JPH10274848A - Radiation sensitive composition and radiation sensitive composition for color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To reduce production cost by adding a specified compd. having unsatd. groups and carboxyl groups to a radiation sensitive compsn. SOLUTION: This radiation sensitive compsn. contains a compd. having unsatd. groups and carboxyl groups obtd. by allowing tetracarboxylic acid dianhydride represented by formula I to react with a compd. represented by formula II and/or a compd. having unsatd. groups and carboxyl groups obtd. by allowing a compd. represented by formula III to react with an acid anhydride represented by formula IV. In the formula I, R1 is a pentavalent org. group. In the formula II, R2 is a monovalent org. group having at least one radiation polymerizable unsatd. bond. In the formula III, R4 is a divalent org. group and R5 is OH or a monovalent org. amino group. In the formula IV, R6 is a monovalent org. group having at least one radiation polymerizable unsatd. bond.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a radiation-sensitive composition containing a compound having an unsaturated group and a carboxyl group having a specific structure. More specifically, the present invention relates to a radiation-sensitive composition for a color filter containing the unsaturated group- and carboxyl group-containing compound, which is used for a color liquid crystal display device, a color image pickup tube element, and the like.

[0002] Furthermore, the present invention relates to a color filter using the composition.

[0003]

2. Description of the Related Art When colorizing a liquid crystal display device or a solid-state image pickup device, a color filter composed of finely processed colored pixels is generally used. As a colorant for each pixel forming such a color filter, a dye or a pigment is used. In particular, in recent years, a method using a pigment has become mainstream because of its excellent heat resistance, light resistance, and chemical resistance. It is getting.

As a method of manufacturing a color filter, there are methods such as a photolithography method, a printing method, and an electrodeposition method. From the viewpoint of the quality of a product to be obtained and the manufacturing cost, a photolithography method is used. The law has become mainstream.

[0005] In the photolithography method, a radiation-sensitive colored composition is used as a material. Generally, a pigment dispersion comprising a pigment, a dispersant and a solvent is added to a binder polymer, a polyfunctional monomer, and a photopolymerizable polymer. It was prepared by adding an initiator and the like. As a binder polymer to be used, an acrylic polymer is mainly used. As the polyfunctional monomer, a polyfunctional acrylic compound which is liquid at room temperature is widely used.

[0006]

Recently, in the production of a color filter by a photolithography method, reduction of the exposure time has been studied for the purpose of further reducing the production cost. However, when a conventional radiation-sensitive colored composition is used, if the exposure amount in the photolithography step is small, photocrosslinking does not proceed sufficiently, patterning cannot be performed well, or the hardness of the obtained color filter is insufficient. There was a problem.

[0007] Regarding the above problems, for example, an improvement method such as increasing the number of polyfunctional monomers which are photopolymerizable components is taken. However, if too much is introduced, tackiness occurs in the film before exposure, which causes a new problem that the photomask for patterning is soiled. Further, since a commonly used polyfunctional monomer has low solubility in a developing solution, increasing the amount of the polyfunctional monomer is not an effective improvement method in terms of the above-mentioned problems from the viewpoint of developability.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel radiation-sensitive composition containing a compound containing an unsaturated group and a carboxyl group.

Another object of the present invention is to provide a radiation-sensitive composition capable of producing a color filter having high hardness with a small amount of exposure.

As a result of intensive studies on the above problems, it has been found that, by adding an unsaturated group- and carboxyl group-containing compound having a specific structure to a radiation-sensitive composition, the patterning characteristics are excellent even with a small exposure dose, and the hardness is low. It has been found that high color filters can be obtained.

That is, in the present invention, the expression (1)

[0012]

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Wherein R ₁ represents a tetravalent organic group. A tetracarboxylic dianhydride represented by the formula (2):

[0014]

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[Wherein, R ₂ represents at least one monovalent organic group having a radiation-polymerizable unsaturated bond;
R ₃ represents a monovalent organic group selected from a hydroxyl group and an amino group. And / or a compound containing an unsaturated group and a carboxyl group (hereinafter, referred to as “specific reactant a.”) Obtained by reacting the compound represented by the formula
Equation (3)

[0016]

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[0017] [wherein, R ₄ represents a divalent organic group, R ₅
Represents a monovalent organic group selected from a hydroxyl group and an amino group. And a compound represented by the formula (4)

[0018]

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[In the formula, R ₆ represents a monovalent organic group having at least one radiation-polymerizable unsaturated bond. The present invention provides a radiation-sensitive composition containing an unsaturated group and a carboxyl group-containing compound (hereinafter, referred to as “specific reactant b.”) Obtained by reacting the acid anhydride represented by the formula (1).

Further, (A) a specific reactant a. And / or specific reactants b. And (B) a colorant; (C) a binder polymer and a polyfunctional monomer; (D) a photopolymerization initiator; and (E) a solvent. A coloring composition is provided.

It also relates to a color filter containing this composition.

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, each component of the radiation-sensitive coloring composition for a color filter of the present invention will be described in detail.

(A) Compound containing unsaturated group and carboxyl group “Specific reactant a.” The specific reactant a. Can be easily obtained by reacting a tetracarboxylic dianhydride with a compound containing an unsaturated group (compound selected from alcohol, phenol and amine).

Specific Reactants of the Invention a. Is essentially the formula (5)

[0025]

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[0026] In the formula, R ₇ represents a tetravalent organic group, R ₈
It is, -o -, - N (R 10) -, showed more divalent organic group selected, R ₉ has at least one radiation polymerizable unsaturated bond, a monovalent organic group. Also, R ₁₀
Represents a hydrogen atom or an alkyl group. ] It is a compound represented by these. In the present invention, this compound can be used after being isolated, or can be used in the form of a mixture. In addition, the isolated compounds may be used alone or in combination.
It is possible to use a combination of more than one kind.

Specific examples of such tetracarboxylic dianhydride include butanetetracarboxylic dianhydride, 1,
2,3,4-cyclobutanetetracarboxylic dianhydride,
1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride Anhydride, 3,5,6-tricarboxynorbornane-2-acetic acid dianhydride, 2,3
4,5-tetrahydrofurantetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofural) -3
-Methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, 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-
Aliphatic acid dianhydrides such as 1,2,3,4-tetrahydro-6-methyl-1-naphthalenesuccinic anhydride; pyromellitic dianhydride; 3,3 ', 4,4'-benzophenonetetra Carboxylic dianhydride, 3,3 ', 4,4'-
Biphenylsulfonetetracarboxylic dianhydride, 1,
4,5,8-naphthalenetetracarboxylic dianhydride,
2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ', 4,4'-biphenylethertetracarboxylic dianhydride, 3,3', 4,4'-dimethyldiphenylsilanetetracarboxylic Acid 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-dicarboxyphenoxy) 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, bis (triphenylphthalic acid) ) Aromatic tetracarboxylic dianhydride such as -4,4'-diphenylmethane dianhydride; Formula (6)

[0028]

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Equation (7)

[0030]

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An aromatic ring-containing aliphatic tetracarboxylic dianhydride represented by the following formula:

[0032]

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Wherein R ₁₁ represents a divalent organic group. ];
Formula (9) containing silicon

[0034]

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The following can be mentioned.

Among these, butanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 5- (2,5-dioxotetrahydrofural) -3-methyl-3-cyclohexene -1,2-
Dicarboxylic dianhydride, 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-methyl-1-naphthalene succinic anhydride, 3,3 ', 4,4'
-Benzophenonetetracarboxylic dianhydride, 3,
3 ', 4,4'-perfluoroisopropylidene diphthalic anhydride, 1,2,3,4-cyclobutanetetracarboxylic acid, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid A compound represented by the formula (6):
Among the compounds represented by the formula (8), the compound represented by the formula (10)

[0037]

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Equation (11)

[0039]

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Equation (12)

[0041]

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Equation (13)

[0043]

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Wherein R represents hydrogen or an alkyl group. ] And the formula (9) can be mentioned as preferred examples.

More preferred examples include butanetetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 3,4-diamine in consideration of the solubility of the obtained reactant in a solvent. Carboxy-1,2,
3,4-tetrahydro-1-naphthalene succinic anhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-6-methyl-1-naphthalene succinic anhydride,
3,3'4,4'-benzophenonetetracarboxylic dianhydride, 3,3 ', 4,4'-perfluoroisopropylidene diphthalic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic acid , 1,3-dimethyl-1,2,2
Examples include 3,4-cyclobutanetetracarboxylic acid, Formula (9), and Formula (10).

Among the compounds containing an unsaturated group represented by the general formula (2), alcohol compounds are most preferable in terms of solubility of the obtained reactant and less coloring.

Examples of the alcohol compound include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 2-acryloyloxyethyl-2-hydroxypropyl phthalate, and 2-hydroxy-3-phenoxy. Propyl acrylate, 2-acryloyloxyethyl-
Preferred examples include 2-hydroxyethylphthalic acid, glycerin diacrylate, methacrylates of the above compounds, 2-hydroxy-3-acryloyloxypropyl methacrylate, pentaerythritol triacrylate, and the like. These are used alone or in combination of two or more.

For the purpose of adjusting the degree of crosslinking and the like, a part of the compound containing an unsaturated group represented by the general formula (2) may be replaced with a similar compound containing no unsaturated group. It is possible.

Tetracarboxylic dianhydride and a compound of the general formula (2)
Is preferably 0.4 to 3.0 equivalents, more preferably 1.6 to 2.4 equivalents to 1 equivalent of tetracarboxylic dianhydride. Is equivalent. "Specific reactant b." Specific reactant b. Used in the present invention. Can be easily obtained by reacting the compound represented by the formula (3) with an acid anhydride containing a photopolymerizable unsaturated group.

Specific reactants of the invention b. Is substantially the formula (14)

[0051]

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[0052] In the formula, R ₁₂ represents a divalent organic group, R ₁₃
It is-o-or -N (R) - shows the, R ₁₄ represents a monovalent organic group having at least one photopolymerizable group. R represents a hydrogen atom or an alkyl group. ] It is a compound represented by these. In the present invention, this compound can be isolated and used. The isolated compounds can be used alone or in combination of two or more.

Among the compounds represented by the formula (3), diols and diamines are advantageous in terms of reactivity with acid anhydrides.

As such a diol compound, ordinary polyesters and various diols used as raw materials for polycarbonate can be used without any particular limitation.

Specific examples include alkanediols such as hexanediol, octanediol, and 3,3-bis (hydroxymethyl) heptane; ethylene glycol, triethylene glycol, propylene glycol,
Alkylene glycols such as bis (hydroxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane, 2,2
-Bis (4-hydroxycyclohexyl) propane,
1,4-bis (hydroxymethyl) cyclohexane,
3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5
5] alicyclic-containing diols such as undecane; m-
Xylylene glycol, p-xylylene glycol,
1,3-bis (2-hydroxyethoxy) benzene,
1,4-bis (2-hydroxyethoxy) benzene, bis [4- (2-hydroxyethoxy) phenyl] sulfone, bis [4- (2-hydroxyethoxy) -3,5
-Bromophenyl] sulfone, bis (2) -terephthalate
-Hydroxyethyl) ester, tetrabromobisphenol A bis (2-hydroxyethyl) ester, 2,
6-bis (hydroxymethyl) -p-cresol, 2,
6-bis (hydroxymethyl) pyridine, 9.9-bis (4- (2-hydroxyethoxy) phenyl) fluorene, 2,2-bis [4- (2-hydroxyethoxy) phenyl] hexafluoropropane, 4,5 Aromatic-containing diols such as -bis (hydroxymethyl) imidazole and 2,3-bis (hydroxymethyl) naphthalene; N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid, N, N -Bis (2-hydroxyethyl) -3-aminopropionitrile, N, N-bis (2-hydroxyethyl) aniline, N, N-bis (2
-Hydroxyethyl) -3-chloroaniline, N, N-
Bis (2-hydroxyethyl) disulfide, N, N-
Bis (2-hydroxyethyl) -n-dodecylamine,
N, N-bis (2-hydroxyethyl) ethylamine,
N, N-bis (2-hydroxyethyl) glycine, N,
N'-bis (2-hydroxyethyl) oxamide,
1,3-bis [1- (2-hydroxyethyl) -4-piperidyl] propane, N, N-bis (2-hydroxyethyl) -m-toluidine, N, N-bis (2-hydroxyethyl) -p Diols containing tertiary amines such as toluidine, N, N-bis (2-hydroxypropyl) aniline; Formula (15)

[0056]

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Diols containing a double bond represented by the following formulas: 1,2-bis (2-hydroxyethylthio) ethane, 1,3-bis (hydroxypropyl) tetramethylsiloxane, 2,2'-bis ( (Hydroxymethyl) diphenyl ether, 3,6-bis (hydroxymethyl) dulene, 2- (2,2-diethoxyethyl) -1,3-
Propanediol, 2,2-bis (hydroxymethyl)
Propionic acid and the like can be mentioned.

These diol compounds are appropriately selected depending on the use and the situation. For example, when it is desired to improve the transparency of the specific polymer, an aliphatic or alicyclic diol is effective, and for improving the heat resistance of the specific polymer, an aromatic-containing diol is effective.

Preferred examples of the diol used in the present invention include triethylene glycol, bis (hydroxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane,
2,2-bis (4-hydroxycyclohexyl) propane, 1,4-bis (hydroxymethyl) cyclohexane, 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10- Tetraoxaspiro [5,5] undecane, m-xylylene glycol, p
-Xylylene glycol, 1,3-bis (2-hydroxyethoxy) benzene, 1,4-bis (2-hydroxyethoxy) benzene, terephthalic acid bis (2-hydroxyethyl) ester, tetrabromobisphenol A bis (2- (Hydroxyethyl) ester, 2,6-bis (hydroxymethyl) -p-cresol, 9.9-bis (4- (2-hydroxyethoxy) phenyl) fluorene, 1,3-bis (hydroxypropyl) tetramethylsiloxane, 2,2-bis [4- (2-hydroxyethoxy) phenyl] hexafluoropropane, formula (15)
Of the compounds represented by the formulas (16) to (18)

[0060]

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[0061]

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[0062]

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And the like.

More preferably, those having a fluorene skeleton are preferable from the viewpoint of solubility in general-purpose resist solvents such as propylene glycol monomethyl ether acetate and cyclohexanone. As a specific example,
9.9-bis (4- (2-hydroxyethoxy) phenyl) fluorene can be mentioned. These are used alone or in combination of two or more.

As the acid anhydride represented by the formula (4),
Equation (19)

[0066]

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Equation (20)

[0068]

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The compounds represented by the following formulas can be mentioned as preferred examples. This form of acid anhydride is usually synthesized by reacting an alcohol compound containing an unsaturated group with trimellitic chloride anhydride. As the alcohol compound, a specific reactant a. Since the above-mentioned alcohol used in the production of the compound can be used as it is, it is possible to obtain a similar compound having a variety. These are used alone or in combination of two or more.

For the purpose of adjusting the degree of crosslinking and the like, a part of the acid anhydride containing an unsaturated group represented by the formula (4) is replaced with an acid anhydride containing no unsaturated group. Is also possible.

The use ratio of the compound of the formula (3) and the acid anhydride is such that the acid anhydride is used in an amount of 0.4 to 1 equivalent of the formula (3).
It is preferably 3.0 equivalents, more preferably 1.6 equivalents.
２2.4 equivalents.

The specific compound a. A specific compound b. In each case, the carboxyl group concentration in the specific compound (the weight of carboxyl group in the molecule) is changed by changing the molecular weight of the compound (tetracarboxylic dianhydride, alcohol, diol, carboxylic acid anhydride, etc.) as each raw material. %) Can be controlled to some extent, which is effective in controlling alkali solubility.

Specific Reactants of the Invention a. A specific reactant b.
Can be easily obtained by heating each of the above-mentioned raw materials usually in an organic solvent. For example, if the reaction site is
In the case of a reaction between an acid anhydride group and a hydroxyl group, 80 to 130
C., preferably at a reaction temperature of 90 to 120.degree. C., while taking care not to thermally polymerize the unsaturated groups contained.
In the case of a reaction between an acid anhydride group and an amino group, 0 to 1
The reaction is carried out at a reaction temperature of 00C, preferably 30-60C.

The amount of the organic solvent used is preferably such that the total amount of the raw materials used in the reaction is 10 to 50% by weight based on the total amount of the reaction solution, but is not particularly limited. .

In the above reaction for obtaining the specific reactant of the present invention, an acid catalyst, a base catalyst or the like can be used for the purpose of conducting the reaction at a lower temperature and in a shorter time.

There is no problem even if various thermal polymerization inhibitors such as hydroquinone are used for the purpose of preventing thermal polymerization of the radiation-polymerizable unsaturated group.

The specific reactant a. A specific reactant b. Is moderately hard, and has a photopolymerizable unsaturated group, so photocrosslinking occurs during exposure,
It is effective for improving the patterning characteristics and increasing the hardness of the color filter film. Furthermore, since it contains a carboxylic acid at the same time, even if it is introduced in a large amount, it does not impair the developability and is optimal as a component of the radiation-sensitive composition. Also,
Since it is a low molecular compound, there is also an advantage that a difference in dissolution rate hardly occurs unlike a polymer.

The radiation-sensitive colored composition for a color filter of the present invention comprises the specific reactant a. And / or specific reactants b. It is characterized by containing.

In the present invention, the proportion of the unsaturated group- and carboxyl group-containing compound used is determined by the amount of the colorant 1
The amount is usually 5 to 500 parts by weight, preferably 10 to 300 parts by weight based on 00 parts by weight.

In this case, if the content of the unsaturated group- and carboxyl group-containing compound is less than 5 parts by weight, the hardness of the obtained color filter tends to be insufficient. In some cases, the concentration of the colorant decreases, so that it may be difficult to achieve the desired color density as a thin film.

(B) Colorant The colorant in the present invention is not particularly limited in color tone, and is appropriately selected according to the use of the color filter.
Further, an organic colorant or an inorganic colorant may be used.

The organic colorant specifically means a dye, an organic pigment, a natural pigment, and the like. The inorganic colorant specifically includes an inorganic pigment and an inorganic salt called an extender. However, since color filters are required to have high-precision color development and heat resistance, the colorant in the present invention has a high color development property, and a colorant having high heat resistance, particularly heat-resistant decomposition resistance. Is preferable, and an organic colorant is usually preferable, and an organic pigment is particularly preferable.

Examples of the organic pigment include a color index (CI; The Society of Dyers and Colorist).
Compounds classified as Pigment (published by s company), specifically, those having a color index (CI) number as shown below.

CI Pigment Yellow 12, CI Pigment Yellow 13, CI Pigment Yellow 14, CI
Pigment Yellow 17, CI Pigment Yellow 2
0, CI Pigment Yellow 24, CI Pigment Yellow 31, CI Pigment Yellow 55, CI Pigment Yellow 83, CI Pigment Yellow 93, CI Pigment Yellow 109, CI Pigment Yellow 11
0, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 153, CI Pigment Yellow 154, CI Pigment Yellow 16
6, CI Pigment Yellow 168; CI Pigment Orange 36, CI Pigment Orange 43, CI Pigment Orange 51; CI Pigment Red 9, CI Pigment Red 97,
CI Pigment Red 122, CI Pigment Red 1
23, CI Pigment Red 149, CI Pigment Red 176, CI Pigment Red 177, CI Pigment Red 180, CI Pigment Red 215; CI Pigment Violet 19, CI Pigment Violet 23, CI Pigment Violet 29; CI Pigment Blue 15, CI Pigment Blue 1
5: 3, CI Pigment Blue 15: 6; CI Pigment Green 7, CI Pigment Green 3
6; CI Pigment Brown 23, CI Pigment Brown 25; CI Pigment Black 1, Pigment Black 7.

Examples of the inorganic colorant include, for example, titanium oxide, barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, red iron oxide (III), cadmium red, and ultramarine blue. , Navy blue, chromium oxide green, cobalt green,
Amber, titanium black, synthetic iron black, carbon black and the like can be mentioned.

The colorant in the present invention can be used together with a dispersant, if desired. As such dispersants, specifically, for example, cationic, anionic,
Examples of the surfactant include nonionic, amphoteric, silicone-based, and fluorine-based surfactants.

Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether and polyoxyethylene oleyl ether; polyoxyethylene octyl phenyl ether; Polyoxyethylene alkyl phenyl ethers such as ethylene nonyl phenyl ether; polyethylene glycol diesters such as polyethylene glycol dilaurate and polyethylene glycol distearate;
Sorbitan fatty acid esters; fatty acid-modified polyesters; tertiary amine-modified polyurethanes; and the like, and more specifically, trade names such as KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Yushi Kagaku Kogyo), F-Top (manufactured by Tochem Products), Megafac (manufactured by Dainippon Ink and Chemicals), Florard (manufactured by Sumitomo 3M), Asahi Guard, Surflon (manufactured by Asahi Glass), and the like.

These surfactants can be used alone or in combination of two or more.

The surfactant is used in an amount of usually 30 parts by weight or less, preferably 0 to 20 parts by weight, based on 100 parts by weight of the colorant.

Further, as the colorant in the present invention, a pigment particle whose surface is modified with a polymer can be used, if desired. As the modifying polymer, for example,
Examples include polymers described in Japanese Patent Application No. 7-66514 and various commercially available polymers / oligomers for dispersion.

The coloring agents described above can be used alone or in combination of two or more.

(C) Binder Polymer and Multifunctional Monomer <Binder Polymer> As the binder polymer in the present invention, a developer which acts as a binder for a colorant and is used in a development step in producing a color filter, Particularly preferably, an appropriate polymer can be used as long as it is soluble in an alkali developer.

The preferred binder polymer in the present invention is a polymer containing a carboxyl group, particularly an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter simply referred to as “carboxyl group-containing unsaturated monomer”). ") And another copolymerizable ethylenically unsaturated monomer (hereinafter, simply referred to as" other unsaturated monomer "). Carboxyl group-containing copolymer ").

Examples of the carboxyl group-containing unsaturated monomer include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, ethacrylic acid, and cinnamic acid; Unsaturated dicarboxylic acids (anhydrides) such as maleic acid, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride and mesaconic acid; trivalent or higher unsaturated polycarboxylic acids (anhydrides) Can be mentioned.

These unsaturated monomers having a carboxyl group can be used alone or in combination of two or more.

The other unsaturated monomers include, for example, styrene, α-methylstyrene, vinyltoluene,
Chlorostyrene, methoxystyrene, formula (21)

[0097]

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Equation (22)

[0099]

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Aromatic vinyl compounds such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl Acrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, allyl acrylate, allyl methacrylate, phenyl methacrylate, cyclohexyl methacrylate, benzyl acrylate, benzyl methacrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, isobornyl methacrylate , Dicyclopen Unsaturated carboxylic acid esters such as dienyl methacrylate; unsaturated carboxylic acid aminoalkyl esters such as aminoethyl acrylate, aminoethyl methacrylate, aminopropyl acrylate and aminopropyl methacrylate; unsaturated carboxylic acids such as glycidyl acrylate and glycidyl methacrylate Glycidyl esters; vinyl carboxylate esters such as vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl benzoate; unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether, methacryl glycidyl ether; acrylonitrile, methacrylic acid Vinyl cyanide compounds such as lonitrile, α-chloroacrylonitrile, vinylidene cyanide; acrylamide, methacrylamide, α-chloro Unsaturated amides or unsaturated imides such as acrylamide, N-hydroxyethyl acrylamide, N-hydroxyethyl methacrylamide, maleimide, N-phenylmaleimide, N-cyclohexylmaleimide; aliphatics such as 1,3-butadiene, isoprene, chloroprene Conjugated dienes; macromonomers having a monoacryloyl group or a monomethacryloyl group at a polymer molecular chain terminal such as polystyrene, polymethyl acrylate, polymethyl methacrylate, polybutyl acrylate, polybutyl methacrylate, and polysilicone. .

These other unsaturated monomers can be used alone or in combination of two or more.

As the carboxyl group-containing copolymer, acrylic acid and / or methacrylic acid and methyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl methacrylate, styrene,
A copolymer with at least one other unsaturated monomer selected from the group consisting of a polystyrene macromonomer and a polymethyl methacrylate macromonomer is preferred.

Specific examples of the preferred carboxyl group-containing copolymer include (meth) acrylic acid / benzyl (meth)
Acrylate copolymer, (meth) acrylic acid / methyl (meth) acrylate copolymer, (meth) acrylic acid /
Benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / benzyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer, (meth) acrylic acid / methyl (meth)
Acrylate / polystyrene macromonomer copolymer,
(Meth) acrylic acid / methyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (Meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer, and the like.

The copolymerization ratio of the carboxyl group-containing unsaturated monomer in the carboxyl group-containing copolymer is usually 5
５０50% by weight, preferably 10-40% by weight. In this case, if the copolymerization ratio of the carboxyl group-containing unsaturated monomer is less than 5% by weight, the solubility of the obtained radiation-sensitive composition in an alkali developing solution tends to decrease, and if it exceeds 50% by weight. During development with an alkali developer, the formed pixels tend to fall off the substrate and the pixel surface tends to be rough.

The proportion of the binder polymer used in the present invention is usually 1 to 100 parts by weight of the colorant (B).
0 to 1000 parts by weight, preferably 20 to 500 parts by weight.

In this case, when the use ratio of the binder polymer is less than 10 parts by weight, for example, there is a possibility that the alkali developability may be reduced or background stain or a film residue may occur in a region other than a portion where a pixel is formed. On the other hand, when the amount exceeds 1,000 parts by weight, the concentration of the colorant relatively decreases, so that it may be difficult to achieve the target color concentration as a thin film.

<Polyfunctional Monomer> Examples of the polyfunctional monomer in the present invention include ethylene glycol,
Diacrylates or dimethacrylates of alkylene glycols such as propylene glycol; diacrylates or dimethacrylates of polyalkylene glycols such as polyethylene glycol and polypropylene glycol; tri- or higher valents such as glycerin, trimethylolpropane, pentaerythritol, and dipentaerythritol Polyacrylate or polymethacrylate of polyhydric alcohol; polyester, epoxy resin, urethane resin,
Oligoacrylates or oligomethacrylates such as alkyd resins, silicone resins and spirane resins; di (meth) acrylates of hydroxyl-terminated polymers such as hydroxy-terminated polybutadiene, hydroxy-terminated polyisoprene, hydroxy-terminated polycaprolactone; Trisacryloyloxyethyl phosphate, trismethacryloyloxyethyl phosphate and the like can be mentioned.

Of these polyfunctional monomers, polyacrylates or polymethacrylates of trihydric or higher polyhydric alcohols are preferred, and specific examples of the formula (23)

[0109]

Embedded image

A compound represented by the formula: trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate,
Pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate and the like can be mentioned. In particular, the formula (23) shown above,
Trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate have high pixel strength, excellent smoothness of the pixel surface, and have a low surface area other than where pixels are formed. Dirt,
This is preferred because it is unlikely to cause film residue and the like.

A part of the polyfunctional monomer used in the present invention may be replaced with a monofunctional monomer as long as the effects of the present invention are not impaired. As such a monofunctional monomer, the monomer used as a raw material of the binder polymer described above can be applied as it is, and further, for example, ω-carboxy-polycaprolactone mono (meth) acrylate, methoxytriethylene glycol (meth) acrylate, Methoxydipropylene glycol (meth) acrylate, 2-hydroxy-3-
Phenoxypropyl (meth) acrylate and 2-acryloyloxyethyl succinic acid can be mentioned.

The proportion of the monofunctional monomer to the polyfunctional monomer is 0 to 9 for the total of 100 of the polyfunctional monomer and the monofunctional monomer.
0% by weight, preferably 0 to 50% by weight.

The proportion of the polyfunctional monomer used in the present invention is usually 5 to 500 parts by weight, preferably 20 to 3 parts by weight, per 100 parts by weight of the binder polymer shown above.
00 parts by weight.

In this case, if the proportion of the polyfunctional monomer used is less than 5 parts by weight, the pixel strength or the smoothness of the pixel surface tends to be insufficient. , And there is a tendency for background contamination and film residue to occur easily in a region other than the portion where the pixels are formed.

(D) Photopolymerization Initiator The photopolymerization initiator in the present invention is a compound which decomposes or breaks a bond upon irradiation with light to polymerize the above-mentioned polyfunctional monomer such as a radical species, a cationic species, or an anionic species. A compound that generates an active species that can be initiated is meant.

Examples of such a photopolymerization initiator include compounds having an imidazole ring, compounds having a benzoin bond, other photoradical generators, compounds having a trihalomethyl group, and the like.

As the compound having an imidazole ring, for example, the compounds described in Japanese Patent Application No. 7-66514 are effective.

Of these, in particular, 2,2'-bis (2-
(Chlorophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) biimidazole,
2,2'-bis (2-bromophenyl) -4,4 ',
5,5'-tetrakis (4-ethoxycarbonylphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis ( 2,4-dichlorophenyl)
-4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,4-dibromophenyl)-
4,4 ', 5,5'-tetraphenylbiimidazole,
2,2'-bis (2,4,6-trichlorophenyl)-
4,4 ', 5,5'-Tetraphenylbiimidazole and 2,2'-bis (2,4,6-tribromophenyl) -4,4', 5,5'-tetraphenylbiimidazole are preferred.

Compounds having a benzoin bond and other photoradical generators include, for example, 2-hydroxy-
2-methyl-1-phenylpropan-1-one, 1-
(4-Isopropylphenyl) -2-hydroxy-2-
Methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenylketone,
2,2-dimethoxy-2-phenylacetophenone, 2
-Methyl- (4-methylthiophenyl) -2-morpholino-1-propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, benzophenone, 2, 4-diethylthioxanthone, 3,3-dimethyl-4-methoxybenzophenone, 4-azidobenzaldehyde, 4-azidoacetophenone, 4-azidobenzalacetophenone, azidopyrene, 4-diazodiphenylamine, 4-diazo-
4'-methoxydiphenylamine, 4-diazo-3-methoxydiphenylamine, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, dibenzoyl, benzoin isobutyl ether, N-phenylthioacridone, Triphenylpyrylium perchlorate and other product names include Irgacure series and Darocur series manufactured by Ciba-Geigy.

Among these, product name CGI-369
(Ciba Geigy; (2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane-1-
ON), Product name CGI-1700 (manufactured by Ciba-Geigy)
Etc. are particularly preferred.

Specific examples of the compound having a trihalomethyl group include 1,3,5-tris (trichloromethyl) triazine.

These photo-radical generators can be used alone or in combination of two or more.

In the present invention, the photopolymerization initiator component (B) contains a biimidazole compound, a compound having a benzoin bond, another photoradical generator or a compound having a trihalomethyl group, if necessary. ,
Photosensitizers, curing accelerators, etc., photocrosslinking agents or photosensitizers composed of high molecular compounds (hereinafter, “polymer photocrosslinking / sensitizers”
That. ) May be used in combination.

As the sensitizer, for example, 4,4'-
Bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, ethyl-4-dimethylaminobenzoate, 2-
Ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4'-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone, and the like. Can be.

These sensitizers can be used alone or in combination of two or more.

Examples of the curing accelerator include 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, and 2,5
-Dimercapto-1,3,4-thiadiazole, 2-mercapto-4,6-dimethylaminopyridine, 1-phenyl-5-mercapto-1H-tetrazole, 3-mercapto-4-methyl-4H-1,2,4 -Triazole and the like.

These curing accelerators can be used alone or in combination of two or more.

Further, the polymer photocrosslinking / sensitizer and the like are
A polymer compound having a functional group capable of functioning as a photocrosslinking agent and / or a photosensitizer in a main chain and / or a side chain, such as a condensate of 4-azidobenzaldehyde and polyvinyl alcohol, A condensate of 4-azidobenzaldehyde with a phenol novolak resin,
Acryloylphenylcinnamoyl ester homopolymer or copolymer, 1,4-polybutadiene, 1,2
-Polybutadiene and the like.

These polymeric photocrosslinking / sensitizers can be used alone or in combination of two or more.

Among the other photoradical generators, sensitizers and curing accelerators, 2-hydroxy-2-methyl-1-
Phenylpropan-1-one, 2-methyl- (4-methylthiophenyl) -2-morpholino-1-propane-
1-one, 2-benzyl-2-dimethylamino-1-
(4-morpholinophenyl) butan-1-one, 4,
4'-bis (dimethylamino) benzophenone, 4,
4'-bis (diethylamino) benzophenone and 2
-It is preferable to use a combination of mercaptobenzothiazole or the like in that the formed pixels are less likely to fall off the substrate during development, and the pixel strength and sensitivity are high.

The proportion of the photopolymerization initiator (D) used in the present invention is usually 0.01 to 200 parts by weight, preferably 1 to 1 part by weight, per 100 parts by weight of the polyfunctional monomer (C).
20 parts by weight, particularly preferably 1 to 50 parts by weight.

In this case, if the total use ratio of these compounds is less than 0.01 part by weight, curing by radiation irradiation becomes insufficient, and there is a possibility that a pattern may be dropped, chipped or undercut, while 200 parts by weight may be caused. Exceeds
The formed pattern easily falls off the substrate during development,
In addition, background contamination, film residue, and the like are likely to occur in a region other than the portion where the pattern is formed.

The proportion of the other photoradical generator used in the present invention is preferably not more than 80% by weight of the entire photopolymerization initiator (D), and the proportion of the sensitizer and / or the curing accelerator is preferably not more than 80% by weight. , (D) is preferably 80% by weight or less of the entire photopolymerization initiator.

The proportion of the polymer photocrosslinking / sensitizer used in the present invention is preferably not more than 50% by weight of the entire photopolymerization initiator (D).

(E) Solvent The solvent in the present invention includes the above (A), (B),
The components (C) and (D) and other optional components to be added as described below are dissolved or dispersed, and do not react with these components and have appropriate volatility. Can be selected and used.

Examples of such a solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether,
Diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono (Poly) alkylene glycol monoalkyl ethers such as propyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, and tripropylene glycol monoethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene Recall monomethyl ether acetate, and propylene glycol monoethyl ether acetate (poly) alkylene glycol monoalkyl ether acetates; diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether,
Other ethers such as diethylene glycol diethyl ether and tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone and 3-heptanone; alkyl lactates such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; Ethyl hydroxy-2-methylpropionate,
Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-
Ethyl ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate,
Ethyl acetate, butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate,
Other esters such as ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate; aromatic hydrocarbons such as toluene and xylene; N-methylpyrrolidone, N, N-dimethylformamide And nitrogen-containing (amide-based) solvents such as N, N-dimethylacetamide and the like.

These solvents can be used alone or in combination of two or more.

Further, together with the solvent, benzyl ethyl ether, dihexyl ether, acetonylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, High boiling solvents such as diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate can also be used in combination.

These high-boiling solvents can be used alone or in combination of two or more.

Among the above solvents, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone , 2-heptanone, 3-heptanone, 2-
Ethyl hydroxypropionate, 3-methyl-3-methoxybutyl propionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate Butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, ethyl pyruvate and the like, and γ-butyrolactone as the high boiling solvent is preferred.

The proportion of the solvent used in the present invention is not particularly limited, but is usually (A), (B), (C),
(D) and the total amount of the various other additives described later is adjusted to be 5 to 50% by weight, and more preferably to 10 to 40% by weight. And the stability of the composition.

As described above, the radiation-sensitive composition of the present invention contains (A) to (E) as components.
An organic acid may be contained in order to further improve the solubility in an alkali developing solution and to reduce the remaining undissolved matter after the development processing.

Such an organic acid has a molecular weight of 10
An aliphatic carboxylic acid or a phenyl group-containing carboxylic acid of not more than 00 is preferable.

Among these organic acids, aliphatic dicarboxylic acids and aromatic dicarboxylic acids such as malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid and phthalic acid are alkali-soluble, It is preferable from the viewpoint of solubility in a solvent, prevention of background contamination in a region other than a portion where a pixel is formed, and the like.

The above-mentioned organic acids can be used alone or in combination of two or more.

The proportion of the organic acid used in the present invention is usually 10% by weight or less, preferably 0.001 to 10% by weight, more preferably 0.01 to 10% by weight, based on the whole composition.
1% by weight.

In this case, the use ratio of the organic acid is 10% by weight.
When the value exceeds, the adhesion of the formed pixel to the substrate tends to decrease.

Further, the radiation-sensitive composition of the present invention may contain various additives as necessary.

Examples of such additives include fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol, polyethylene glycol monoalkyl ether and polyfluoroalkyl acrylate; nonionic surfactants and cationic surfactants. And surfactants such as anionic surfactants; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N -(2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-
Aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidylpropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3 Adhesion promoters such as -chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl-6-t
-Butylphenol) and antioxidants such as 2,6-di-t-butylphenol; UV-absorption such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenone Agents; aggregation preventing agents such as sodium polyacrylate; thermal crosslinking agents such as epoxy compounds, melamine compounds and bisazide compounds;

<Method of Forming Color Filter> Next, a method of forming a color filter using the radiation-sensitive composition of the present invention will be described.

First, a light-shielding layer is formed so as to partition a portion where a pixel pattern is to be formed on the surface of a transparent substrate, and a radiation-sensitive composition in which, for example, a red pigment is dispersed is applied onto the substrate. And pre-baking to evaporate the solvent to form a coating film.

Next, after this coating film was irradiated with radiation through a photomask, development processing was performed, and the unirradiated portion of the coating film was dissolved and removed, whereby red pixels were arranged in a predetermined pattern. Form a pixel array.

After that, using each radiation-sensitive composition in which a green or blue pigment is dispersed, each composition is applied, prebaked, irradiated with radiation, and developed in the same manner as described above to obtain a green pixel array and By sequentially forming a blue pixel array on the same substrate, a color filter in which red, green, and blue pixel arrays of three primary colors are arranged on the substrate is obtained.

Examples of the transparent substrate used for forming a color filter include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamide imide, and polyimide. These transparent substrates may be subjected to an appropriate pretreatment such as a chemical treatment with a silane coupling agent or the like, a plasma treatment, an ion plating, a sputtering, a gas phase reaction method, or a vacuum deposition, if desired.

When applying the radiation-sensitive composition to the transparent substrate, an appropriate coating method such as spin coating, casting coating, and roll coating can be employed.

The coating thickness is usually a film thickness after drying.
It is 0.1 to 10 μm, preferably 0.2 to 5.0 μm, particularly preferably 0.2 to 3.0 μm.

As the radiation used for forming the color filter, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray and the like can be used.
Radiation in the range of 450 nm is preferred.

The irradiation energy amount of the radiation is preferably 1 to 1000 mJ / cm ² .

Examples of the alkaline developer include sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline,
1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5-diazabicyclo- [4.3.0] -5-
An aqueous solution such as nonene is preferred.

Further, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant or the like can be added to the alkali developer.

After the alkali development, washing is usually carried out with water.

As the developing treatment method, a shower developing method, a spray developing method, a dip (immersion) developing method, a paddle (liquid puddle) developing method, and the like can be applied. preferable.

The color filter thus formed is extremely useful for, for example, a color liquid crystal display device, a color image pickup tube element, a color sensor and the like.

[0164]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

<Specific reactant a. Synthesis Example 1> Synthesis Example 1 In a 500 ml four-necked flask, 69.41 g (310 mmol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride and 2-hydroxyethyl as an alcohol compound 80.59 g (619 mmol) of methacrylate, propylene glycol monomethyl ether acetate 150 as a solvent
g, 0.62 g (2.9 mmol) of tetraethylammonium bromide was charged as a catalyst, and heated at 110 ° C. with stirring. This reaction solution was initially white dot, but gradually dissolved, and completely dissolved after 2 hours. After dissolution, the reaction is allowed to proceed for 4 hours to obtain the desired specific reactant a. A solution of (a1) was obtained.

Synthetic Examples 2 to 5 The same reaction as in Synthetic Example 1 was carried out except that the starting compounds were changed, to obtain the desired compounds (a2) to (a5). Table 1 summarizes the synthesis results.

[0167]

[Table 1]

<Specific reactant b. Synthesis Example 6> Synthesis Example 6 In a 500 ml four-necked flask, as a diol compound, 9.9-bis (4- (2-hydroxyethoxy) phenyl) fluorene 64.80 g (148 mmol),
Compound 8 represented by the formula (19) as an acid anhydride compound
5.20 g (296 mmol), 150 g of propylene glycol monomethyl ether acetate as a solvent, 0.5 g of tetraethylammonium bromide as a catalyst
9 g (2.8 mmol) were charged and, with stirring, 11 g
Heated at 0 ° C. This reaction solution was in the form of white dots, but gradually dissolved. After complete dissolution, the reaction is allowed to proceed for 4 hours to obtain the desired specific reactant b. (B1)
Was obtained.

Synthesis Example 7 In a 500 ml four-necked flask, 9.9-bis (4-aminophenyl) fluorene 2 was added as a diamine compound.
2.60 g (65 mmol) as an acid anhydride compound
37.40 g of a compound represented by the formula (17) (130 mm
ol), 240 g of propylene glycol monomethyl ether acetate as a solvent, 0.26 g (1.2 mmol) of tetraethylammonium bromide as a catalyst
And heated at 60 ° C. with stirring. This reaction solution was in the form of white dots, but gradually dissolved. After complete dissolution, the reaction is allowed to proceed for 4 hours to obtain the desired specific reactant b. A solution of (b2) was obtained.

Example 1 Synthesis Example 1 was used as the component (A).
Specific reaction product (a1) synthesized in the above: 40 parts by weight of a dissolved propylene glycol monomethyl ether acetate solution, and as the component (B), a red pigment (CIPigment Red17)
7): A pigment dispersion obtained by dispersing 100 parts by weight of a dispersant, and as a component (C), a methacrylic acid / benzyl methacrylate / 2-hydroxyethyl methacrylate / polystyrene macromonomer copolymer (copolymerization weight ratio: 15)
/ 60/15/10, weight average molecular weight: 28000):
40 parts by weight, and 40 parts by weight of dipentaerythritol hexaacrylate, 2,2 ′ as the component (D)
-Bis (2-chlorophenyl) -4,4 ', 5,5'-
Tetraphenylbiimidazole: 10 parts by weight and 4,4 '
-Bis (diethylamino) benzophenone: 10 parts by weight, as the component (E), propylene glycol monomethyl ether acetate: 800 parts by weight (including the solvent for the specific reactant a1 and the solvent for the pigment dispersion), cyclohexanone: 100 parts by weight Was mixed to prepare a radiation-sensitive composition. Next, a light-shielding layer is provided on the surface of a transparent substrate made of soda glass having a silica (SiO ₂ ) film for preventing elution of sodium ions formed thereon so as to partition a portion where a pixel pattern is to be formed, and then spinning is performed. The radiation-sensitive composition was applied using a coater, and pre-baked on a hot plate at 80 ° C. for 2 minutes to form a film having a thickness of 1.5 μm.
m was formed.

Then, after cooling the substrate, the wavelength of 365 was applied to the coating film through a photomask using a high-pressure mercury lamp.
50 mJ including nm, 405 nm and 436 nm light
/ Cm ² of ultraviolet rays.

Next, the substrate was developed under the conditions described below, air-dried, and further post-baked at 180 ° C. for 30 minutes to form a pixel having a red pixel pattern of 20 μm × 20 μm on each side. An array was made.

In the obtained pixel array, no missing or missing pattern was observed. When the cross section of the pattern was observed with a scanning electron microscope, no undercut was observed.
When the pixel array was observed with an optical microscope, no undissolved matter was found in a region where no pattern was formed on the substrate. The measured pencil hardness of the obtained pixel was 5H.

<Developing Conditions> Developing solution: 0.2% by weight aqueous solution of tetramethylammonium hydroxide (25 ° C.) Developing device: Shower developing device Developing time: 1 minute Rinse time: 1 minute (ultra pure water) Shower pressure : 0.2 kg / cm ² <Examples 2 to 7> As the component (A), the specific reactant (a
In the same manner as in Example 1, except that the specific reactants (a2) to (a5) and (b1) to (b2) obtained in Synthesis Examples 2 to 7 were used instead of 1), the radiation-sensitive composition was used. Is prepared,
A pixel array was prepared. Table 2 shows the evaluation results.

[0175]

[Table 2]

<Comparative Example 1> A pigment dispersion in which 100 parts by weight of red face (CIPigment Red177) was dispersed using a dispersant as the component (B), and methacrylic acid / benzyl methacrylate / 2- as the component (C). Hydroxyethyl methacrylate / polystyrene macromonomer copolymer (copolymerization weight ratio: 15/60/15/10, weight average molecular weight: 28000): 60 parts by weight, and dipentaerythritol hexaacrylate: 60 parts by weight, (D)
As a component, 2,2'-bis (2-chlorophenyl)-
4,4 ', 5,5'-tetraphenylbiimidazole:
10 parts by weight and 4,4'-bis (diethylamino) benzophenone: 10 parts by weight, as the component (E), propylene glycol monomethyl ether acetate: 800 parts by weight (including the solvent for the pigment dispersion), cyclohexanone: 100 parts by weight The parts were mixed to prepare a radiation-sensitive composition.

Using this radiation-sensitive composition, a pixel array having a red pixel pattern formed on a substrate was produced in the same manner as in Example 1. Most of the pattern of the obtained pixel array was missing, and the pencil hardness of the remaining portion was measured. As a result, the cured film for 3H and the color filter was considerably soft.

Comparative Example 2 In Example 1, a methacrylic acid / methyl methacrylate / 2-hydroxyethyl methacrylate / polystyrene macromonomer copolymer (copolymer weight ratio: 15/60) was used as the binder polymer.
/ 15/10, weight average molecular weight: 29000), a radiation-sensitive composition was prepared in the same manner as in Comparative Example 1 to prepare a pixel array having a red pixel pattern formed on a substrate. A part of the obtained pixel array was missing a pattern, and the pencil hardness of the remaining part was measured. As a result, the cured film for 3H and the color filter was soft.

<Comparative Example 3> In Comparative Example 1, the component (C), methacrylic acid / benzyl methacrylate / 2-hydroxyethyl methacrylate / polystyrene macromonomer copolymer (copolymerization weight ratio: 15/60/15/1)
0, weight average molecular weight: 28000) and 40 parts by weight of dipentaerythritol hexaacrylate.
A radiation-sensitive composition was prepared in the same manner as in Comparative Example 1 except that the amount was changed to parts by weight.

Using this radiation-sensitive composition, it was applied to a substrate and prebaked in the same manner as in Example 1, but exposure could not be performed because tackiness (stickiness) was generated in the coating film.

[0181]

According to the present invention, by using a compound having an unsaturated group and a carboxyl group having a specific structure, it is possible to obtain a color filter which can be patterned and has high hardness even with a small exposure. A radiation-sensitive colored composition for photolithography is obtained. The color filter formed using the radiation-sensitive coloring composition of the present invention has excellent reliability and is effectively used for display devices such as desktop calculators, watches, clocks, coefficient display boards, word processors, personal computers, and liquid crystal televisions. Can be

The unsaturated group- and carboxyl group-containing compound having a specific structure according to the present invention can be used for a resist, an overcoat film, etc.
It is widely applicable to photosensitive spacers.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Atsushi Kumano 2--11-24 Tsukiji, Chuo-ku, Tokyo Inside Nippon Gosei Rubber Co., Ltd.

Claims (2)

[Claims] (1) Formula (1) [In the formula, R ₁ represents a tetravalent organic group. And a tetracarboxylic dianhydride represented by the formula (2): [Wherein, R ₂ represents at least one monovalent organic group having a radiation-polymerizable unsaturated bond, and R ₃ represents a monovalent organic group selected from a hydroxyl group and an amino group. ]
And / or a compound containing an unsaturated group and a carboxyl group, and / or a compound represented by the formula (3): [In the formula, R ₄ represents a divalent organic group, and R ₅ represents a monovalent organic group selected from a hydroxyl group and an amino group. And a compound represented by the formula (4): [In the formula, R ₆ represents a monovalent organic group having at least one radiation-polymerizable unsaturated bond. A radiation-sensitive composition comprising an unsaturated group and a carboxyl group-containing compound, obtained by reacting the acid anhydride represented by the formula (1). 2. (A) a compound containing an unsaturated group and a carboxyl group according to claim 1, (B) a colorant, (C) a binder polymer, and a polyfunctional monomer, (D) a photopolymerization initiator, and (E) A radiation-sensitive composition for a color filter, comprising a solvent.