring the colored pattern. To form. At this time, particularly as the radiation to be used, ultraviolet rays are preferably used for g rays, h rays, i rays and the like.

As the substrate, for example, soda glass, pyrex glass, quartz glass used in liquid crystal display devices, etc., and transparent conductive films attached thereto, or photoelectric conversion device substrates used in solid state imaging devices, for example, silicon substrates, etc. Can be mentioned. These substrates are generally formed with block stripes that isolate each pixel.

As the developing solution, any composition can be used as long as it is a composition in which the radiation-sensitive coloring composition of the present invention is dissolved and the radiation irradiation part is not dissolved. Specifically, combinations of various organic solvents and alkaline aqueous solutions can be used.

Examples of the organic solvent include the above-mentioned solvents used when adjusting the composition of the present invention.

As alkali, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, An alkaline aqueous solution in which alkaline compounds such as pyrrole, piperidine, and 1,8-diazabicyclo- [5.4.0] -7-undecene are dissolved at a concentration of 0.001 to 10% by weight, preferably 0.01 to 1% by weight. This is used. Moreover, when using the developing solution which consists of such alkaline aqueous solution, after image development, it washes with water generally.

(Example)

Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example.

Example 1

Bindering resin: 40 parts of benzyl methacrylate and methacrylic acid

Copolymer (weight average molecular weight 30000; acid value 120)

C.I. Pigment Blue # 15: 6 Part 50

200 parts of propylene glycol monomethyl ether acetate

Disperse throughout the day with a send mill.

Next, the following component is added.

40 parts of acrylate unit

(1) 15% by weight of hexaacrylate with six ethylene oxide added to dipentaerythritol

(2) 85% by weight of pentaacrylate obtained by adding six ethylene oxides to dipentaerythritol

Part 3 of the photopolymerization initiator represented by Formula (1)

0.01 parts of hydroxynonmonomethyl ether

150 parts of propylene glycol monomethyl ether acetate

After mixing the said components uniformly, it filters by the filter of 1 micrometer of pore diameters, and obtains the radiation sensitive coloring composition (coating composition for color filters) of this invention. This composition is apply | coated to the glass substrate for color filters so that a dry film thickness may be set to 1.5 micrometers, it is made to dry at 90 degreeC for 2 minutes, and a uniform coating film is obtained. The pigment density | concentration at this time is 37 weight% in conversion of solid content. The average particle size is 0.07 mu m.

The exposure amount of 100mj / cm <2> is irradiated through the mask of 20 micrometers width using the ultrahigh pressure mercury lamp of 2.5Kw. Next, it develops by immersing in 0.1% of sodium carbonate aqueous solution.

The film thickness and line width after development were measured, and the results are shown in Table 1.

In addition, the acid value of the binder resin was dissolved in 200 ml of acetone / methyl ethyl ketone mixed solvent (1: 1 weight ratio), and 5 ml of water was added thereto, followed by titration with a KOH water solution to neutralize the amount of KOH required for neutralization. It is expressed in mg. In addition, the weight average molecular weight of binder resin is made into GPC method (polystyrene conversion).

(Examples 2 to 5 and Comparative Examples 1 to 3)

In Example 1, Example 1 is repeated except having changed the kind and compounding ratio of a photoinitiator as follows. The results are shown in 1.

Example 2

3 parts photoinitiator represented by the said General formula (4)

Example 3

5 parts photoinitiator represented by the said General formula (6)

Example 4

5 parts photoinitiator represented by the said General formula (5)

Example 5

5 parts photoinitiator represented by the said General formula (2)

Comparative Example 1

5 parts photopolymerization initiator (Compound B)

Comparative Example 2

Oxanthone part 5

Comparative Example 3

4- (p-chlorophenyl) -2,6-bis (trichloromethyl) -s-triazine 5 parts

(Examples 6 to 8)

In Example 1, it is performed similarly to Example 1 except changing the compounding quantity of a pigment and changing a pigment concentration as shown in Table 2. The film thickness after development is shown in Table 2 together with the film thickness of Example 1.

(Comparative Examples 3 to 5)

In the comparative example 1, it carries out similarly to the comparative example 1 except changing the compounding quantity of a pigment and changing a pigment concentration as shown in Table 2. The film thickness after development is shown in Table 2 together with the film thickness of Comparative Example 1.

Evaluation results Initiator species Film thickness after development (µm) Linewidth Sensitivity (μm) Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 Compound (1) Compound (4) Compound (6) Compound (5) Compound (2) Compound B Thioxanthone Compound A 1.481.461.471.451.420.890.801.05 23.023.223.323.223.013.112.114.0

Compound A: 4- (p-chlorophenyl) -2,6-bis (trichloromethyl) -s-triazine

Pigment concentration Post-development film thickness Pigment concentration Film thickness after development Example 1 Example 6 Example 7 Example 8 37.0% 32.0% 28.0% 20.0% 1.48 μm 1.421.401.42 Comparative Example 1 Comparative Example 4 Comparative Example 5 Comparative Example 6 37.0% 32.0% 28.0% 20.0% 0.89 μm 0.681.031.20

Compound B:

From the results of Table 1 and Table 2, by using a specific photoinitiator in the present invention, the pigment concentration is increased to reduce the film thickness, and a sufficient line width can be maintained, thereby forming an excellent pattern, which is excellent in sensitivity and developability.

In the radiation sensitive colored composition of the present invention, the exposed portion is sufficiently cured even at the high concentration of the raw material, and developability is good. Therefore, it is used suitably for manufacturing the color filter used for a liquid crystal element and a solid-state image sensor.

Claims (14)

In a radiation sensitive coloring composition containing a radiation sensitive component, a binder resin, a pigment, and a solvent, the radiation sensitive component is at least one member selected from the group consisting of compounds represented by the following formulas (I) to (VI): A radiation sensitive coloring composition comprising a photopolymerization initiator. (Wherein, R ₁ each independently represents a hydrogen atom, a hydroxy group, a carbon atom having 1 to 3 alkyl groups or an alkoxy group; R ₂ and R ₃ are each independently a hydrogen atom or 1 to 3 carbon atoms; One alkoxy group, one of R ₂ and R ₃ is an alkoxy group, R ₄ represents a hydrogen atom, one to three alkyl groups or an alkoxy group, and R ₅ and R ₆ are each independently a carbon atom 1 It represents one to three alkyl groups; R ₇ represents a hydrogen atom, a hydroxy group, one carbon atom to 3 alkyl or alkoxy group; T represents a group represented by the following formula; m is an integer of 1~3, n is 1 to Is an integer of 4.) A radiation sensitive colored composition according to claim 1, wherein the photopolymerization initiator is at least one selected from formulas (I) to (IV). The radiation-sensitive coloring composition according to claim 1, wherein the photopolymerization initiator is at least one selected from the following general formulas (1) to (6). The radiation-sensitive coloring composition according to claim 1, wherein the content of the photopolymerization initiator selected from general formulas (I) to (VI) is 5 to 100% by weight based on the total photopolymerization initiator in the composition. The radiation-sensitive coloring composition according to claim 1, wherein the content of the photopolymerization initiator selected from general formulas (I) to (VI) is 20 to 100% by weight relative to the total photopolymerization initiator in the composition. The radiation sensitive colored composition according to claim 1, wherein the content of the photopolymerization initiator in the composition is 1 to 30% by weight based on the radiation sensitive component. The radiation sensitive colored composition according to claim 1, wherein the content of the photopolymerization initiator in the composition is 3 to 15% by weight relative to the radiation sensitive component. The radiation sensitive colored composition according to claim 1, wherein the binder resin has a carboxyl group and has an acid value of 30 to 200. The radiation-sensitive colored composition according to claim 1, wherein the binder resin has a carboxyl group in the side chain. The radiation-sensitive colored composition according to claim 1, wherein the content of the binder resin is 5 to 80% by weight based on the total solid components of the radiation-sensitive colored composition. The radiation-sensitive colored composition according to claim 1, wherein the content of the binder resin is 20 to 60% by weight based on the total solid components of the radiation-sensitive colored composition. The radiation-sensitive colored composition according to claim 1, wherein the average particle diameter of the pigment is 0.01 µm to 0.1 µm, and the pigment concentration is 30% by weight or more in terms of solid content. The radiation-sensitive colored composition according to claim 1, wherein the pigment has an average particle diameter of 0.01 µm to 0.08 µm. The radiation-sensitive colored composition according to claim 1, wherein the pigment concentration is 35 to 80% by weight in terms of solid content.