JPH10273525A - Alkaline solution-soluble polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polymer soluble in an alkaline solution, by reacting a tetracarboxylic acid dianhydride and a diol and reacting a reaction mixture of these compounds and a compound selected from an alcohol, an amine and an acid anhydride which have at least one unsaturated bond. SOLUTION: One equivalent of a tetracarboxylic acid dianhydride represented by formula I, wherein R1 is a tetravalent organic group, such as 1,2,3,4- cyclobutanetetracarboxylic acid, and 0.5 to 1.5 equivalent of a diol represented by formula II, wherein R2 is a divalent organic group, such as 2,2-bis(4- hydroxycyclohexyl)propane, are heated and reacted in a solvent such as propylene glycol monomethyl ether acetate to produce a polymer represented by formula III, wherein R1 and R2 are as defined for formula I and II, respectively. Subsequently, into a reaction mixture containing the polymer, a compound selected from among an alcohol, an amine and an acid anhydride which have at least one unsaturated bond, such as 2-hydroxyethyl acrylate, 4-amino-4'- methoxystilbene and maleic anhydride, respectively, is added and reacted as a capturing agent, to provide a desired polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel alkali-soluble polymer containing a carboxyl group.

Further, a radiation-sensitive composition containing the polymer, a radiation-sensitive composition for a color filter which is also used in a color liquid crystal display device or a color image pickup tube element, and the like, and a radiation-sensitive composition containing the polymer are used. Also related to color filters.

[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 excellent in pigment dispersibility and resist properties 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.

[0008] On the other hand, although an attempt has been made to improve the binder polymer, the acrylic polymer currently used has a soft main chain skeleton, so that no significant improvement can be expected, and an increase in the hardness of the polymer itself is desired. Was rare.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel alkali-soluble polymer containing a carboxyl group.

Another object of the present invention is to provide a novel alkali-soluble polymer containing a carboxyl group which can be contained in a radiation-sensitive coloring composition and which can produce a color filter having a high hardness even with a small exposure. Is to provide.

As a result of intensive studies on the above problems, it has been found that, by using a novel polyester-based carboxyl group-containing polymer as a binder polymer, a color filter having excellent patterning characteristics and high hardness can be obtained even with a small amount of exposure. Was found to be possible.

That is, the first aspect of the present invention is the following formula (1)

[0013]

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[In the formula, R ₁ represents a tetravalent organic group. A tetracarboxylic dianhydride represented by the following formula (2):

[0015]

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[In the formula, R ₂ represents a divalent organic group. A diol represented by the following formula:
Carboxyl group-containing alkali-soluble polymer (hereinafter, referred to as
In the second embodiment, a tetracarboxylic dianhydride represented by the above formula (1), a diol represented by the above formula (2), A carboxyl group-containing alkali-soluble polymer (hereinafter, referred to as "specific polymer b.") Obtained by reacting an alcohol, amine, or acid anhydride containing at least one unsaturated bond capable of photopolymerization. Call).

In connection with these first and second embodiments, the specific polymer a. Wherein the above formula (2) is 9.9-bis (4- (2-hydroxyethoxy) phenyl) fluorene a. Or a specific polymer b. To provide a carboxyl group-containing alkali-soluble polymer according to the above. And / or a specific polymer b. A radiation-sensitive composition containing the alkali-soluble polymer of the specific polymer a. And / or a specific polymer b. An alkali-soluble polymer, a colorant, a polyfunctional monomer, a photopolymerization initiator, and a solvent for providing a radiation-sensitive composition for a color filter. Providing a color filter comprising the composition is also included.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

(A) Alkali-soluble polymer (binder polymer) “Specific polymer a.” The specific polymer a. Can be easily obtained by reacting a tetracarboxylic dianhydride with a diol compound.

The specific polymer of the present invention a. Is substantially the following general formula (3)

[0021]

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Wherein R ₁ and R ₂ are the same as described above.

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 (4)

[0024]

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And equation (5)

[0026]

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An aromatic ring-containing aliphatic tetracarboxylic dianhydride represented by the following general formula (6):

[0028]

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Wherein R ₃ represents a divalent organic group. ];
Formula (7) containing silicon

[0030]

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Compounds represented by the following formulas:

Among these, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, butanetetracarboxylic acid Dianhydride, 2,3,5-
Tricarboxycyclopentyl acetic acid 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-naphthalenesuccinic anhydride, 3,4-dicarboxy-1,2,2
3,4-tetrahydro-6-methyl-1-naphthalene succinic anhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-perfluoroisopropylate Of the didiphthalic anhydride, the compound represented by the formula (4) and the compound represented by the general formula (6), the compounds represented by the formulas (8) to (11)

[0033]

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[0034]

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[0035]

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[0036]

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Wherein R represents hydrogen or an alkyl group. ] And the compound represented by the formula (7) 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 polymer 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 Acid, 1,3-dimethyl-1,2,2
3,4-cyclobutanetetracarboxylic acid, and compounds represented by the above formulas (4), (8) and (10) can be mentioned.

The compounds shown above can be used alone or in combination of two or more.

As the diol compound, ordinary polyesters and various diols used as raw materials for polycarbonate can be applied to the specific polymer of the present invention without any particular limitation.

Examples of such diol compounds include alkyl diols such as hexane diol, octane diol, and 3,3-bis (hydroxymethyl) heptane; alkylene glycols such as ethylene glycol, triethylene glycol and propylene glycol; (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, and other alicyclic group-containing diols; 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, terephthal Acid bis (2-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-toluidine, N, N-bis (2
Diols containing a tertiary amine such as -hydroxypropyl) aniline; the following general formula (12)

[0042]

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[ _Ra represents a divalent organic group, and _Rb represents hydrogen or an alkyl group. Diols containing a double bond represented by the formula: 1,2-bis (2-hydroxyethylthio)
Ethane, 1,3-bis (hydroxypropyl) tetramethylsiloxane, 2,2'-bis (hydroxymethyl)
Diphenyl ether, 3,6-bis (hydroxymethyl) durene, 2- (2,2-diethoxyethyl)-
Examples thereof include 1,3-propanediol and 2,2-bis (hydroxymethyl) propionic acid.

These diol compounds are appropriately selected according to 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 represented by the above formula (1
Among the compounds represented by 2), formulas (13) to (15)

[0046]

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[0047]

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[0048]

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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.

By adjusting the molecular weight of the diol compound used in the reaction, the carboxyl group content of the polymer of the present invention can be controlled to some extent, which is effective in controlling alkali solubility.

In addition to the above-mentioned tetracarboxylic dianhydride and a diol compound, a monofunctional acid anhydride, an alcohol, an amine or the like may be reacted to block the terminal of the polymer without any problem. .

The proportion of the tetracarboxylic dianhydride and the diol compound used is preferably 0.5 to 1.5 equivalents of the total amount of the diol compound per 1 equivalent of the total amount of the tetracarboxylic dianhydride. From the viewpoint of the viscosity of the obtained polymer, it is more preferably 0.8 to 1.2 equivalents.

"Specific polymer b."
A specific polymer b. Is obtained by sealing the terminal of the polymer represented by the general formula (3) with a substituent having a photopolymerizable unsaturated group, and substantially comprises the following general formula (16)

[0055]

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[Wherein R ₁ and R ₂ are the same as above. R ₄
Represents a monovalent organic group containing a photopolymerizable unsaturated group. Or the following general formula (17)

[0057]

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Wherein R ₁ , R ₂ and R ₄ are as defined above. Or the following general formula (18)

[0059]

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Wherein R ₁ and R ₂ are the same as above. R ₅
Represents a divalent organic group containing a photopolymerizable unsaturated group. ].

The polymer represented by the above formula (16) can be easily obtained by reacting a tetracarboxylic anhydride with a diol compound and a monofunctional alcohol containing a photopolymerizable unsaturated group. . As the tetracarboxylic anhydride and the diol compound, the compounds described above can be applied as they are.

Examples of the monofunctional alcohol containing a photopolymerizable unsaturated group for terminal capping include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate,
2-hydroxybutyl acrylate, 2-acryloyloxyethyl-2-hydroxypropyl phthalate, 2-
Hydroxy-3-phenoxypropyl acrylate, 2
-Acryloyloxyethyl-2-hydroxyethylphthalic acid, glycerin diacrylate, methacrylates of the above compounds, 2-hydroxy-3-acryloyloxypropyl methacrylate, pentaerythritol triacrylate, and the like can be mentioned as preferred examples. . These are used alone or in combination of two or more.

For the purpose of adjusting the degree of crosslinking and the like, it is also possible to replace a part of the photopolymerizable monofunctional alcohol containing an unsaturated group with a similar compound containing no unsaturated group. .

The polymer represented by the above formula (17) can be easily obtained by reacting a tetracarboxylic anhydride with a diol compound and a monofunctional amine having a photopolymerizable unsaturated group. . As the tetracarboxylic anhydride and the diol compound, the compounds described above can be applied as they are.

Preferred examples of the monofunctional amine having a photopolymerizable unsaturated group for terminal capping include 4-amino-4'-methoxystilbene 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, it is also possible to replace a part of the photopolymerizable unsaturated group-containing monofunctional amine with a similar compound containing no unsaturated group. . Among them, those containing a thiol group such as 6-amino-2-mercaptobenzothiazole, 2-amino-5-mercapto-1,3,4-thiazole, 4-aminothiophenol, It is particularly preferable because it can function as a curing accelerator.

The polymer represented by the above formula (18) can be easily obtained by reacting a tetracarboxylic acid anhydride with a diol compound and furthermore an acid anhydride containing a photopolymerizable unsaturated group. . As the tetracarboxylic anhydride and the diol compound, the compounds described above can be applied as they are.

As the monofunctional acid anhydride containing a photopolymerizable unsaturated group for terminal capping, maleic anhydride represented by the following general formula (19):

[0069]

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[In the formula, R ₆ represents a monovalent organic group containing a photopolymerizable unsaturated group. The compound shown by these] can be mentioned as a preferable example. In particular, the general formula (1)
The acid anhydride of 9) can be easily synthesized usually by reacting an alcohol compound containing an unsaturated group with trimellitic chloride anhydride, so that a variety of compounds can be obtained. It is.

These may be used alone or in combination of two or more.

For the purpose of adjusting the degree of crosslinking and the like, it is also possible to replace a part of the monofunctional acid anhydride containing a photopolymerizable unsaturated group with a similar compound containing no unsaturated group. And examples of such compounds include:
Examples include phthalic anhydride.

The proportions of the tetracarboxylic dianhydride, the diol compound, the alcohol, the amine and the acid anhydride can be used in the case where the terminal terminating agent is an alcohol, per one equivalent of the acid anhydride group of the tetracarboxylic dianhydride. On the other hand, the total amount of the hydroxyl groups of the diol compound and the alcohol is preferably 0.5 to 1.5 equivalents, and from the viewpoint of the viscosity of the obtained polymer,
More preferably, it is 0.8 to 1.2 equivalents.

When the terminal stopper is an amine, the total amount of the hydroxyl group of the diol compound and the amino group of the amine is 0.5 to 1 equivalent of the acid anhydride group of the tetracarboxylic dianhydride.
The amount is preferably 1.5 equivalents, and more preferably 0.8 to 1.2 equivalents from the viewpoint of the viscosity of the obtained polymer.

In the case where the terminal terminator is an acid anhydride, the hydroxyl group of the diol compound is added in an amount of 0.5 to 0.5 with respect to 1 equivalent of the total amount of the acid anhydride groups of the tetracarboxylic dianhydride and the acid anhydride compound.
The amount is preferably 1.5 equivalents, and more preferably 0.8 to 1.2 equivalents from the viewpoint of the viscosity of the obtained polymer.

Specific Polymer of the Invention a. A specific polymer 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 ° C., and in the case of a reaction between an acid anhydride group and an amino group, 0 to 100 ° C .;
The reaction is preferably performed at a reaction temperature of 30 to 60 ° C.

In particular, the specific polymer b. Is usually synthesized through a two-step reaction as described below.

In the case of the general formulas (16) and (17), first, the tetracarboxylic dianhydride and the diol are added in a molar ratio of 90 to 90 in such a state that the tetracarboxylic dianhydride becomes excessive. The reaction is carried out at a temperature of 120 ° C.

After sufficiently reacting the acid anhydride with the alcohol, the mixture is once cooled to room temperature, and then a monoalcohol or a monoamine is charged into the above reaction solution. In the case of a monoamine, the desired polymer can be obtained by reacting at a temperature of 30 ° C.

In the case of the general formula (18), first, the tetracarboxylic dianhydride and the diol are reacted at a temperature of 90 to 120 ° C. in a molar ratio conversion so that the diol becomes excessive.

After the acid anhydride and the alcohol are sufficiently reacted, the mixture is once cooled to room temperature, and then the acid anhydride is charged into the above reaction solution and reacted at a reaction temperature of 90 to 120 ° C. And the desired polymer can be obtained.

In general, the amount of the organic solvent used is such that the total amount of the starting materials used in the reaction is 10 to 10% of the total amount of the reaction solution.
It is preferable that the content be 50% by weight, but there is no particular limitation.

The type of the organic solvent is not particularly limited as long as it can dissolve the polymer obtained by the reaction.
Considering harmfulness to the human body and solubility of the polymer, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, cyclohexanone,
Methyl hydroxypropionate, ethyl 2-hydroxypropionate, N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, γ-
Butyrolactone and the like can be mentioned as preferred examples.

In the above reaction for obtaining the specific polymer of the present invention, an acid catalyst or a base catalyst can be used for the purpose of conducting the reaction at a lower temperature and in a shorter time. Coalescing b. When synthesizing the compound, 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.

Further, for the purpose of controlling the alkali solubility of the specific polymer, the carboxylic acid of the specific polymer can be crushed by reacting with a monofunctional epoxy compound or the like. When a compound having a radiation-polymerizable multiple bond such as (meth) acrylate in its structure is used as a monofunctional epoxy compound, the polymer has more crosslinking points, which is effective for radiation curing. The reaction between a carboxylic acid and an epoxy compound is well known in the art. Usually, in an appropriate organic solvent, a component such as a catalyst such as triethylamine or triphenylphosphine, or a thermal polymerization such as hydroquinone or phenothiazine is used. The reaction can be easily performed by heating in the presence of an inhibitor.

The specific polymer a. A specific polymer b. Has a carboxyl group, is soluble in an alkaline aqueous solution, and has a hard main chain skeleton compared to conventional acrylic resins, so that a component of a color filter coloring composition for obtaining a color filter having high hardness As the best. Further, the specific polymer b. Has an unsaturated group which can be photopolymerized, so that photocrosslinking occurs at the time of exposure, which is effective for improving patterning characteristics and further increasing the hardness of the color filter.

Specific Polymer of the Invention a. And / or a specific polymer b. Can be contained as a binder polymer in the coloring composition for a color filter.

Further, the coloring composition for a color filter may contain other polymers other than the above-mentioned specific polymer to such an extent that the effects of the present invention are not impaired.

The polymer is not particularly limited as long as it does not break the pigment dispersion system. However, considering the alkali developing performance, a polymer containing a carboxyl group is preferable, and one or more carboxyl groups are particularly preferable. Group-containing ethylenically unsaturated monomer (hereinafter simply referred to as "carboxyl group-containing unsaturated monomer") and another copolymerizable ethylenically unsaturated monomer (hereinafter simply referred to as "other unsaturated monomer"). (Hereinafter simply referred to as “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, mesaconic acid; trivalent or higher unsaturated polycarboxylic acids (anhydrides) Can be mentioned.

These carboxyl group-containing unsaturated monomers 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 (20)

[0093]

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Equation (21)

[0095]

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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 di-enyl methacrylate; aminoethyl acrylate,
Unsaturated carboxylic acid aminoalkyl esters such as aminoethyl methacrylate, aminopropyl acrylate and aminopropyl methacrylate; unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate; vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate Carboxylic acid vinyl esters; unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether, methacryl glycidyl ether; acrylonitrile;
Vinyl cyanide compounds such as methacrylonitrile, α-chloroacrylonitrile and vinylidene cyanide; acrylamide, methacrylamide, α-chloroacrylamide, N-hydroxyethylacrylamide, N-hydroxyethylmethacrylamide, maleimide, N-phenylmaleimide, N Unsaturated amides or unsaturated imides such as cyclohexylmaleimide; aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; polystyrene, polymethyl acrylate, polymethyl methacrylate, polybutyl acrylate, polybutyl methacrylate, poly Macromonomers having a monoacryloyl group or a monomethacryloyl group at the terminal of a polymer molecular chain such as silicone can be exemplified.

These other unsaturated monomers can be used alone or as a mixture of two or more.

Examples of the carboxyl group-containing copolymer include 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 radiation-sensitive composition for a color filter is usually such that the total amount of the binder polymer is 10 to 1,000 parts by weight, preferably 100 parts by weight of the colorant (B) described later. Is 20-5
Preferably, the amount is 00 parts by weight.

In this case, if 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.

(B) Colorant The colorant used in these compositions (radiation-sensitive composition or radiation-sensitive composition for color filter) is not particularly limited in color tone, and is suitable for use in color filters. It is appropriately selected according to the requirements, and may be an organic colorant or an inorganic colorant.

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 123, CI Pigment Red 14
9, CI Pigment Red 176, CI Pigment Red 177, CI Pigment Red 180, CI Pigment Red 215; CI Pigment Violet 19, C.I.
CI Pigment Violet 23, CI Pigment Violet 29; CI Pigment Blue 15, CI Pigment Blue 15: 3, CI Pigment Blue 15: 6;
I. Pigment Green 7, CI Pigment Green 3
6; CI Pigment Brown 23, CI Pigment Brown 25; CI Pigment Black 1, Pigment Black 7.

Specific examples of the inorganic colorant include 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 these compositions can be used together with a dispersant, if desired. Specific examples of such dispersants include cationic, anionic, 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.

The coloring agent in these compositions is
If desired, pigment particles whose surfaces are modified with a polymer can also be used. As the modifying polymer,
For example, polymers described in Japanese Patent Application No. 7-66514 and various commercially available dispersing polymers / oligomers can be mentioned.

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

(C) Polyfunctional Monomers Examples of the polyfunctional monomers used in these compositions include diacrylates or dimethacrylates of alkylene glycols such as ethylene glycol and propylene glycol; and polyethylene glycols and polypropylene glycols. Diacrylates or dimethacrylates of polyalkylene glycols; polyacrylates or polymethacrylates of trihydric or higher polyhydric alcohols such as glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol; polyesters, epoxy resins, urethane resins, alkyd resins Acrylates or oligomethacrylates such as silicone, silicone resin and spirane resin; both ends hydroxypolybutadiene, both ends hydroxypolyisoprop Di (meth) acrylates of hydroxyl-terminated polymers such as ren and hydroxyl-terminated hydroxypolycaprolactone; trisacryloyloxyethyl phosphate, trismethacryloyloxyethyl phosphate, and the like.

Of these polyfunctional monomers, polyacrylates or polymethacrylates of trihydric or higher polyhydric alcohols are preferred, and specific examples of the formula (22)

[0116]

Embedded image

A compound represented by the formula: trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate,
Pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate and the like can be mentioned. In particular, the formula (22) 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.

The polyfunctional monomers used in these compositions may be partially replaced with monofunctional monomers 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 above-mentioned “carboxyl group-containing copolymer” 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 exemplified.

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 in these compositions is usually 5 to 500 parts by weight, preferably 20 to 300 parts by weight, based on 100 parts by weight of the above-mentioned (A) binder polymer. .

In this case, if the use ratio of the polyfunctional monomer 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 used in these compositions is a compound which decomposes or breaks a bond upon irradiation with light and has the above-mentioned polyfunctionality such as radical species, cation species and anion species. A compound that generates an active species that can initiate polymerization of the monomer.

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.

Examples of the compound 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, Examples of the product include triphenylpyrylium perchlorate and Irgacure series and Darocure series manufactured by Ciba-Geigy under product names.

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 these compositions, it is necessary to contain (D) a biimidazole compound, a compound having a benzoin bond, another photoradical generator or a compound having a trihalomethyl group as a photopolymerization initiator component. Accordingly, a sensitizer, a curing accelerator, or the like, a photocrosslinking agent or a photosensitizer (hereinafter, referred to as “polymer photocrosslinking
It is called "sensitizer." ) 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 above-mentioned polymer photocrosslinking / sensitizing agent, etc.
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 photo-radical 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 these compositions is usually 0.01 to 200 parts by weight, preferably 1 to 120 parts by weight, per 100 parts by weight of the (C) polyfunctional monomer. Parts, 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 missing, chipped or undercut, while 200 parts by weight may be produced. 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 these compositions is preferably not more than 80% by weight of the total photopolymerization initiator (D), and the use of a sensitizer and / or a curing accelerator is preferred. The proportion is preferably not more than 80% by weight of the entire photopolymerization initiator (D).

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

(E) Solvents The solvents in these compositions include (A)
It dissolves or disperses the components (B), (C) and (D) and other optional components which will be added as will be described later, does not react with these components, and has appropriate volatility. As long as it is used, it can be appropriately 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, from the viewpoint of solubility, pigment dispersibility, coatability, etc., 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 these compositions is not particularly limited, but is usually (A), (B),
The total weight of (C), (D), and other various additives described below is adjusted to be 5% to 50% by weight, and more preferably 10% to 40%. Are preferred from the viewpoint of applicability, stability of the composition and the like.

This radiation-sensitive composition was, as described above,
It contains (A) to (E) as a component, and may further contain an organic acid in order to further improve the solubility in an alkali developing solution and to reduce the remaining of 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 these compositions is usually 10% by weight or less, preferably 0.001 to 10% by weight, more preferably 0.1% by weight, based on the whole composition.
0.01 to 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 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;

Next, a method for forming a color filter using the radiation-sensitive composition 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 coated on 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.

Thereafter, using the respective radiation-sensitive compositions in which the green or blue pigments are dispersed, the respective compositions are coated, 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.

As the transparent substrate used for forming the color filter, for example, glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, polyimide and the like can be mentioned. 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, roll coating and the like can be adopted.

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 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 radiation 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.

In addition, a suitable 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 performed 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.

[0171]

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

<Polymer Characteristic Analysis> The viscosity was measured by measuring the viscosity of a 30% propylene glycol methyl ether acetate solution of each polymer with an EM viscometer manufactured by Tokyo Keiki (measuring temperature: 25 ° C.).

Nuclear magnetic resonance spectrum ( ¹ H-NMR)
Was measured using JEOL's JNM-EX90A type (90 MHz). The measurement samples were prepared by allowing a specific polymer was taken out from propylene glycol methyl ether acetate solution (the solution after the polymerization) by reprecipitation by n- hexane, dissolved in DMSO-d ₆ is deuterium solvent.

<Specific polymer a. Production> Example 1 In a 500 ml four-necked flask, 30.44 g (136 mmol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride and 9.9-bis as diol compound 59.56 g of (4- (2-hydroxyethoxy) phenyl) fluorene (136
mmol), 210 g of propylene glycol monomethyl ether acetate as a solvent, and 0.27 g (1.3 mmol) of tetraethylammonium bromide as a catalyst.
1) and heated at 110 ° C. with stirring. The reaction solution was cloudy at first, but gradually dissolved and completely dissolved after 1 hour. After dissolution, the target specific polymer a. (A1) was obtained.
The viscosity of a 30% propylene glycol monomethyl ether acetate solution of this polymer is 197 mP · s (25
° C). The NMR spectrum of the polymer is shown in FIG.
It was shown to.

Examples 2 to 8 The reaction was carried out in the same manner as in Example 1 except that the starting compounds were changed to obtain the desired compounds (a2) to (a).
8) was obtained. The implementation results are summarized in Table 1.

[0176]

[Table 1]

<Specific polymer b. Example 9 30.86 g (138 mmol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as a tetracarboxylic dianhydride and 9.9-bis as a diol compound in a 500 ml four-necked flask 57.35 g of (4- (2-hydroxyethoxy) phenyl) fluorene (131
mmol), 210 g of propylene glycol monomethyl ether acetate as a solvent, and 0.27 g (1.3 mmol) of tetraethylammonium bromide as a catalyst.
1) and heated at 110 ° C. with stirring. The reaction solution was cloudy at first, but gradually dissolved and completely dissolved after 1 hour. After dissolution, the reaction was allowed to proceed for 6 hours, and the mixture was once cooled to room temperature (about 25 ° C.). Then, 2
1.79 g of hydroxyethyl methacrylate (14 m
mol) is poured into the above reaction solution and reacted at 100 ° C. for 4 hours to obtain the desired specific polymer b. (B1) was obtained.

Examples 10 to 11 Except that the starting compounds were changed, the reaction was carried out in the same manner as in Example 9 to obtain the desired compounds (b2) to (b).
3) was obtained. The results of the implementation are summarized in Table 2.

[0179]

[Table 2]

Example 12 As the component (A), the specific polymer (a) synthesized in Example 1 was used.
1): 60 parts by weight, as the component (B), a red pigment (CI
Pigment Red 177): a pigment dispersion in which 100 parts by weight is dispersed using a dispersant, dipentaerythritol hexaacrylate: 60 parts by weight as a component (C), and 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 component (E), propylene glycol monomethyl ether acetate: 600 parts by weight (including the solvent for the pigment dispersion), cyclohexanone: 300 parts by weight Was mixed to prepare a radiation-sensitive composition.

Next, a light-shielding layer was provided on the surface of a transparent substrate made of soda glass, on which a silica (SiO ₂ ) film for preventing sodium ions from being eluted was formed, so as to partition a portion for forming a pixel pattern. Thereafter, the radiation-sensitive composition was applied using a spin coater, and prebaked 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 using a high pressure mercury lamp through a photomask.
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.

[0184] 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 13 to 22 Specific reactants (a2) to (a8) obtained in Examples 2 to 11 instead of the specific polymer (a1) as the component (A).
A radiation-sensitive composition was prepared and a pixel array was prepared in the same manner as in Example 12, except that (b1) to (b3) were used. Table 3 shows the evaluation results.

[0186]

[Table 3]

Comparative Example 1 As a binder polymer, methacrylic acid / benzyl methacrylate / 2-hydroxyethyl methacrylate /
Polystyrene macromonomer copolymer (copolymer weight ratio:
15/60/15/10, weight average molecular weight: 2800
0): 60 parts by weight, a red pigment (CI
Pigment Red 177): a pigment dispersion obtained by dispersing 100 parts by weight using a dispersant, dipentaerythritol hexaacrylate: 60 parts by weight as a component (C), 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 Was 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. 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 2 As a binder polymer, methacrylic acid / methyl methacrylate / 2-hydroxyethyl methacrylate / polystyrene macromonomer copolymer (copolymer weight ratio: 1)
5/60/15/10, weight average molecular weight: 29000)
A radiation-sensitive composition was prepared in the same manner as in Comparative Example 1 except for using, to prepare a pixel array in which a red pixel pattern was 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.

[0190]

According to the present invention, by using a novel carboxyl group-containing polyester polymer, it is possible to obtain a color filter that can be patterned with a small amount of exposure and has high hardness. A radiation-sensitive colored composition for lithography 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

Further, since the novel carboxyl group-containing polyester polymer of the present invention is soluble in an aqueous alkaline solution, if the type of photosensitizer and the type of additive are selected, it can be used for various resists, for example, It is widely applicable to overcoat films and photosensitive spacers.

[Brief description of the drawings]

FIG. 1 is an NMR chart of a specific polymer a1 prepared in Example 1.

FIG. 2 is an NMR chart for a specific polymer a4 prepared in Example 4.

FIG. 3 is an NMR chart for a specific polymer a5 prepared in Example 5.

FIG. 4 is an NMR chart for a specific polymer a6 prepared in Example 6.

FIG. 5: Specific polymer b2 prepared according to Example 10
3 is an NMR chart for the present invention.

 ────────────────────────────────────────────────── ─── 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) The following formula (1): [In the formula, R ₁ represents a tetravalent organic group. And a tetracarboxylic dianhydride represented by the following formula (2): [In the formula, R ₂ represents a divalent organic group. A carboxyl group-containing alkali-soluble polymer obtained by reacting a diol represented by the formula: (2) Formula (1) [In the formula, R ₁ represents a tetravalent organic group. And a tetracarboxylic dianhydride represented by the formula (2): [In the formula, R ₂ represents a divalent organic group. A carboxyl group-containing alkali-soluble polymer obtained by reacting the diol represented by formula (I) with an alcohol, amine or acid anhydride containing at least one unsaturated bond capable of photopolymerization.