JP2009169231A - Colored photosensitive composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To solve the problem that a colored pattern formed using the conventional colored photosensitive composition has unsatisfactory solvent resistance. <P>SOLUTION: A colored photosensitive resin composition comprises a binder component (A), a photopolymerization initiator (B) and a colorant (C), wherein the reaction product (A1) of a tetracarboxylic acid dianhydride with a compound having one hydroxyl group and one or more photopolymerizable unsaturated bonds is contained as the binder component (A), and the binder component (A) has a weight average molecular weight of 300-1,500. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a colored photosensitive composition.

  The pixel of the color filter used in the liquid crystal display device is formed using a colored photosensitive composition.

In the formation of each pixel, in detail, a colored photosensitive composition containing any one of three colors of red, green, and blue is applied on a substrate using a coating apparatus, and a volatile component is applied. After removal by means of heating or the like, exposure is performed through a mask, and in the case of a negative type, the unexposed portion is developed, and in the case of a positive type, the exposed portion is developed and removed with a developing solution such as an alkaline aqueous solution and removed. A pattern is formed, and the obtained colored pattern is subjected to heat treatment (hereinafter sometimes referred to as post-baking) to form a pixel. Then, the same operation is performed using the remaining two colored photosensitive compositions to form a colored pattern by the same operation, and finally, a color filter having pixels of three colors of red, green, and blue is obtained. Form.
As the colored photosensitive composition, for example, those containing a binder resin (a), a colorant (b), a photopolymerizable compound (c) and a photopolymerization initiator (d) are known. As a), an alkali-soluble resin is usually used, and specifically, a binder resin containing a large amount of a copolymer having a high average molecular weight is known (see Patent Document 1).
Moreover, the coloring photosensitive composition containing the dipentaerythritol pentaacrylate succinic acid monoester which has an acidic group is known as a photopolymerizable compound (c) (patent document 2).

JP-A-9-134004, page 3, right column, lines 6-11 Example 3 of JP2007-192892A

  However, for example, the colored photosensitive composition described in Patent Document 1 containing a copolymer of methacrylic acid and benzyl methacrylate as a binder resin, or dipentaerythritol pentaacrylate succinic acid monoester having an acidic group In the colored photosensitive composition described in Patent Document 2 containing the above, the solvent resistance of the colored pattern formed using this composition is not always satisfactory.

The inventor of the present invention has arrived at the present invention as a result of intensive studies on new means capable of solving the above-mentioned problems.
That is, the present invention provides the following inventions.
1. In a colored photosensitive composition containing a binder component (A), a photopolymerization initiator (B) and a colorant (C), tetracarboxylic dianhydride, one hydroxyl group and one as a binder component (A) A colored photosensitive composition comprising a reaction product (A1) with a compound having a photopolymerizable unsaturated bond, wherein the binder component (A) has a weight average molecular weight of 300 to 1,500.
2. A reaction product (A1) of a tetracarboxylic dianhydride with a compound having one hydroxyl group and one or more photopolymerizable unsaturated bonds is a tetracarboxylic dianhydride, one hydroxyl group and two 2. The colored photosensitive composition according to 1 above, which is a reaction product with the compound having an unsaturated double bond.
3. 3. The colored photosensitive composition according to claim 1 or 2, wherein the colorant (C) is a dye.
4). The colored photosensitive composition according to any one of the preceding items 1 to 3, further comprising a photopolymerizable compound (A2) having no carboxyl group as the binder component (A).
5. 5. The colored photosensitive composition according to 4 above, wherein the photopolymerizable compound (A2) having no carboxyl group contains the photopolymerizable compound (A2-1) having a hydroxyl group.
6). 6. The colored photosensitive composition according to 4 or 5, wherein the photopolymerizable compound (A2) having no carboxyl group includes the compound (A3) represented by the formula (I).

[In Formula (I), R ¹ represents an alkylene group having 1 to 4 carbon atoms.
R ² represents a group having a polymerizable unsaturated bond.
m represents an integer of 1 to 4. ]

7). The coloring pattern formed using the coloring photosensitive composition in any one of the preceding 1-6.
8). A pixel obtained by heat-treating the colored pattern described in 7 above.
9. A color filter including the pixel as described in 8 above.
10. 10. A liquid crystal display device comprising the color filter as described in 9 above.

  The colored photosensitive composition of this invention can form the coloring pattern and coating film excellent in solvent resistance.

  Hereinafter, the present invention will be described in detail.

  The colored photosensitive composition of the present invention comprises, as a binder component (A), a reaction product (A1) of a tetracarboxylic dianhydride and a compound having one hydroxyl group and one or more photopolymerizable unsaturated bonds. Containing.

Examples of tetracarboxylic dianhydride include butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutane. Tetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 3,5,6-tricarboxynorbornane-2- Acetic dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid Acid dianhydride, 1,4-bis (2,5-dioxotetrahydro-3-furanyl) benzene, bicyclo [2,2,2] -oct-7-ene-2,3,5,6 Tetracarboxylic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic anhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-6 An aliphatic acid dianhydride such as methyl-1-naphthalene succinic anhydride;
Pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenylsulfone tetracarboxylic dianhydride, 1,4,5, 8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyl ether tetracarboxylic dianhydride, 3,3 ′, 4,4′-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3 ′, 4,4′-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4′-bis ( 3,4-dicar Boxyphenoxy) diphenylpropane dianhydride, 3,3 ′, 4,4′-perfluoroisopropylidene diphthalic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, bis (Phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4 , 4′-diphenyl ether dianhydride, aromatic tetracarboxylic dianhydrides such as bis (triphenylphthalic acid) -4,4′-diphenylmethane dianhydride;
Examples include compounds having the following structure.

[In Formula (II), R ³ represents an alkylene group having 1 to 5 carbon atoms. ]

  Examples of the alkylene group having 1 to 5 carbon atoms include methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, propylene group, ethylethylene group, 1,2-dimethylethylene group, and 1,1-dimethylethylene group. 2,2-dimethylethylene group,

  Among the above compounds, preferably 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, 5- (2,5-dioxotetrahydro-3-furanyl)- Examples include 3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, and ethylene glycol bistrimellitic anhydride ester. .

The photopolymerizable unsaturated bond in the compound having one hydroxyl group and two or more photopolymerizable unsaturated bonds is derived from, for example, a (meth) acryl group.
In the present specification, the description of the (meth) acryl group represents at least one group selected from the group consisting of an acryl group and a methacryl group. The description of (meth) acrylate represents at least one selected from the group consisting of acrylate and methacrylate.

  Examples of the compound having one hydroxyl group and two or more photopolymerizable unsaturated bonds include glycerin di (meth) acrylate, trimethylolpropane di (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, and pentaerythritol tris. (Meth) acrylate, dipentaerythritol penta (meth) acrylate, etc. are mentioned, Preferably glycerol di (meth) acrylate and pentaerythritol tri (meth) acrylate are mentioned.

The reaction of tetracarboxylic dianhydride with a compound having one hydroxyl group and two or more photopolymerizable unsaturated bonds is carried out, for example, by stirring and mixing under heating as necessary. .
The temperature during the reaction is usually 0 to 200 ° C, preferably 30 to 180 ° C, more preferably 40 to 160 ° C. When the temperature during the reaction is within the above range, the progress of the reaction can be appropriately adjusted, and the reaction between the unreacted raw material during the progress of the reaction and the component (A1) that is the reaction product obtained. This is preferable because undesirable side reactions can be suppressed.

In the above reaction, a polymerization inhibitor can be used in order to suppress side reactions. Examples of the polymerization inhibitor include oxygen and hydroquinone monomethyl ether. When these polymerization inhibitors are used, the amount thereof is usually 5,000 ppm or less, preferably 700 ppm or less in the reaction system.
The reaction proceeds even without catalyst, but a catalyst may be used if necessary. Examples of the catalyst that can be used include basic compounds such as triethylamine, pyridine, N-methylimidazole, diazabicycloundecene, diazabicyclooctane, and ammonium salts such as trimethylbenzylammonium chloride and tetrabutylammonium bromide. In addition, other known catalysts such as acids and alkalis can also be used.
The reaction proceeds even without solvent, but a solvent may be used, alkylene glycol monoalkyl acetates such as propylene glycol monomethyl ether acetate, ethers such as diethylene glycol dimethyl ether, ketones such as methyl ethyl ketone, esters such as ethyl acetate , And aromatic hydrocarbons such as toluene can be used.

  Examples of the reaction product (A1) of tetracarboxylic dianhydride with a compound having one hydroxyl group and one or more photopolymerizable unsaturated bonds include 3,4-dicarboxy-1,2,2, for example. Reaction product of 1 mol of 3,4-tetrahydro-1-naphthalene succinic dianhydride and 2 mol of pentaerythritol triacrylate, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid Reaction product of 1 mol of dianhydride and 2 mol of glycerin diacrylate, reaction product of 1 mol of 4,4′-biphenylsulfone tetracarboxylic dianhydride and 2 mol of pentaerythritol triacrylate, 4,4′-biphenylsulfone Reaction product of 1 mol of tetracarboxylic dianhydride and 2 mol of glycerin diacrylate, 5- (2,5-dioxotetrahydro-3-furani ) -3-Methyl-3-cyclohexene-1,2-dicarboxylic dianhydride 1 mol and pentaerythritol triacrylate 2 mol, 5- (2,5-dioxotetrahydro-3-furanyl) -3 Reaction product of 1 mol of methyl-3-cyclohexene-1,2-dicarboxylic dianhydride and 2 mol of glycerin diacrylate Reaction product of ethylene glycol bistrimellitic anhydride ester and 2 mol of pentaerythritol triacrylate, ethylene glycol A reaction product of bistrimellitic anhydride ester and 2 mol of glycerin diacrylate, and the like, preferably 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride 1 Reaction product of 2 mol of pentaerythritol triacrylate and 5- (2 5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride 1 mol and pentaerythritol triacrylate 2 mol, ethylene glycol bistrimellitic anhydride A reaction product of an ester and 2 mol of pentaerythritol triacrylate is exemplified.

  The content of the reaction product (A1) between the tetracarboxylic dianhydride and one hydroxyl group and a compound having one or more photopolymerizable unsaturated bonds is the mass with respect to the total amount of the binder component (A). The fraction is preferably 10 to 99% by mass, more preferably 30 to 99% by mass. When the content of the reaction product (A1) of the tetracarboxylic dianhydride with one hydroxyl group and one or more photopolymerizable unsaturated bonds is in the above range, It is preferable because film loss is unlikely to occur, the unexposed area is easily removed and development residues are unlikely to occur.

  The colored photosensitive composition of the present invention may contain a photopolymerizable compound (A2) having no carboxyl group. The photopolymerizable compound (A2) having no carboxyl group can be a monofunctional monomer, a bifunctional monomer, or another polyfunctional monomer having three or more functions.

  Monofunctional monomers include benzyl (meth) acrylate, cyclohexyl (meth) acrylate, tricyclodecanyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxypropyl ( (Meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, 2-hydroxy-3- Examples include phenoxypropyl (meth) acrylate, nonylphenyl carbitol (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate, and N-vinylpyrrolidone.

  Bifunctional monomers include ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, glycerin di (meth) acrylate, 1,3-butanediol di (meth) acrylate, and tetramethylene glycol di (meth). Acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, hexanediol di (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1 , 6-hexanediol di (meth) acrylate, bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, heptanediol di (meth) acrylate , Octanediol di (meth) acrylate, nonanediol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, pentaerythritol di (meth) acrylate, methylenebis- (meth) acrylamide, 1,6-hexamethylene Bis- (meth) acrylamide, xylylene bis (meth) acrylamide, etc. are mentioned.

  Other trifunctional or higher polyfunctional monomers include trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane tri ((meth) acryloyloxypropyl) ether, pentaerythritol tri ( (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, sorbitol tri (meth) acrylate, sorbitol tetra (meth) acrylate, sorbitol penta (meth) acrylate , Sorbitol hexa (meth) acrylate, tri ((meth) acryloyloxyethyl) isocyanurate, diethylenetriamine tris (meth) acrylic De formula (III), include compounds represented by the formula (IV).

[In Formula (III), R ^{4 to} R ⁹ each independently represent a hydrogen atom or any group of Formulas (III-1) to (III-3).

However, among R ^{4 to} R ⁹ , at least four groups are any groups of formulas (III-1) to (III-3), and at least one group of R ^{4 to} R ⁹ is represented by formula (III -2) or formula (III-3). ]

Among them, a compound in which six groups are a group represented by formula (III-2) and a compound in which six groups are a group represented by formula (III-3) are preferable.
Furthermore, a vinyl monomer represented by the formula (IV) is added to a polyisocyanate compound having two or more isocyanate groups in one molecule such as tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, polyisocyanate. Vinyl urethane compounds obtained by the above method.

[In Formula (IV), R ¹⁰ and R ¹¹ each independently represents a hydrogen atom or a methyl group. ]

  As the vinyl urethane compound, for example, a compound containing two or more polymerizable vinyl groups in one molecule can be used (Japanese Patent Publication No. 48-41708). Examples of the compound containing a polymerizable vinyl group include urethane acrylates as described in the above-mentioned JP-A No. 51-37193, and further, Journal of Japan Adhesion Association Vol. 20, No. 7, pages 300 to 308 (1984), which are introduced as photocurable monomers, can also be used.

As the photopolymerizable compound (A2) having no carboxyl group, a photopolymerizable compound (A2-1) having a hydroxyl group is preferably used.
Examples of the photopolymerizable compound having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 3-hydroxybutyl. (Meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol di (Meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, sorbitol tri (meth) acrylate, sorbitol tetra (meth) acrylate, Ruby penta (meth) acrylate.
Moreover, the compound (A2-2) represented by Formula (I) is also preferably used as the photopolymerizable compound (A2) having no carboxyl group.

[In Formula (I), R ¹ represents an alkylene group having 1 to 6 carbon atoms.
R ² represents a group having a polymerizable unsaturated bond.
m represents an integer of 1 to 6. ]

  Examples of the alkylene group having 1 to 6 carbon atoms include a methylene group, an ethylene group, an n-propylene group, an isopropylene group, an n-butylene group, an isobutylene group, an n-pentylene group, an isopentylene group, a neopentylene group, and an n-hexylene group. And an isohexylene group, preferably an ethylene group and an n-propylene group.

  Specific examples of the group having a polymerizable unsaturated bond include a (meth) acryl group.

  Examples of the compound represented by the formula (I) include ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, Examples include propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, hexanediol di (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, and tetraethylene glycol di (meth) acrylate. Preferably, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and 1,3-butanediol di (meth) acrylate are used.

  These photopolymerizable compounds (A2) can be used alone or in combination of two or more. Among these, it is more preferable to use a compound represented by the formula (I) in combination with a trifunctional or higher polyfunctional monomer.

The content of the photopolymerizable compound (A2) having no carboxyl group is a mass fraction when the total amount of the binder component (A) is 100% by mass, preferably 1 to 90% by mass, more preferably 1 to 70% by mass. When the content of the photopolymerizable compound (A2) having no carboxyl group is within the above range, the strength, smoothness, and reliability of the exposed area are improved, and the solubility in the developer is not impaired. There is a tendency and preferable.
The acid value of the binder component (A) is preferably 20 mgKOH / g or more and 150 mgKOH / g or less, more preferably 40 mgKOH / g or more and 120 mgKOH / g or less.

In the colored photosensitive composition of the present invention, the weight average molecular weight of the binder component (A) is 300 or more and 1500 or less.
The said weight average molecular weight is calculated | required based on Formula (1).

Mw = (M1 × W1) / (W1 + W2) + (M2 × W2) / (W1 + W2) (1)

Mw; (A) weight average molecular weight M1; (A1) molecular weight or weight average molecular weight M2; (A2) molecular weight or weight average molecular weight W1; (A1) use ratio W2 in (A); (A2) Usage ratio in (A)

The molecular weight of each of the component (A1) and the component (A2) (weight average molecular weight in the case of a mixture) may exceed 1,500, but when one component exceeds Mw1,500, Decreasing the use ratio in the binder component (A), selecting the other components having a Mw of less than 1,500, and increasing the use ratio of the component in the binder component (A), the formula (1) The weight average molecular weight of the binder component (A) obtained on the basis of the weight can be 1,500 or less.
In the present invention, the weight average molecular weight of the binder component (A) obtained by the formula (1) is from 300 to 1,500, preferably from 300 to 1,200, more preferably from 400 to 1,000.
When the weight average molecular weight of the binder component (A) is in the above range, the solvent resistance of the colored pattern or coating film formed using the colored photosensitive composition containing the binder component (A) is improved. There is a tendency and preferable.

The colored photosensitive composition of the present invention can contain a curing agent (A3) as the binder component (A).
A hardening | curing agent (A3) is used in order to harden a resin pattern by the heat processing after image development, and to improve the mechanical strengths, such as a recovery rate. As such a curing agent (A3), for example, a photopolymerizable compound (A1) having one or more carboxyl groups and two or more photopolymerizable unsaturated bonds reacting with a carboxyl group by being heated. ) May be cross-linked or polymerized alone.

  Moreover, the compound which can superpose | polymerize independently by heating may be sufficient, and a pattern hardens | cures by superposing | polymerizing alone. Examples of such compounds include epoxy compounds, oxetane compounds, and methylol compounds.

  Examples of the epoxy compound include bisphenol A-based epoxy resins, hydrogenated bisphenol A-based epoxy resins, bisphenol F-based epoxy resins, hydrogenated bisphenol F-based epoxy resins, novolac-type epoxy resins, other aromatic epoxy resins, and alicyclic rings. Epoxy resins, heterocyclic epoxy resins, glycidyl ester resins, glycidyl amine resins, epoxy resins such as epoxidized oils, brominated derivatives of these epoxy resins, aliphatics other than epoxy resins and brominated derivatives thereof , Alicyclic or aromatic epoxy compounds, triglycidyl isocyanurate, and the like.

  Examples of oxetane compounds include carbonate bisoxetane, xylylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, cyclohexanedicarboxylic acid bisoxetane, bis [3- (3-ethyloxetanyl) methyl] ether, 1,4-bis { 3- (3-ethyloxetanyl) methoxy} benzene, 1,4-bis [3- (3-ethyloxetanyl) methoxy] methylbenzene, 1,4-bis [3- (3-ethyloxetanyl) methoxy] cyclohexane, 1 , 4-bis [3- (3-ethyloxetanyl) methoxy] methylcyclohexane and the like.

  Examples of the methylol compound include alkoxymethylated amino resins such as alkoxymethylated melamine resins and alkoxymethylated urea resins. Here, as the alkoxymethylated melamine resin, methoxymethylated melamine resin, ethoxymethylated melamine resin, propoxymethylated melamine resin, butoxymethylated melamine resin and the like, as alkoxymethylated urea resin, for example, methoxymethylated Examples include urea resins, ethoxymethylated urea resins, propoxymethylated urea resins, butoxymethylated urea resins.

When using the said hardening | curing agent (A3) in the coloring photosensitive composition of this invention, this can be used individually or in combination of 2 or more types, respectively. When it contains the said hardening | curing agent (A3), it is preferable that the content is 0.1 to 30% by mass fraction with respect to solid content of a coloring photosensitive composition.
It is preferable for the amount of the curing agent (A3) to be in the above-mentioned range since the decrease in solubility and sensitivity of the colored photosensitive composition layer in the developer can be suppressed.

When (A3) is included, the weight average molecular weight of (A) is obtained based on the formula (2).

Mw = (M1 × W1) / (W1 + W2 + W3) + (M2 × W2) / (W1 + W2 + W3) + (M3 × W3) / (W1 + W2 + W3) (2)

Mw; (A) weight average molecular weight M1; (A1) molecular weight or weight average molecular weight M2; (A2) molecular weight or weight average molecular weight M3; (A3) molecular weight or weight average molecular weight W1; (A1) (A1) ) Usage ratio W2; (A2) usage ratio W3 in (A); (A3) usage ratio in (A)

The molecular weights of (A1), (A2) and (A3) (weight average molecular weight in the case of a mixture) may exceed 1,500, but if a certain component exceeds Mw1,500, The binder component (A) is used in a lower ratio, the other component having a Mw of less than 1,500 is selected, and the other component in the binder component (A) is used in a higher ratio. The weight average molecular weight of (A) can be 1,500 or less. The weight average molecular weight of the binder component (A) is preferably 300 or more and 1,500 or less, more preferably 300 or more and 1,200 or less.
When the weight average molecular weight of the binder component (A) is in the above range, the resolution of the colored photosensitive composition containing the binder component tends to be good, which is preferable.

  The colored photosensitive composition of the present invention contains a photopolymerization initiator (B). Examples of the photopolymerization initiator (B) include acetophenone compounds, biimidazole compounds, oxime compounds, triazine compounds, acylphosphine oxide compounds, benzoin compounds, benzophenone compounds, thioxanthone compounds, anthracene compounds. Compounds, preferably acetophenone compounds, biimidazole compounds, oxime compounds, triazine compounds, and acylphosphine oxide compounds.

  Examples of the acetophenone compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl] -2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholino Propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2- (2-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) ) -Butanone, 2- (3-methylbenzyl) -2-dimethylamino-1- (4-morpholinofe) L) -butanone, 2- (4-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-ethylbenzyl) -2-dimethylamino-1- (4-morpholino) Phenyl) -butanone, 2- (2-propylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-butylbenzyl) -2-dimethylamino-1- (4-morpholino) Phenyl) -butanone, 2- (2,3-dimethylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2,4-dimethylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-chlorobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- 2-bromobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (3-chlorobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- ( 4-chlorobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (3-bromobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- ( 4-bromobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- ( 3-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (4-methoxybenzyl) -2-dimethyl Tylamino-1- (4-morpholinophenyl) -butanone, 2- (2-methyl-4-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-methyl-4 -Bromobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-bromo-4-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, Examples include 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one oligomers, and preferably 2-methyl-1- (4-methylthiophenyl) -2- Examples include morpholinopropan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one.

  Examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole and 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 (trialkoxy) Phenyl) biimidazole (for example, see JP-B-48-38403, JP-A-62-174204, etc.), and the phenyl group at the 4,4′5,5′-position is substituted with a carboalkoxy group. Imidazole compounds (see, for example, JP-A-7-10913) and the like, preferably 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,3-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole may be mentioned.

  Examples of the oxime compound include O-ethoxycarbonyl-α-oximino-1-phenylpropan-1-one, a compound represented by formula (3), a compound represented by formula (4), and the like.

  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) Ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine, and the like. 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine and the like.

  Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

  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.

  Other examples of the photopolymerization initiator include 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, and titanocene compounds. .

Further, as a photopolymerization initiator having a group capable of causing chain transfer, a photopolymerization initiator described in JP-T-2002-544205 can be used.
As a photoinitiator which has the group which can raise | generate the said chain transfer, the photoinitiator represented by Formula (5)-(10) is mentioned, for example.

  The photopolymerization initiators may be used alone or in combination of two or more.

Further, the photopolymerization initiator may be used in combination with the photopolymerization initiation assistant (B-1). By using the photopolymerization initiator (B-1) in combination with the photopolymerization initiator auxiliary agent (B-1), the resulting colored photosensitive composition becomes more sensitive, so when using this to form a colored pattern, Since productivity of a coloring pattern improves, it is preferable.
Examples of the photopolymerization initiation assistant (B-1) include amine compounds, carboxylic acid compounds, polyfunctional thiol compounds, and compounds represented by the formula (V). As the amine compound, an aromatic amine compound is particularly preferable.

Examples of the amine compound include aliphatic amine compounds such as triethanolamine, methyldiethanolamine, and triisopropanolamine;
Methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, Aromatic amine compounds such as 4,4′-bis (dimethylamino) benzophenone (common name; Michler's ketone) and 4,4′-bis (diethylamino) benzophenone are exemplified.
Examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthiol. Examples include aromatic heteroacetic acids such as acetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.
Examples of the polyfunctional thiol compound include hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, and trimethylolpropane. Tristhioglycolate, butanediol bisthiopropionate, trimethylolpropane tristhiopropionate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, trishydroxyethyltristhio Propionate, pentaerythritol tetrakis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane And the like.

[In Formula (V), Ring X represents an aromatic ring having 6 to 12 carbon atoms which may be substituted with a halogen atom.
Y represents an oxygen atom or a sulfur atom.
R ¹² represents an alkyl group having 1 to 6 carbon atoms.
R ¹³ represents an alkyl group having 1 to 12 carbon atoms which may be substituted with a halogen atom or an aryl group which may be substituted with a halogen atom. ]

Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.
Examples of the aromatic ring having 6 to 12 carbon atoms include a benzene ring and a naphthalene ring.

  Examples of the aromatic ring having 6 to 12 carbon atoms which may be substituted with a halogen atom include a benzene ring, a methylbenzene ring, a dimethylbenzene ring, an ethylbenzene ring, a propylbenzene ring, a butylbenzene ring, a pentylbenzene ring, a hexylbenzene ring, Examples include cyclohexylbenzene ring, chlorobenzene ring, dichlorobenzene ring, bromobenzene ring, dibromobenzene ring, phenylbenzene ring, chlorophenylbenzene ring, bromophenylbenzene ring, naphthalene ring, chloronaphthalene ring, bromonaphthalene ring, and the like.

  Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, 1-methyl-n-propyl group, 2-methyl-n-propyl group, tert- Butyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2- Examples include dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, n-hexyl group, cyclohexyl group and the like.

Examples of the alkyl group having 1 to 12 carbon atoms which may be substituted with a halogen atom include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, 1-methyl-n-propyl group, 2- Methyl-n-propyl group, tert-butyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl- n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, n-hexyl group, cyclohexyl group, 1-chloro-n-butyl group, 2-chloro-n- A butyl group, 3-chloro-n-butyl group, etc. are mentioned.

  The aryl group which may be substituted with a halogen atom includes a phenyl group, a chlorophenyl group, a dichlorophenyl group, a bromophenyl group, a dibromophenyl group, a chlorobromophenyl group, a biphenyl group, a chlorobiphenyl group, a dichlorobiphenyl group, and a bromophenyl group. , Dibromophenyl group, naphthyl group, chloronaphthyl group, dichloronaphthyl group, bromonaphthyl group, dibromonaphthyl group and the like.

  The compound represented by formula (V) is preferably 2- (2-naphthoylmethylene) -3-methylbenzothiazoline represented by formula (V-1), represented by formula (V-2). 2-Benzoylmethylene-3-methyl-naphtho [1,2-d] thiazoline and 2- (4-biphenoylmethylene) -3-methyl-naphtho [1,2-d] thiazoline represented by the formula (V-3) Is mentioned.

Content of a photoinitiator (B) is a mass fraction with respect to the total amount of a binder component (A), Preferably it is 0.1-40 mass%, More preferably, it is 0.5-30 mass%. .
The content of the photopolymerization initiation assistant (B-1) is a mass fraction with respect to the total amount of the binder component (A), preferably 0.01 to 50% by mass, more preferably 0.1 to 0.1%. 40% by mass.
When the total amount of the photopolymerization initiator (B) is in the above range, the colored photosensitive composition becomes highly sensitive, the strength of the colored pattern formed using the colored photosensitive composition, and the colored pattern. The smoothness on the surface tends to be good, which is preferable. In addition to the above, when the amount of the photopolymerization initiation assistant (B-1) is in the above range, the sensitivity of the resulting colored photosensitive composition is further increased, and formed using the colored photosensitive composition. This is preferable because the productivity of the colored pattern substrate is improved.

The colored photosensitive composition of the present invention contains a colorant (C). Examples of the colorant include dyes and pigments, preferably dyes. In addition, as long as the effect of this invention is not impaired, you may use together a dye and a pigment.
Examples of the dye include acid dyes, basic dyes, direct dyes, sulfur dyes, vat dyes, naphthol dyes, reactive dyes, and disperse dyes, which can be selected from conventionally known dyes for use in color filters.
Examples of the dye include JP-A 64-90403, JP-A 64-91102, JP-A-1-94301, JP-A-6-11614, JP 2592207, US Pat. No. 808,501, US Pat. No. 5,667,920, US Pat. No. 5,059,500, JP-A-5-333207, JP-A-6-35183, JP-A-6 -51115 gazette, Unexamined-Japanese-Patent No. 6-194828, etc. are mentioned.
The chemical structure of the dye includes pyrazole azo, anilino azo, aryl azo, pyrazolo triazole azo, pyridone azo, triphenyl methane, anthraquinone, anthrapyridone, benzylidene, oxonol, cyanine, polymethine, Phenothiazine, pyrrolopyrazole, azomethine, xanthene, phthalocyanine, quinophthalone, benzopyran, indigo, dioxazine, coumarin, squarylium, and preferably pyrazole azo, anilinoazo, pyrazolotriazole azo , Pyridone azo, anthraquinone, anthrapyridone, phthalocyanine, dioxazine, quinophthalone, xanthene, more preferably pyrazole azo, pyridone azo, Taroshianin system, quinophthalone, and the like xanthene.

Examples of the pigment include organic pigments and inorganic pigments, and compounds classified as pigments by Color Index (published by The Society of Dyers and Colorists).
Specifically, for example, C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, Yellow pigments such as 147, 148, 150, 153, 154, 166, 173, 194, 214;
C. I. Orange pigments such as CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;
C. I. Red pigments such as CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265;
C. I. Blue pigments such as CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60;
C. I. Violet color pigments such as CI Pigment Violet 1, 19, 23, 29, 32, 36, 38;
C. I. Green pigments such as CI Pigment Green 7 and 36;
C. I. Brown pigments such as CI Pigment Brown 23 and 25;
C. I. And black pigments such as CI Pigment Black 1 and 7. Among them, C.I. I. Pigment yellow 138, 139, 150, C.I. I. Pigment red 177, 209, 254, C.I. I. Pigment red violet 23, C.I. I. Pigment blue 15: 6 and C.I. I. It is preferable that at least one pigment selected from CI Pigment Green 36 is contained. These pigments may be used alone or in combination of two or more.

  Among the above-mentioned pigments, organic pigments may be rosin-treated, surface treated with a pigment derivative or pigment dispersant introduced with an acidic group or basic group, or grafted onto the pigment surface with a polymer compound, if necessary. Treatment, atomization treatment by a sulfuric acid atomization method, or the like, cleaning treatment by an organic solvent or water for removing impurities, removal treatment by ion exchange method of ionic impurities, or the like may be performed.

  As the pigment dispersant, commercially available surfactants can be used, for example, silicone-based, fluorine-based, ester-based, cationic-based, anionic-based, nonionic-based, and amphoteric surfactants. Each is used alone or in 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.), Fluorado (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard, Surflon (manufactured by Asahi Glass Co., Ltd.), Solsperse (manufactured by Geneca Co., Ltd.), EFKA (manufactured by EFKA CHEMICALS Co., Ltd.), PB821 (manufactured by Ajinomoto Co., Inc.), etc. Is mentioned.

Content of a coloring agent (C) is 1-70 mass% with respect to solid content of a colored photosensitive composition, Preferably it is 10-50 mass%. When the content of the colorant (C) is in the above range, the desired spectrum can be obtained.
Here, the solid content of the colored photosensitive composition refers to the total amount obtained by removing the solvent component from the colored photosensitive composition.

The colored photosensitive composition of the present invention may contain a solvent (D). The solvent (D) can be various organic solvents used in the field of colored photosensitive 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 methyl ethyl 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 lactate, propyl lactate, butyl lactate, ethyl 3-ethoxypropionate and methyl 3-methoxypropionate;
and cyclic esters such as γ-butyrolactone.
Among the above solvents, from the viewpoints of coating properties and drying properties, an organic solvent having a boiling point of 100 to 200 ° C. is preferable among the above solvents. Specifically, alkylene glycol alkyl ether acetates and esters are used. Preferred examples include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate and methyl 3-methoxypropionate.
These solvents (D) can be used alone or in admixture of two or more.
Content of the solvent (D) in the colored photosensitive composition of this invention is a mass fraction with respect to a colored photosensitive composition, Preferably it is 40-90 mass%, More preferably, it is 50-85 mass%. When the content of the solvent (D) is within the above range, when applied by a spin coater, slit & spin coater, slit coater (sometimes called a die coater or curtain flow coater), an ink jet or the like. The coating property is expected to be good, and is preferable.

The colored photosensitive composition of the present invention contains a surfactant, an adhesion improver, an antioxidant, an ultraviolet absorber, a light stabilizer, a sensitizer, an electron donor, a chain transfer agent, and a filler as necessary. An additive (E) such as
As the surfactant, at least one selected from the group consisting of silicone surfactants, fluorine surfactants, and silicone surfactants having fluorine atoms may be contained.
Examples of the silicone-based surfactants include trade names such as Torresilicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, 29SHPA, and SH30PA (produced by Torresilicone); trade name polyether-modified silicone oil SH8400 (Trade name KP321, KP322, KP323, KP324, KP326, KP340 and KP341 (manufactured by Shin-Etsu Silicone)); trade names TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446 , TSF4452 and TSF4460 (manufactured by GE Toshiba Silicone Co., Ltd.).
Furthermore, the colored photosensitive composition of the present invention can also contain other surfactants such as an acrylic polymer surfactant and a vinyl polymer surfactant.
Examples of the acrylic polymer surfactant include Disparon (trade name) OX-880, OX-881, OX-883, OX-70, OX-77, OX-77HF, OX-60, and OX-60. OX-710, OX-720, OX-740, OX-750, OX-8040, 1970, 230, L-1980-50, L-1982-50, L-1983-50 L-1984-50, L-1985-50, LAP-10, LAP-20, LAP-30 and LHP-95 (manufactured by Enomoto Kasei Co., Ltd.); trade names BYK-352, BYK -354, BYK-355, BYK-356, BYK-357, BYK-358, BYK-359, BYK-361 and BYK-390 (manufactured by BYK Chemie Japan); Efcar (trade name) LP3 Such as 78 (Efka Chemicals Co., Ltd.) and the like.
Examples of the vinyl polymer surfactant include Disparon (trade name) 1922, 1927, 1950, 1951, P-410, P-410HF, P-420, P-425, and PD-7. And LHP-90 (manufactured by Enomoto Kasei Co., Ltd.).
Examples of the adhesion improver 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.
Examples of the antioxidant include 2,2′-thiobis (4-methyl-6-tert-butylphenol), 2,6-di-tert-butyl-4-methylphenol, Irganox 3114 (manufactured by Ciba Specialty Chemicals) ) And the like.
Examples of the ultraviolet absorber include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole, alkoxybenzophenone, and the like.
Examples of the chain transfer agent include dodecyl mercaptan and 2,4-diphenyl-4-methyl-1-pentene.
Examples of the filler include glass, silica, and alumina.

For example, the colored photosensitive composition can be applied onto a substrate as described below, and exposed and developed to form a negative pattern. Examples of the substrate include a transparent glass plate, a silicon wafer, a polycarbonate substrate, a polyester substrate, an aromatic polyamide substrate, a polyamideimide substrate, and a resin substrate such as a polyimide substrate. On the substrate, a black matrix, a coloring pattern, a transparent pattern for adjusting a film thickness, a TFT, and the like may be formed.
The layer composed of the colored photosensitive composition can be formed by, for example, a method of applying the colored photosensitive composition on the substrate.
The coating is performed by, for example, a spin coating method, a casting coating method, a roll coating method, a slit and spin coating method, a slit coating method, a die coating method, or a curtain flow coating method. After application, a colored photosensitive composition layer is formed by volatilizing volatile components such as a solvent by heating and drying (pre-baking), vacuum drying, or a combination of both. The thickness of the colored photosensitive composition layer is usually 1 to 6 μm.
Next, the colored photosensitive composition layer is irradiated with radiation through a mask. The mask pattern is appropriately selected according to the target pattern of the cured resin pattern. As the radiation, for example, light rays such as g-line and i-line are used. For the radiation irradiation, it is preferable to use a device such as a mask aligner or a stepper, for example.
After irradiation with radiation, the colored photosensitive composition layer is developed. Development can be performed on the colored photosensitive composition layer after exposure by, for example, a paddle method, an immersion method, a spray method, or a shower method.
As the developer, an alkaline aqueous solution is usually used. As the alkaline aqueous solution, an aqueous solution of an alkaline compound is used, and the alkaline compound may be an inorganic alkaline compound or an organic alkaline compound.

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 concentration of the alkaline compound in the alkaline developer is preferably 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 preferably in the range of 0.01 to 10% by mass, more preferably 0.05 to 8% by mass, and more preferably 0.1 to 5% by mass.

  Next, the colored photosensitive composition layer is washed with water after development, and further subjected to a post-baking step at 150 to 230 ° C. for 10 to 60 minutes as necessary to obtain a pixel.

By using the colored photosensitive composition of the present invention, pixels can be formed on the substrate through the above steps.
In the obtained pixel, the angle of the pixel with respect to the substrate is preferably less than 90 degrees. When the angle is within the above range, it is preferable that the ITO wiring is not easily broken when the liquid crystal display device is formed.

  Since these pixels have good solvent resistance, they can be used for color filters used in display devices such as liquid crystal display devices, electroluminescence, and plasma display panels.

  Therefore, by incorporating the pixels thus obtained into a display device such as a liquid crystal display device, an excellent quality display device can be manufactured with high yield.

  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.

Example 1
Corresponds to 1 mol of 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride and 2 mol of pentaerythritol triacrylate ((A1)) ) (MK ESTER CBX-SK03; manufactured by Shin-Nakamura Chemical Co., Ltd.) 98 parts,
2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine 10 parts, Irgacure I-907 6 parts (corresponding to (B); manufactured by Ciba Specialty Chemicals),
C. I. Solvent Red 125 (equivalent to (C); manufactured by Ciba Specialty Chemicals) 38 parts KBM-503 (3-methacryloyloxypropyltrimethoxysilane; manufactured by Shin-Etsu Chemical Co., Ltd .; adhesion improver) 2 parts,
416 parts of propylene glycol monomethyl ether acetate,
Were mixed to obtain a colored photosensitive composition 1. The weight average molecular weight of the binder component (A) in the obtained colored photosensitive composition 1 was 546.
The results obtained as follows are shown in Table 1.

<Pattern formation>
The colored photosensitive composition 1 was spin-coated on a 2-inch square glass substrate (Eagle 2000; manufactured by Corning) and prebaked at 100 ° C. for 3 minutes. After cooling, the exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) was set with the distance between the substrate coated with the colored photosensitive composition 1 and the quartz glass photomask having the patterns described in the following evaluation items being 100 μm. Was irradiated with light at an exposure amount of 500 mJ / cm ² (based on 365 nm) in an air atmosphere.

  After light irradiation, the substrate was developed by immersing the coating film in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 23 ° C. for 80 seconds, washed with water, and then in an oven. And post-baking at 180 ° C. for 20 minutes. After standing to cool, the film thickness of the obtained cured pattern was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.) and found to be 2.0 μm.

<Solvent resistance>
In the exposure process, the same operation is performed except that no photomask is used, and a coating film is prepared. The chromaticity x1 is measured using a colorimeter (OSP-200; manufactured by Olympus Optical Co., Ltd.). It was. After the obtained coating film was immersed in N-methylpyrrolidone at 23 ° C. for 30 minutes, the chromaticity x2 was measured.

  When the color difference (difference between chromaticity x1 and x2) is 0.01 or less, the solvent resistance is good and is described as ◯, and when it is out of the above range, it is marked as x.

<Pattern shape>
In the exposure step, a pattern formed using a photomask on which a 100 μm line and space pattern was formed as a photomask was observed using a scanning electron microscope (S-4000; manufactured by Hitachi, Ltd.). .
The pattern shape was determined as a forward taper when the angle of the pattern side wall with respect to the substrate was less than 90 degrees and a reverse taper when the angle was 90 degrees or more.
A forward taper is preferred because the ITO wiring is less likely to break during the formation of the liquid crystal display device.

Example 2
As the binder component (A), a reaction of 1 mol of 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride with 2 mol of pentaerythritol triacrylate Product (MK ESTER CBX-SK03; Shin-Nakamura Chemical Co., Ltd.) (equivalent to (A1)) 58 parts,
20 parts of dipentaerythritol hexaacrylate (corresponding to (A2))
20 parts of ethylene glycol dimethacrylate (corresponding to (A2-1))
A colored photosensitive composition 2 was obtained by mixing in the same manner as in Example 1 except that was used. The weight average molecular weight of the binder component (A) in the obtained colored photosensitive composition 2 was 518.
Evaluation was performed in the same manner as in Example 1 except that the colored photosensitive composition 2 was used in place of the colored photosensitive composition 1. The results are shown in Table 1.

Example 3
As the binder component (A), a reaction of 1 mol of 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride with 2 mol of pentaerythritol triacrylate Product (MK ESTER CBX-SK03; manufactured by Shin-Nakamura Chemical Co., Ltd.) (equivalent to (A1)) 78 parts
1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol (EHPE3150; manufactured by Daicel Chemical Industries) (equivalent to (A3)) 20 parts,
A colored photosensitive composition 3 was obtained by mixing in the same manner as in Example 1 except that was used. The weight average molecular weight of the binder component (A) in the obtained colored photosensitive composition 3 was 882.
Evaluation was performed in the same manner as in Example 1 except that the colored photosensitive composition 3 was used in place of the colored photosensitive composition 1. The results are shown in Table 1.

Comparative Example 1
As binder component (A),
1 mol of 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride and 2 mol of pentaerythritol triacrylate (MK ESTER CBX-SK03) ; Shin-Nakamura Chemical Co., Ltd.) (equivalent to (A1)) 87 parts,
Methacrylic acid / benzyl methacrylate copolymer (Mw = 10000) 11 parts,
A colored photosensitive composition H1 was obtained by mixing in the same manner as in Example 1 except that was used. The weight average molecular weight of the binder component (A) of the obtained colored photosensitive composition H1 was 1585.
Evaluation was performed in the same manner as in Example 1 except that the colored photosensitive composition H1 was used instead of the colored photosensitive composition 1. The results are shown in Table 1.

Comparative Example 2
As a binder component (A), dipentaerythritol pentaacrylate succinic acid monoester (TO-1382; manufactured by Toagosei Co., Ltd.) (corresponding to (A1)) 60 parts, dipentaerythritol hexaacrylate (Kayarad DPHA; Nippon Kayaku) Co., Ltd.) (corresponding to (A1)) A colored photosensitive composition H2 was obtained by mixing in the same manner as in Example 1 except that 40 parts were used. The weight average molecular weight of the binder component (A) of the obtained colored photosensitive composition H2 was 613.
Evaluation was performed in the same manner as in Example 1 except that the colored photosensitive composition H2 was used instead of the colored photosensitive composition 1. The results are shown in Table 1.

From the results of Examples 1 to 3 shown in Table 1, the colored photosensitive composition of the present invention in which the weight average molecular weight of the binder component (A) is 1500 or less is the solvent resistance of the colored pattern formed using this. Excellent.
On the other hand, the colored photosensitive composition H1 containing the binder component (A) having a weight average molecular weight of 1,585 in Comparative Example 1 was only poor in solvent resistance.
In addition, the colored photosensitive composition H2 containing 1 mol of trimellitic anhydride and 1 mol of dipentaerythritol pentaacrylate as the binder component (A) in Comparative Example 2 was also inferior in solvent resistance.
Moreover, when forming a colored pattern using the colored photosensitive composition of this invention, it turns out that the shape of the pattern obtained is a forward taper shape, and shows a preferable pattern shape as a pattern for color filters.

  According to the colored photosensitive composition of the present invention, a pattern and a coating film excellent in solvent resistance can be formed.

Claims (9)

  In the photosensitive resin composition containing a binder component (A), a photopolymerization initiator (B), and a colorant (C), tetracarboxylic dianhydride, one hydroxyl group and one as a binder component (A) A colored photosensitive composition comprising a reaction product (A1) with a compound having a photopolymerizable unsaturated bond, wherein the binder component (A) has a weight average molecular weight of 300 to 1,500.   A reaction product (A1) of a tetracarboxylic dianhydride with a compound having one hydroxyl group and one or more photopolymerizable unsaturated bonds is a tetracarboxylic dianhydride, one hydroxyl group and two The colored photosensitive composition according to claim 1, which is a reaction product with a compound having the above unsaturated double bond.   The colored photosensitive composition according to claim 1 or 2, wherein the colorant (C) is a dye.   The colored photosensitive composition according to any one of claims 1 to 3, further comprising a photopolymerizable compound (A2) having no carboxyl group as the binder component (A).   The colored photosensitive composition of Claim 4 in which the photopolymerizable compound (A2) which does not have a carboxyl group contains the photopolymerizable compound (A2-1) which has a hydroxyl group. The colored photosensitive composition of Claim 4 or 5 in which the photopolymerizable compound (A2) which does not have a carboxyl group contains the compound (A3) represented by Formula (I).

[In Formula (I), R ¹ represents an alkylene group having 1 to 4 carbon atoms.
R ² represents a group having a polymerizable unsaturated bond.
m represents an integer of 1 to 4. ]   The coloring pattern formed using the coloring photosensitive composition in any one of Claims 1-6.   A color filter comprising the colored pattern according to claim 7.   A liquid crystal display device comprising the color filter according to claim 8.