TWI511986B - Blocked isocyanate group-containing polymer, composition comprising same and use thereof - Google Patents

Description

Polymer containing blocked isocyanato group, comprising the composition of the polymer and use thereof

The present invention relates to a novel curable polymer containing a blocked isocyanate group and use thereof, and more particularly to a curable polymer suitable as a photosensitive material for a color filter, and a polymer composition containing the curable polymer a photosensitive polymer composition containing a photopolymerization initiator in the polymer composition, a color filter formed of the photosensitive polymer composition, a method for producing the color filter, and the filter Image display component made of color.

In recent years, from the viewpoint of resource saving or energy saving, photosensitive polymer compositions which are hardenable by active energy rays such as ultraviolet rays or electron wires are widely used in various fields of coating, printing, coating, and adhesives. . Further, in the field of electronic materials such as printed wiring boards, a photosensitive polymer composition which is hardenable by an active energy ray is also used for a solder resist or a color filter resist.

The color filter is generally formed of a transparent substrate such as a glass substrate and formed in a transparent The red (R), green (G), and blue (B) pixels on the substrate, the black matrix formed on the boundary of the pixel, and the protective film formed on the pixel and the black matrix. The color filter having such a configuration is usually manufactured by sequentially forming a black matrix, a pixel, and a protective film on a transparent substrate. As a method of forming a pixel and a black matrix (hereinafter referred to as a "coloring pattern" for a pixel and a black matrix), various manufacturing methods are proposed. Among them, a pigment/dye dispersion method which is formed by a lithography method in which coating, exposure, development, and baking are repeated using a photosensitive polymer composition as a resist, is excellent in durability such as light resistance and heat resistance. Since it is possible to give a color pattern with few defects such as pinholes, it has become the mainstream now.

Generally, the photosensitive polymer composition used in the lithography method contains an alkali-soluble resin, a reactive diluent, a photopolymerization initiator, a colorant, and a solvent. In the pigment/dye dispersion method, the above advantages are obtained, but on the other hand, since the pattern of the black matrix, R, G, and B is repeatedly formed, the alkali-soluble resin of the binder of the coating film is required to have high heat decomposition resistance and heat resistance. Yellow degeneration. As a new material meeting this requirement, the inventors previously proposed to use an alicyclic monomer with ethoxylated o-phenylphenol (meth) acrylate (i.e., 2-phenylphenoxy (meth) acrylate). A copolymer having a structure derived from an alkylene oxide and a (meth) acrylate of an aryl residue represented by a base ethyl ester) (Patent Document 1).

When this copolymer is used, a photosensitive polymer composition having excellent thermal decomposition resistance and heat yellowing resistance can be obtained as compared with a conventionally known resin containing a maleimide-containing monomer as a copolymerization component. Further, the copolymer preferably has a carboxyl group in the molecule and has an acid value of 20 to 300. KOHmg/g (refer to claim 2 of Patent Document 1) is more preferably an unsaturated group in the molecule (refer to claim 3 of Patent Document 1). However, the photosensitive polymer composition prepared by using the copolymer has a pattern showing excellent performance when the coating film after alkali development is baked at a high temperature of, for example, 230 ° C, but the baking temperature is lower than that. At 200 ° C, the solvent resistance of the formed pattern becomes insufficient, and as a result, the reliability of the obtained color filter cannot be said to be sufficient. Further, when a dye is generally used as a coloring material, a coloring pattern having a high luminance can be expected as compared with a case where a pigment is used. However, when the above copolymer is used in a dye dispersion method, it is often impossible to obtain a dye-based color filter. The performance expected of the materials used in the device.

In addition, it is also known to use ethylene oxide (EO) modified with p-cumylphenol or propylene oxide (PO) modified (meth) acrylate with (meth)acrylic acid and/or (methyl) When a copolymer of acrylate is used, a photosensitive coloring composition excellent in dispersion stability of a pigment can be obtained, and when an ethylenic double bond is introduced into a side chain of the copolymer, the sensitivity of the photosensitive coloring composition can be improved (Patent Document) 2). However, as described in Patent Document 1, the material is insufficient in heat resistance, and after alkali development, when cured at a relatively low-temperature baking temperature of, for example, less than 200 ° C, the solvent resistance of the resulting pattern is obtained. It may not be sufficient.

On the other hand, there has been reported a photosensitive polymer composition containing a polymer (a) having a constituent unit derived from a blocked isocyanate compound, a photopolymerizable monomer (b), and a photopolymerization initiator (c). The resin pattern is excellent in adhesion to a substrate (Patent Document 3). It is preferred that the polymer (a) contains an acid group in the molecule, whereby it can have good developability (see According to paragraph 0024). However, this material is excellent in the point of the adhesion of the resin pattern to the substrate, but when the amount of exposure is small, there is a problem that development is difficult.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] WO2012/141000

[Patent Document 2] JP-A-2004-101728

[Patent Document 3] JP-A-2010-197567

The present invention has been made to solve the problems as described above, and a main object thereof is to provide a novel curable polymer which is excellent in sensitivity or developability even when used as a material for a photosensitive polymer composition. The baking temperature at the time of pattern formation also has sufficient solvent resistance. Still another object is to provide a polymer composition capable of forming a coating film excellent in solvent resistance. Further, another object of the invention is to provide a photosensitive polymer composition which is excellent in sensitivity or developability, and which can form a pattern excellent in solvent resistance even when the baking temperature is lowered, and is suitable as a material for a color filter; Provided is a highly reliable color filter and a method of manufacturing the same; and an image display element including the color filter.

The inventors have focused on the problem in order to solve the problems as described above. As a result, it has been found that a curable polymer containing the acid group and the polymerizable unsaturated group described in Patent Documents 1 and 2 and the blocked isocyanato group described in Patent Document 3 is used as the photosensitive polymer composition. The material was unexpectedly excellent in not only the developing property and the sensitivity at the time of alkali development, but also the solvent resistance of the obtained pattern was excellent even when the baking temperature at the time of pattern formation was lowered, and the present invention was finally completed.

According to the present invention, the first invention provides a curable polymer characterized by containing an acid group, a polymerizable unsaturated group, and a blocked isocyanate group in a molecule, and the weight average molecular weight in terms of polystyrene is 1,000~50,000. Further, the second invention provides a polymer composition comprising the curable polymer (A), a solvent (B), and optionally a reactive diluent (C); further, the third invention provides a photosensitive The polymer composition contains the curable polymer (A), the solvent (B), the reactive diluent (C), the photopolymerization initiator (D), and any coloring material (E). Furthermore, the fourth invention provides a color filter formed using the photosensitive polymer composition, and a fifth invention provides a method of manufacturing a color filter, which is the photosensitive material containing a coloring material. It is applied to a substrate, exposed by a mask, and patterned by alkali to form a pattern, and then baked at a temperature of 210 ° C or lower. The sixth invention provides an image display element including the color filter.

According to the present invention, it is possible to obtain good sensitivity or developability, and at the same time, it has sufficient solvent resistance hardening even if the baking temperature at the time of pattern formation is lowered. A curable polymer of a coating film, and a photosensitive polymer composition containing the curable polymer. Moreover, since the cured coating film formed from the photosensitive polymer composition of the present invention is excellent in sensitivity and developability, and excellent in solvent resistance, it is highly valuable in various resisting fields, and is used as a color filter. When a photosensitive material for a device is used, a color filter having a coloring pattern excellent in solvent resistance can be obtained. Further, since the crosslinking reaction proceeds sufficiently even if the baking temperature is lowered, it can be used even in a coloring material which is difficult in heat resistance, and energy consumption can be reduced.

[Formation of the Invention]

The curable polymer of the present invention contains an acid group, a polymerizable unsaturated group, and a blocked isocyanate group in the molecule, and has a weight average molecular weight of 1,000 to 50,000 in terms of polystyrene. Incidentally, in the present specification, since the polymerizable unsaturated group present in the polymer molecule contributes to the crosslinking reaction between the polymers, the polymer is referred to as a "curable polymer".

The structure of the curable polymer is not particularly limited as long as it contains an acid group, a polymerizable unsaturated group, and a blocked isocyanate group in the molecule, but generally has the following (a) blocked isocyanate group The polymerization unit of the monomer is preferably one represented by the following (I) or (II).

(I) for (a) a copolymer containing a blocked isocyanato group-containing monomer, (b) an unsaturated acid monomer, and (d) another monomer as intended, such that (c) contains an acid group a modified polymer which reacts with an unsaturated monomer of a reactive functional group and introduces a polymerizable unsaturated bond in a side chain; (II) a copolymer of (a) a monomer having a blocked isocyanato group, (c) an unsaturated monomer having an acid group and a reactive functional group, and (d) another monomer as intended A modified polymer obtained by reacting (e) an unsaturated monobasic acid and (f) a dibasic acid or an anhydride thereof, and introducing a polymerizable unsaturated bond and an acid group in a side chain.

<Manufacture of Curable Polymer (I)>

The curable polymer represented by the above (I) can be used by (a) a monomer having a blocked isocyanato group, (b) an unsaturated acid monomer, and a desired one according to a usual method ( d) after the other monomer is copolymerized to produce a curable polymer precursor, the acid group derived from the (b) unsaturated acid monomer is reacted with the unsaturated monomer having an acid group and a reactive functional group, It is obtained by introducing a polymerizable unsaturated bond into a side chain.

<Monomer used to produce a hardener polymer precursor>

The blocked isocyanato group-containing monomer used for the production of the copolymer is a terminally blocked isocyanate having a reactive ethylenically unsaturated group such as a vinyl group or a (meth) acryloxy group in the molecule. A compound in which the isocyanato group is blocked in the compound. Preferred examples of the isocyanate compound include compounds represented by the following formula (1).

In the above formula (1), R ¹ represents a hydrogen atom or a methyl group, and R ² represents -CO-, -COOR ³ - (R ³ is an alkylene group having 2 to 6 carbon atoms), or -COO-R ⁴ O- CONH-R ⁵ - (R ⁴ is an alkylene group having 2 to 6 carbon atoms, and R ⁵ is an alkylene group or an extended aryl group having 2 to 12 carbon atoms which may have a substituent). R ^{2 is} preferably -COOR ³ -, and particularly preferably R ³ is an alkylene group having 1 to 4 carbon atoms.

Specific examples of the isocyanate compound represented by the above formula (1) include 2-isocyanatoethyl (meth) acrylate, 2-isocyanatopropyl (meth) acrylate, and 3-iso Cyanate propyl (meth) acrylate, 2-isocyanato-1-methylethyl (meth) acrylate, 2-isocyanato-1,1-dimethylethyl (A) Acrylate, 4-isocyanatocyclohexyl (meth) acrylate, methacryl oxime isocyanate, and the like. Further, a 1:1 reaction product of a 2-hydroxyalkyl (meth)acrylate (the alkyl group is preferably an ethyl group or a n-propyl group, particularly preferably an ethyl group) and a diisocyanate compound may be used. Examples of the diisocyanate compound include hexamethylene diisocyanate, 2,4-(or 2,6-)toluene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), and 3 ,5,5-trimethyl-3-isocyanatomethylcyclohexyl isocyanate (IPDI), m-(or p-) xylene diisocyanate, 1,3-(or 1,4-) double (iso) Cyanate methyl) cyclohexane, diazonic acid diisocyanate, and the like. Among these, from the viewpoint of excellent alkali developability and ease of availability, R ³ of the above formula (1) is preferably an alkylene group (meth) acrylate having a carbon number of 1 to 4, particularly 2 - Isocyanatoethyl (meth) acrylate and 2-isocyanatopropyl (meth) acrylate.

Further, the term "(meth)acrylate" as used herein means that it may be either acrylate or methacrylate, and the description of (meth)acrylic acid means that it may be acrylic acid or methacrylic acid. Either.

Examples of the terminal blocking agent include decylamine such as ε-caprolactam, δ-valeroguanamine, γ-butylimamine, and β-propionamide; methanol, ethanol, and propanol; Alcohols such as butanol, ethylene glycol, methyl cellosolve, butyl cellosolve, methyl carbitol, benzyl alcohol, phenyl cellosolve, decyl alcohol, cyclohexanol, etc.; phenol, cresol, xylenol Ethylphenol, o-isopropylphenol, butyl phenol such as p-tert-butylphenol, p-t-octylphenol, nonylphenol, dinonylphenol, styrenated phenol, oxybenzoate , thymol, p-naphthol, p-nitrophenol, p-chlorophenol, etc.; dimethyl malonate, diethyl malonate, methyl acetate, ethyl acetate, ethyl acetate An active methylene group such as acetone; a thiol group such as butyl thiol, thiophenol or tridecyl thiol; an amine system such as diphenylamine, phenylnaphthylamine, aniline or carbazole; Anthranilate such as acetanilide, acetamidine, p-methoxyaniline, decylamine or benzamide; ruthenium imide such as succinimide succinate or succinimide; imidazole 2-methyl microphone , 2-ethyl-imidazole The imidazole; urea, thiourea, urea and the like of the stretch-ethyl urea; N-phenyl-carbamic acid phenyl ester, 2- Amino formates such as oxazolidinone: imines such as ethyleneimine and polyethylenimine; formaldehyde oxime, acetaldoxime, acetone oxime, methyl ethyl ketone oxime, methyl isobutyl An oxime system such as ketone oxime or cyclohexanone oxime; a hydrogensulfite system such as sodium hydrogen sulfite or potassium hydrogen sulfite.

These blocking agents may be used singly or in combination of two or more. Among these, a capping agent and an alcohol-based capping agent are preferred, and ε-caprolactam and 1-methoxy-2-propanol (i.e., propylene glycol monomethyl ether) are particularly preferred. .

The blocked group protects the isocyanate group having high reactivity, but the terminal group is detached by heating, and an isocyanate group appears. In the present invention, the isocyanate The base reacts with a reactive functional group (i.e., an acid group or a hydroxyl group or an amine group to be contained) contained in the curable polymer or the reactive diluent to form a cured product having a high crosslinking density.

The preferred blocked isocyanate compound has a dissociation temperature of from 100 ° C to 200 ° C, more preferably from 140 ° C to 190 ° C, especially from 150 ° C to 180 ° C. As a specific example of such a compound, the following formula (2) can be exemplified. a reaction product of methacryloxyethyl isocyanate, that is, 2-isocyanatoethyl methacrylate and ε-caprolactam (dissociation temperature: 160 ° C), and the following formula (3) The reaction product of methacryloxyethyl isocyanate and propylene glycol monomethyl ether (dissociation temperature 160 ° C), Karenz MOI-BM (methacryloxyethyl isocyanate and methyl ethyl ketone oxime) Reaction product, manufactured by Showa Denko Co., Ltd., dissociation temperature: 130 ° C), such as Karenz MOI-BP (a reaction product of methacryloxyethyl isocyanate and 3,5-dimethylpyrazole, manufactured by Showa Denko Co., Ltd. A methacrylate having a dissociation temperature of 110 ° C), an acrylate corresponding to the above, and the like.

Further, the dissociation temperature of the blocked isocyanate compound is adjusted to have a concentration of 20% by mass of the n-octanol solution, and 1% by mass of dibutyltin laurate and 3% by mass of equivalent thiophene are added thereto. After the polymerization inhibitor was heated at a predetermined temperature, the ratio of reduction of the compound after 30 minutes was measured by HPLC analysis, and the temperature at which the reduction ratio was 80% or more was regarded as the dissociation temperature.

When the dissociation temperature of the blocked isocyanate compound is excessively low, the storage stability of the produced polymer is lowered, and an unintended crosslinking reaction is likely to occur in the modification reaction described later, and if excessively high, When the baking temperature does not become above the dissociation temperature, it is difficult to improve the solvent resistance of the cured coating film.

The reaction of the isocyanate compound with the blocking agent can be carried out regardless of the presence or absence of the solvent. When using a solvent, it is necessary to use a solvent which is inert to the isocyanate group. When the blocking reaction is carried out, an organic metal salt such as tin, zinc or lead, a tertiary amine or the like may be used as a catalyst, and the reaction is generally carried out at -20 to 150 ° C, but preferably at 0 to 100 ° C. .

(b) the unsaturated acid monomer used for the production of the copolymer, as long as it is a polymerizable unsaturated bond and an acid group, and examples thereof include an unsaturated carboxylic acid or an anhydride thereof, an unsaturated sulfonic acid, and an unsaturated group. Phosphonic acid, etc. Specific examples of preferred unsaturated acid monomers include (meth)acrylic acid, α-bromo (meth)acrylic acid, β-furyl (meth)acrylic acid, crotonic acid, propiolic acid, and cinnamic acid. , α-cyano cinnamic acid, maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, fumaric acid, itaconic acid, itaconic anhydride, An unsaturated carboxylic acid such as citraconic acid or citraconic anhydride or an anhydride thereof; unsaturated of 2-propenylamine-2-methylpropanesulfonic acid, tert-butylacrylamidesulfonic acid, p-styrenesulfonic acid, etc. Sulfonic acid; unsaturated phosphonic acid such as vinylphosphonic acid. Among these, (meth)acrylic acid is preferred. These single systems may be used singly or in combination of two or more. By using (b) an unsaturated acid monomer as a copolymerization component, the resulting hardenable polymerization is greatly improved The alkali developability when the compound is used as a photosensitive material.

In the present invention, (d) other monomers which are copolymerizable with these may be used in combination with (a) a monomer having a blocked isocyanato group and (b) an unsaturated acid monomer. Specific examples of the (d) other monomer include styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, o-chlorostyrene, and m-chlorostyrene, and Aromatic vinyl of chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, p-nitrostyrene, p-cyanostyrene, p-acetamidostyrene Base compound; norbornene (bicyclo[2.2.1]hept-2-ene), 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2- Alkene, tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodec-3-ene, 8-methyltetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodec-3-ene, 8-ethyltetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodec-3-ene, dicyclopentadiene, tricyclo[5.2.1.0 ^2,6 ]non-8-ene, tricyclic [5.2.1.0 ^2,6 ]Indol-3-ene, tricyclo[4.4.0.1 ^2,5 ]undec-3-ene, tricyclo[6.2.1.0 ^1,8 ]und-9-ene, tricyclic [6.2.1.0 ^1,8 ] eleven-4-ene, tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 .0 ^1,6 ]dodec-3-ene, 8-methyltetracycline [4.4 .0.1 ^2,5 .1 ^7,10 .0 ^1,6 ]dodec-3-ene, 8-ethylenetetracyclo[4.4.0.1 ^2,5 .1 ^7,12 ]dodec-3-ene, 8-ethylene tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 .0 ^1,6 ]dodec-3-ene, pentacyclic [6.5.1.1 ^3,6 .0 ^2,7 .0 ^9,13 ] fifteen-4-ene, pentacyclic [7.4. 0.1 ^2,5 .1 ^9,12 .0 ^8,13 ] a cyclic olefin having a norbornene structure such as fifteen-3-ene; a diene of butadiene, isoprene, chloroprene or the like; Methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, second (meth)acrylate Butyl ester, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, amyl (meth)acrylate, neopentyl (meth)acrylate, benzyl (meth)acrylate, (methyl) ) isoamyl acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate, cyclopentane (meth) acrylate Ester, cyclohexyl (meth)acrylate, methylcyclohexyl (meth)acrylate, ethylcyclohexyl (meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, (meth)acrylic acid rosin ester, (meth)acrylic acid norbornyl ester, (meth)acrylic acid 5-methylnorbornyl ester, (meth)acrylic acid 5-ethyl norbornene Ester, dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyloxyethyl acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate , (meth)acrylic acid tetrahydrofurfuryl ester, (meth)acrylic acid 1,1,1-trifluoroethyl ester, (meth)acrylic acid perfluoroethyl ester, (meth)acrylic acid perfluoro-n-propyl ester, (a) Perfluoroisopropyl acrylate, 3-(N,N-dimethylamino)propyl (meth)acrylate, triphenylmethyl (meth)acrylate, phenyl (meth)acrylate, ( Methyl phenyl acrylate, 4-phenoxy phenyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, nonyl benzene (meth) acrylate such as oxypolyethylene glycol mono(meth)acrylate, biphenyloxyethyl (meth)acrylate, naphthalene (meth) acrylate or decyl (meth) acrylate ; (meth)acrylic acid decylamine, (meth)acrylic acid N,N-dimethyl decylamine, (meth)acrylic acid N,N-diethyl decylamine, (meth)acrylic acid N,N-dipropyl Alkylamine, N,N-diisopropyldecylamine (meth)acrylate, decylamine (meth)acrylate, etc.醯Acetylamine; (meth)acrylic acid aniline, (meth)acrylonitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinyldipyrrolidone, vinyl a vinyl compound such as pyridine, vinyl acetate or vinyl toluene; an unsaturated dicarboxylic acid such as diethyl citrate, diethyl maleate, diethyl fumarate or diethyl itaconate Ester; N-phenylmaleimide, N-cyclohexylmaleimide, N-lauryl maleimide, N-(4-hydroxyphenyl)maleimide, etc. Come to imine and so on. These may be used alone or in combination of two or more.

Among these, an aromatic vinyl compound and a cyclic olefin are preferably used. When the aromatic vinyl compound is copolymerized, heat resistance and pigment dispersibility are improved, and when a cyclic olefin is copolymerized, heat resistance, yellowing resistance, and pigment dispersibility are improved.

The ratio of (a) monomer containing blocked isocyanato group, (b) unsaturated acid monomer, and (d) other monomer used in the manufacture of the precursor, usually (a) containing blocked isocyanide The acid group monomer is 1 to 50 mol%, preferably 3 to 40 mol%, more preferably 5 to 20 mol%, and (b) the unsaturated acid monomer is 20 to 90 mol%. Preferably, the amount is 30 to 70 mol%, more preferably 40 to 60 mol%, and (d) the other monomer is 0 to 79 mol%, preferably 5 to 67 mol%, more preferably 20 to 55 mol. ear%.

(a) If the monomer containing a blocked isocyanate group is excessively small, the solvent resistance of the cured coating film is not sufficiently improved, and if it is excessively excessive, the former The storage stability of the flood polymer is deteriorated, and the physical properties of the coating film are likely to be difficult. On the other hand, when (b) the unsaturated acid monomer and (a) are excessively small, the speed of alkali development becomes slow when used as a photosensitive polymer, and conversely, if it is excessively excessive, it becomes difficult to form. Exquisite graphics. In the production of the precursor, (d) the other monomer is not necessarily required, but the heat resistance, the pigment dispersibility, and the properties of the coating film can be suitably improved by using the monomer of (d) in combination. In particular, when an aromatic vinyl compound or a cyclic olefin is used as the monomer (d), since heat resistance, yellowing resistance, and pigment dispersibility are improved as described above, it is preferred to use such an appropriate amount. monomer.

The copolymerization of (a) a monomer having a blocked isocyanato group, (b) an unsaturated acid monomer, and (d) another monomer as desired may be freely polymerized according to the well-known art in the art. The method is carried out in the presence or absence of a polymerization solvent. For example, after these monomers are dissolved in a solvent as desired, a polymerization initiator is added to the solution, and polymerization is carried out at 50 to 130 ° C for 1 to 20 hours. At this time, if the polymerization reaction is carried out at the temperature at which the blocked isocyanate group dissociates, the isocyanate group generated by the dissociation reacts with the acid group to form a gel, so it is preferably at a dissociation temperature lower than the blocked isocyanate group. The temperature is preferably at a temperature of about 20 to 50 ° C below the dissociation temperature.

The solvent which can be used in the copolymerization reaction is not particularly limited, and examples thereof include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, and diethylene glycol. Monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol Monoethyl ether, dipropylene glycol (poly)alkylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether Alkyl ethers; (poly)alkanes such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate Glycol monoalkyl ether acetate; diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran and other ethers; methyl ethyl ketone a ketone such as cyclohexanone, 2-heptanone or 3-heptanone; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, 2- Ethyl hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate Ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methyl Oxybutyl butyl propionate, ethyl acetate, n-butyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate Isobutyl acetate, n-amyl acetate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, acetone An ester of ethyl acetate, n-propyl pyruvate, methyl acetoacetate, ethyl acetate, ethyl 2-oxobutanoate or the like; aromatic hydrocarbons such as toluene and xylene; N-methyl A carboxylic acid amide such as dipyrrolidone, N,N-dimethylformamide or N,N-dimethylacetamide. These solvents may be used alone or in combination of two or more.

Among these, a (poly)alkane monoalkyl ether solvent such as propylene glycol monomethyl ether or a (poly)alkane monoalkyl ether B such as propylene glycol monomethyl ether acetate is preferable. An acid ester solvent, that is, a glycol ether solvent.

The amount of the polymerization solvent to be used is not particularly limited. When the total amount of the monomers added is 100 parts by mass, it is usually 30 to 1,000 parts by mass, preferably 50 to 800 parts by mass. In particular, when the amount of the solvent used is 1,000 parts by mass or less, the decrease in the molecular weight of the copolymer due to chain transfer can be suppressed, and the viscosity of the copolymer can be controlled to an appropriate range. In addition, when the amount of the solvent is 30 parts by mass or more, an abnormal polymerization reaction can be prevented, the polymerization reaction can be carried out stably, and coloring or gelation of the copolymer can be prevented.

Further, the polymerization initiator which can be used in the copolymerization reaction is not particularly limited, and examples thereof include azobisisobutyronitrile, azobisisovaleronitrile, benzammonium peroxide, and t-butylperoxy- 2-ethylhexanoate and the like. These may be used alone or in combination of two or more. When the total amount of the monomers is 100 parts by mass, the polymerization initiator is used in an amount of usually 0.5 to 20 parts by mass, more preferably 1.0 to 10 parts by mass.

<Manufacture of Curable Polymer (I)>

In the present invention, the addition copolymer thus produced is used as a precursor of the curable polymer (I). In the precursor, the acid group derived from the (b) unsaturated acid monomer is reacted with the (c) unsaturated monomer having an acid group and a reactive functional group in the side chain. Introducing a polymerizable unsaturated bond to obtain an acid group containing a target in a molecule, and polymerizing A sclerosing polymer (I) having a weight average molecular weight of 1,000 to 50,000 in terms of polyunsaturated groups and blocked isocyanato groups. Since the polymerizable unsaturated bond is present in the molecule, the sensitivity or developability when the curable polymer is used as the photosensitive material for the color filter is greatly improved.

Preferred examples of the (c) unsaturated monomer having an acid group and a reactive functional group for the reaction are unsaturated compounds having a functional group such as an epoxy group, a hydroxyl group, an amine group or a vinyl ether group. Specific examples thereof include glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate having an alicyclic epoxy group, and a lactone adduct thereof (for example). Cyclomer A200, M100) manufactured by DAICEL Chemical Industry Co., Ltd., mono (meth) acrylate of 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, a freely polymerizable monomer having an epoxy group such as an epoxide of dicyclopentenyl methacrylate or an epoxide of dicyclopentenyloxyethyl (meth)acrylate; (meth)acrylic acid 2 -hydroxyethyl ester, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 2-phenoxy-2(meth)acrylate - a freely polymerizable monomer having a hydroxyl group such as hydroxypropyl ester, 2-(meth)acryloxy-2-hydroxypropyl phthalate or allyl alcohol; and 4-aminostyrene or the like Amine-based free polymerizable monomer; 2-B Ethoxy ethyl (meth) (meth) acrylate of the monomer having a radical polymerizable vinyl ether group and the like. When a freely polymerizable monomer monomer having an epoxy group is used, when an unsaturated bond is introduced by a reaction with an acid group, a hydroxyl group is simultaneously formed, and an acid group can be easily introduced by using the hydroxyl group.

The above precursors and (c) have an acid group and a reactive functional group. The reaction of the saturated monomer can be carried out in accordance with a usual method. For example, two components may be added to the reaction solvent, and a polymerization inhibitor and a catalyst may be further added, and at a temperature at which the blocked isocyanate group in the precursor does not dissociate, for example, at 50 to 150 ° C, preferably 80 to 130 The reaction was carried out at °C. Further, in the modification reaction, since there is no particular problem even if the solvent used in the copolymerization reaction is contained, the modification reaction can be carried out without removing the solvent after completion of the copolymerization reaction.

When this modification reaction is carried out, a polymerization inhibitor may be added for the prevention of gelation as needed. The polymerization inhibitor is not particularly limited, and examples thereof include hydroquinone, methylhydroquinone, and hydroquinone monomethyl ether. Further, the catalyst is not particularly limited, and examples thereof include a tertiary amine such as triethylamine, a quaternary ammonium salt such as triethylbenzylammonium chloride, a phosphorus compound such as triphenylphosphine, and chromium. Chelating compounds and the like.

Thus, a polystyrene-equivalent curable polymer (I) having a weight average molecular weight of 1,000 to 50,000, preferably 3,000 to 40,000 can be obtained. When the molecular weight is less than 1,000, the coloring pattern is liable to occur after alkali development when used as a photosensitive polymer composition. Conversely, if the molecular weight exceeds 50,000, the development time is too long, and the practical time is insufficient. Sex.

Further, the acid value (JIS K6901 5.3) of the curable polymer can be appropriately selected, but when used as a photosensitive polymer, it is usually in the range of 20 to 300 KOH mg/g, preferably 30 to 200 KOH mg/g. When the acid value is less than 20 KOHmg/g, the alkali developability as a photosensitive polymer is lowered. On the other hand, if the acid value exceeds 300 KOHmg/g, the exposed portion (photohardened portion) becomes easily dissolved in the alkali developing solution, and the shape of the pattern changes. insufficient.

Further, the unsaturated group equivalent of the curable polymer (I) is not particularly limited, and is usually in the range of 100 to 4,000 g/mol, preferably 300 to 2,000 g/mol. When the unsaturated group equivalent is 100 g/mol or more, it is effective in improving the physical properties of the coating film and the alkali developing property. Conversely, the amount of the unsaturated group equivalent of less than 4,000 g/mol is effective in further improving the sensitivity. Furthermore, the so-called unsaturated bond equivalent is the mass of the polymer of the unsaturated bond of the polymer per 1 mol of the polymer, which can be obtained by dividing the mass of the polymer by the amount of unsaturated bonds of the polymer (g/mol). . The unsaturated bond equivalent in the present invention is a theoretical value calculated from the amount of the raw material used for introducing the unsaturated bond.

The curable polymer (I) of the present invention contains a blocked isocyanate group in the molecule. The content of the blocked isocyanato group may be appropriately selected, and is usually selected from the range in which the blocked isocyanate group equivalent is from 400 to 6,000, preferably from 1,000 to 5,000. The mass of the blocked isocyanato group contained in the blocked isocyanato group equivalent polymer per 1 mol of the polymer can be obtained by dividing the mass of the polymer by the blocked isocyanato group contained in the polymer. It is obtained by the number of moles (g/mol). In the present invention, the blocked isocyanate group equivalent is a theoretical value calculated from the amount of the monomer having a blocked isocyanate group.

<Manufacture of precursor of hardenable polymer (II)>

The curable polymer represented by the above (II) is obtained by (a) a monomer having a blocked isocyanato group, (c) an unsaturated monomer having an acid group and a reactive functional group, according to a usual method. And use (d) other orders as desired After the precursor is produced by copolymerization to produce a curable polymer (II) precursor, the precursor is reacted with (e) an unsaturated monobasic acid and (f) a polybasic acid or an anhydride thereof to introduce an acid group and a polymerizable property in a side chain. Derived from unsaturated bonds.

<Monomer used to produce a precursor of the curable polymer (II)>

(a) a monomer having a blocked isocyanato group and (d) another monomer used for the production of the precursor are the same as those used in the production of the above-mentioned curable polymer (I). In the case of the curable polymer (I), (b) an unsaturated acid monomer is used as an essential component, but in the case of the curable polymer (II), instead of (b) an unsaturated acid monomer, c) an unsaturated monomer having an acid group and a reactive functional group. Further, a specific example of the component (c) is the same as that of the user of the curable polymer (I), and an unsaturated monomer having an epoxy group, particularly (meth)acrylic acid propylene, is preferably used. ester.

The method for producing the precursor is the same as in the case of the curable polymer (I). An acid group and a polymerizable unsaturated bond are formed by reacting the obtained precursor with (e) an unsaturated monobasic acid and (f) a polybasic acid or an anhydride thereof. The unsaturated monobasic acid used herein may be exemplified as (b) an unsaturated acid monomer used in the production of the curable polymer (I), and (f) a polybasic acid or an anhydride thereof may be used as ( b) an unsaturated polybasic acid and an anhydride thereof exemplified as the unsaturated acid monomer, and may also be an unsaturated polybasic acid having no polymerizability or an anhydride thereof, a saturated polybasic acid or an anhydride thereof. Specific examples of such a compound include malonic acid, succinic acid, glutaric acid, adipic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, hexahydrophthalic acid, and 5-norbornene. - a dibasic acid such as 2,3-dicarboxylic acid, methyl-5-norbornene-2,3-dicarboxylic acid or phthalic acid, a tribasic acid such as trimellitic acid, or pyromellitic acid. Tetraacid, such anhydrides, etc. Among these, it is preferred to use a dicarboxylic anhydride.

In the case where the precursor is a copolymer of an epoxy group-containing unsaturated monomer, by reacting (e) an unsaturated monobasic acid, the epoxy group in the molecule is cleaved to introduce an unsaturated bond in the side chain, and a hydroxyl group is simultaneously formed. . By using this hydroxyl group, an acid group is introduced by reacting with (f) a polybasic acid or an anhydride thereof. Further, in the case where the precursor is a copolymer of a hydroxyl group-containing unsaturated monomer, an unsaturated bond can be introduced into the side chain by reacting a hydroxyl group with (e) an unsaturated monobasic acid and (f) a polybasic acid or an anhydride thereof. At the same time, the acid group is introduced.

These modification reactions can be carried out according to a usual method, for example, two components can be added to the reaction solvent, and a polymerization inhibitor and a catalyst are further added, for example, at a temperature at which the blocked isocyanato group in the precursor does not dissociate, for example. The reaction is carried out at 50 to 150 ° C, preferably at 80 to 130 ° C. In this manner, a curable polymer (II) having a desired acid group, a polymerizable unsaturated group, and a blocked isocyanate group in a molecule and having a weight average molecular weight of 1,000 to 50,000 in terms of polystyrene can be obtained. The range of the weight average molecular weight, the acid value, and the unsaturated bond equivalent of the curable polymer (II) is the same as in the case of the curable polymer (I).

The curable polymer in the present invention is represented by the modified polymers of the above (I) and (II), but is not affected as long as it contains an acid group, a polymerizable unsaturated group, and a blocked isocyanate group. It is defined by its manufacturing method. For example, the desired curable polymer can also be obtained by the following method.

(1) Use of a monomer having a blocked isocyanato group and an epoxy group-containing After the precursor is synthesized by a saturated monomer, the polybasic acid anhydride is reacted to introduce an acid group, and then 2-(meth)acrylomethoxyethyl isocyanate or 2-(meth)acryloylethyl isocyanate is not contained. A method of reacting a saturated bond isocyanate compound with a hydroxyl group formed by cleavage of an epoxy group.

(2) using a blocked isocyanate group-containing monomer and a hydroxyl group-containing unsaturated monomer to synthesize a precursor, and reacting a hydroxyl group in the molecule with a polybasic acid anhydride and an unsaturated bond-containing isocyanate compound, respectively, and introducing an acid Base and unsaturated bond methods.

(3) After using a monomer containing a blocked isocyanate group to produce a reactive functional group (for example, a hydroxyl group or an amine group) containing an acid group and an isocyanato group, using any of the above-described instructions A method of introducing an unsaturated bond and then introducing a blocked isocyanate group into the polymer by reacting an isocyanato group and a reactive functional group in the molecule with a terminally blocked diisocyanate compound.

<Polymer composition>

In the present invention, a polymer composition containing a solvent (B) and an optional reactive diluent (C) in addition to the curable polymer (A) is provided. The solvent (B) is not particularly limited as long as it is an inert solvent which does not react with the curable polymer (A), and the same range as the solvent used in the production of the curable polymer (A) can be used. Specific examples thereof are as described above, and a (poly)alkane monoalkyl ether solvent such as propylene glycol monomethyl ether or a (poly)alkane monoalkyl group such as propylene glycol monomethyl ether acetate is preferably used. An ether acetate solvent, that is, a glycol ether solvent.

The polymer composition of the present invention may be prepared by suitably mixing the desired solvent (B) with the curable polymer (A) which is isolated from the polymerization system, but it is not necessarily required to separate the hardening polymerization from the polymerization system. As the substance (A), the solvent contained at the end of the copolymerization reaction can be used as it is, and the desired solvent can be further added as needed. Further, a solvent contained in other components used in preparing the polymer composition may be used as a component of the solvent (B).

The reactive diluent (C) is a compound having at least one polymerizable ethylenically unsaturated group as a polymerizable functional group in the molecule, and preferably has a plurality of polymerizable functional groups. Such a reactive diluent is not necessarily an essential component of the polymerizable composition, but by using the same together with the curable polymer (A), the strength of the formed cured product or the adhesion to the substrate can be improved.

The monofunctional monomer used as the reactive diluent may, for example, be (meth) acrylamide, hydroxymethyl (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxylate. Methyl (meth) acrylamide, propoxymethyl (meth) acrylamide, butoxy methoxy methyl (meth) acrylamide, methyl (meth) acrylate, (methyl Ethyl acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (methyl) ) 4-hydroxybutyl acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2-(methyl) propylene oxy-2-hydroxypropyl phthalate, glycerol mono (methyl) Acrylate, tetrahydrofurfuryl (meth)acrylate, glycidyl (meth)acrylate, 2,2,2-tri(meth)acrylate (meth) acrylates such as fluoroethyl ester, 2,2,3,3-tetrafluoropropyl (meth)acrylate, and a half (meth) acrylate of phthalic acid derivatives; styrene, α- An aromatic vinyl compound such as methyl styrene, α-chloromethyl styrene or vinyl toluene; a carboxylic acid ester such as vinyl acetate or vinyl propionate; and the like. Further, these may be used alone or in combination of two or more.

On the other hand, examples of the polyfunctional monomer include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, and propylene glycol II. (Meth)acrylate, polypropylene glycol di(meth)acrylate, butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(a) Acrylate, trimethylolpropane tri(meth)acrylate, glycerol di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol five (a) Acrylate, dipentaerythritol hexa(meth) acrylate, 2,2-bis(4-(methyl)propenyloxydiethoxyphenyl)propane, 2,2-bis(4-(A) Acryloxypolyethoxyphenyl)propane, 2-hydroxy-3-(methyl)propenyloxypropyl (meth) acrylate, ethylene glycol diepoxypropyl ether Acrylate, diethylene glycol diepoxypropyl ether di(meth)acrylate, diepoxypropyl phthalate di(meth)acrylate, glycerol triacrylate, glycerol polyglycol Polyether (meth) acrylate a reaction product of a urethane (meth) acrylate (ie, toluene diisocyanate), trimethyl hexamethylene diisocyanate, and hexamethylene diisocyanate with 2-hydroxyethyl (meth) acrylate, a (meth) acrylate such as tris(meth) acrylate of tris(hydroxyethyl)isocyanate; An aromatic vinyl compound such as alkenylbenzene, diallyl phthalate or diallyl phenylphosphonate; a dicarboxylic acid ester such as divinyl adipate; or a cyanuric acid triene cyanide a condensate of a base ester, methylene bis(meth) acrylamide, (meth) acrylamide amine methyl ether, a polyol, and N- hydroxymethyl (meth) acrylamide. Further, these may be used alone or in combination of two or more.

The amount of the curable polymer (A), the solvent (B) and the reactive diluent (C) in the polymer composition can be appropriately selected depending on the purpose of use, but usually relative to the component (A) and (C) 100 parts by mass of the total amount of the components, 10 to 100 parts by mass of the curable polymer (A), 30 to 1,000 parts by mass of the solvent (B), and 0 to 90 parts by mass of the reactive diluent (C), preferably The curable polymer (A) is 20 to 80 parts by mass, the solvent (B) is 50 to 800 parts by mass, and the reactive diluent (C) is 20 to 80 parts by mass. More preferably, the curable polymer (A) is 30 to 75 parts by mass, the solvent (B) is 100 to 700 parts by mass, and the reactive diluent (C) is 25 to 70 parts by mass. When it is blended in this range, it becomes a polymer composition having an appropriate viscosity, and can be used for preparing a photosensitive polymer composition described later, and can also be used as various coatings, adhesives, and binders for printing inks.

<Photosensitive polymer composition>

Further, in the present invention, there is provided a photosensitive polymer composition comprising a curable polymer (A), a solvent (B), a reactive diluent (C), a photopolymerization initiator (D), and any coloring. Agent (E). As The photopolymerization initiator (D) is not particularly limited, and examples thereof include benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin butyl ether; and benzene; Ethyl ketone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 4-(1-tert-butyldioxy-1-methylethyl) Acetophenone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-propan-1-one, 2-benzyl-2-dimethylamino-1- Acetophenones such as (4-morpholinylphenyl)butanone-1; 2-methylindole, 2-pentylindole, 2-tert-butylindole, 1-chloroindole, etc. Anthraquinone; xanthone, thioxanthone, 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone, etc.; a ketal such as ketone dimethyl ketal or benzyl dimethyl ketal; diphenyl ketone, 4-(1-tert-butyldioxy-1-methylethyl)diphenyl ketone And diphenyl ketones such as 3,3', 4,4'-fluorene (t-butyldioxycarbonyl)diphenyl ketone; fluorenylphosphine oxides. These may be used alone or in combination of two or more.

The amount of the photopolymerization initiator (D) in the photosensitive polymer composition is generally 0.1 to 30 by mass based on 100 parts by mass of the total of the component (A) and the component (C) in the photosensitive polymer composition. The portion is preferably 0.5 to 20 parts by mass, more preferably 1 to 15 parts by mass. When it is blended in this range, it becomes a photosensitive polymer composition which has suitable photocurability.

The coloring agent (E) is not particularly limited as long as it is soluble or dispersible in the solvent (B), and examples thereof include a dye and a pigment. As the dye, it is preferred to use a carboxylic acid or the like from the viewpoint of solubility in a solvent (B) or an alkali developing solution, interaction with other components in the photosensitive polymer composition, heat resistance and the like. Acidic acid dyes such as sulfonic acid, A salt of an acid dye and a nitrogen compound, a sulfonamide of an acid dye, or the like.

As an example of such a dye, acid alizarin violet N; acid black 1, 2, 24, 48; acid blue 1, 7, 9, 25, 29, 40, 45, 62, 70, 74, 80, 83 , 90, 92, 112, 113, 120, 129, 147; acid chrome violet K; acid Fuchsin; acid green 1, 3, 5, 25, 27, 50; acid orange 6, 7, 8, 10, 12, 50 , 51, 52, 56, 63, 74, 95; acid red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52 , 57, 69, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 183, 198 , 211, 215, 216, 217, 249, 252, 257, 260, 266, 274; acid violet 6B, 7, 9, 17, 19; acid yellow 1, 3, 9, 11, 17, 23, 25, 29 , 34, 36, 42, 54, 72, 73, 76, 79, 98, 99, 111, 112, 114, 116; food yellow 3 and derivatives thereof. Among these, an acid dye of an azo type, a xanthene type, an anthraquinone type or a phthalocyanine type is preferable. These may be used singly or in combination of two or more kinds depending on the color of the pixel of interest.

As examples of the pigment, CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125 Yellow pigments of 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214, etc.; CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, Orange pigments of 55, 59, 61, 64, 65, 71, 73; CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, Red pigments of 192, 209, 215, 216, 224, 242, 254, 255, 264, 265, etc.; blue pigments of CI Pigment Blue 15, 15:3, 15:4, 15:6, 60, etc.; CI pigment Purple pigments of purple 1, 19, 23, 29, 32, 36, 38; green pigments of CI pigment green 7, 36, 58; tin pigments of CI pigment brown 23, 25; CI pigment black 1, 7, Black pigment such as carbon black, titanium black, or iron oxide.

These may be used singly or in combination of two or more kinds depending on the color of the pixel of interest. Furthermore, the above dyes and pigments may be used in combination according to the color of the target. The amount of the colorant (E) is usually 5 to 80 parts by mass, preferably 5 to 70 parts by mass, based on 100 parts by mass of the total of the component (A) and the component (C) in the photosensitive polymer composition. More preferably, it is 10 to 60 parts by mass.

When a pigment is used as the coloring agent (E), a well-known dispersing agent may be blended in the photosensitive polymer composition from the viewpoint of improving the dispersibility of the pigment. As the dispersing agent, a polymer dispersing agent excellent in dispersion stability over time is preferably used. Examples of the polymer dispersant include a urethane dispersant, a polyethylenimine dispersant, a polyoxyethylene alkyl ether dispersant, and a polyoxyethylene glycol diester dispersant. A sorbitan fatty ester dispersant, an aliphatic modified ester dispersant, or the like. As such a polymer dispersing agent, EFKA (EFKA CHEMICALS BV (EFKA)), Disperbyk (manufactured by BYK Chemical Co., Ltd.), Disparlon (manufactured by Nanben Chemical Co., Ltd.), SOLSPERS (manufactured by Zeneca Co., Ltd.), or the like can be used. The product name is marketed. The blending amount of the dispersing agent can be appropriately set depending on the type of the pigment or the like to be used.

When the photosensitive polymer composition contains the colorant (E), the curable polymer (A), the solvent (B), the reactive diluent (C), the photopolymerization initiator (D), and the colorant (E) The compounding amount is generally 100 parts by mass based on the total amount of the component (A) and the component (C) in the photosensitive polymer composition, and the curable polymer (A) is 10 to 90 parts by mass, and the solvent (B) is 30 to 1,000 parts by mass, the reactive diluent (C) is 10 to 90 parts by mass, the photopolymerization initiator (D) is 0.1 to 30 parts by mass, and the colorant (E) is 5 to 80 parts by mass, preferably hardened. The polymer (A) is 20 to 80 parts by mass, the solvent (B) is 50 to 800 parts by mass, the reactive diluent (C) is 20 to 80 parts by mass, and the photopolymerization initiator (D) is 0.5 to 20 parts by mass. The coloring agent (E) is 5 to 70 parts by mass, more preferably the curing polymer (A) is 30 to 75 parts by mass, the solvent (B) is 100 to 700 parts by mass, and the reactive diluent (C) is 25 to 70 parts by mass, the photopolymerization initiator (D) is 1 to 15 parts by mass, and the colorant (E) is 10 to 60 parts by mass. Further, when the photosensitive polymer composition does not contain the colorant (E), the amount of the curable polymer (A), the solvent (B), the reactive diluent (C), and the photopolymerization initiator (D) is also The above numerical range can be employed.

The polymer composition and the photosensitive polymer composition of the present invention may be blended with a well-known additive such as a well-known coupling agent, a leveling agent, or a thermal polymerization inhibitor in addition to the above components in order to impart specified characteristics. The compounding amount of such additives is not particularly limited as long as it does not impair the effects of the present invention.

The photosensitive polymer composition of the present invention can be produced by mixing the above components using a well-known mixing device. Also, as desired, can also be the first After preparing the polymer composition containing the curable polymer (A) and the solvent (B), the reactive diluent (C), the photopolymerization initiator (D), and the coloring agent (E) of any component are mixed. Manufacturing.

The photosensitive polymer composition obtained as described above is suitable as a resist because it has alkali developability. When the photosensitive polymer composition is cured, the baking temperature can be appropriately selected in the range of 250 ° C or less. However, since the curable polymer of the present invention is excellent in curability at low temperatures, compared with conventional materials, Can reduce the baking temperature. For example, when the photosensitive polymer composition is used in the pigment/dye dispersion method, the baking temperature can be lowered to 210 ° C or lower. The lower the baking temperature, the more advantageous it is in terms of energy consumption, and in the case of the dye dispersion method, the original characteristics of the dye are easily obtained. From such a viewpoint, the baking temperature is preferably 210 ° C or lower, preferably 200 ° C or lower, more preferably 190 ° C or lower. The lower limit of the baking temperature is not necessarily the same depending on the type of blocked isocyanato group contained in the curable polymer, but it must be at least the dissociation temperature of the blocked isocyanate group, and is usually 100 ° C or more. Preferably, it is 150 ° C or more, more preferably 160 ° C or more. If the baking temperature is excessively low, it is difficult to sufficiently improve the solvent resistance of the coating film. Further, the time required for baking can be suitably selected, and it is usually from 10 minutes to 4 hours, preferably from 20 minutes to 2 hours.

The photosensitive polymer composition of the present invention is suitable as a resist, and is particularly preferably used as a resist for use in a color filter such as an organic EL display, a liquid crystal display device, a solid-state image sensor such as a CCD or a CMOS. In addition, the photosensitive polymer composition of the present invention can be used for various coatings by imparting a cured film excellent in solvent resistance and curing properties at low temperatures. Coating, adhesive, adhesive for printing ink, etc.

<color filter>

Next, a color filter prepared by using the photosensitive polymer composition of the present invention will be described. The color filter of the present invention has a color pattern formed using the above-described photosensitive polymer composition. The color filter is generally composed of a substrate, RGB pixels formed thereon, a black matrix and a pixel formed at boundaries of respective pixels, and a protective film formed on the black matrix. In this configuration, the pixels and the black matrix (colored pattern) are formed using the above-described photosensitive polymer composition, and other configurations are known.

Next, an embodiment of a method of manufacturing a color filter will be described. First, a color pattern is formed on the substrate. Specifically, a black matrix and RGB pixels are sequentially formed on the substrate. The material of the substrate is not particularly limited, and a glass substrate, a ruthenium substrate, a polycarbonate substrate, a polyester substrate, a polyamide substrate, a polyimide substrate, a polyimide substrate, an aluminum substrate, or the like can be suitably used. Printed wiring board, array board, etc.

The coloring pattern can be formed by lithography. Specifically, after the photosensitive polymer composition is applied onto a substrate to form a coating film, the coating film is exposed by a mask of a predetermined pattern, and the exposed portion is photocured. Then, after the unexposed portion is developed with an aqueous alkali solution, a specified pattern can be formed by baking.

The coating method of the photosensitive polymer composition is not particularly limited, and a screen printing method, a roll coating method, a curtain coating method, and a spray coating method can be used. Method, spin coating method, etc. Further, after the application of the photosensitive polymer composition, if necessary, heating may be performed by a heating means such as a circulating oven, an infrared heater or a hot plate to volatilize the solvent (B). The heating conditions are not particularly limited, and can be appropriately set depending on the type of the photosensitive polymer composition to be used. Generally, it can be heated at a temperature of 50 ° C to 120 ° C for 30 seconds to 30 minutes.

Next, the formed coating film is partially exposed by irradiating an active energy ray such as ultraviolet rays or excimer laser light through a negative mask. The amount of the energy ray to be irradiated can be appropriately selected in accordance with the composition of the photosensitive polymer composition, and is, for example, preferably 30 to 2000 mJ/cm ² . The light source for exposure is not particularly limited, and a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, a metal halide lamp, or the like can be used.

The aqueous alkali solution for development is not particularly limited, and an aqueous solution of sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide or potassium hydroxide; ethylamine, diethylamine, dimethylethanolamine or the like can be used. An aqueous solution of an amine compound; tetramethylammonium, 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyl Ethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamide ethylaniline, 3-methyl-4-amino-N-ethyl-N-β- An aqueous solution of methoxyethyl aniline and a p-phenylenediamine compound such as a sulfate, a hydrochloride or a p-toluenesulfonate. Further, in such an aqueous solution, an antifoaming agent or a surfactant may be added as needed. Further, it is preferably washed with water and dried after development by the aqueous alkali solution.

The baking conditions are not particularly limited, and the heat treatment can be carried out in accordance with the type of the photosensitive polymer composition to be used. Previously known sensitometry When the baking temperature is 200 ° C or less, the solvent resistance becomes insufficient. However, the photosensitive polymer composition of the present invention can exhibit sufficient resistance even when baked at a temperature of 200 ° C or lower. Solvent coating film (see Example 6 and Example 8). Therefore, the baking temperature can be lowered, and the processing time can be shortened when baking at a high temperature, which is a great advantage in manufacturing. From such a viewpoint, heating is usually carried out at a temperature of 210 ° C or lower, preferably 200 ° C or lower, and particularly preferably at a temperature of 190 ° C or lower for 10 minutes to 4 hours, preferably 20 minutes to 2 hours.

By using a photosensitive polymer composition for a black matrix and a photosensitive polymer composition for red, green, and blue pixels, the coating, exposure, development, and baking as described above are repeated in this order to form The desired color pattern. Further, in the above, a method of forming a color pattern by photohardening is described, but instead of a photopolymerization initiator (D), a photosensitive polymerization in which a curing accelerator and a well-known epoxy resin are blended may be used. The composition of the object is coated by an inkjet method and heated to form a desired color pattern. Next, a protective film is formed on the coloring pattern (each pixel of RGB and the black matrix). The protective film is not particularly limited, and those skilled in the art can be used.

The color filter produced in this manner is excellent in sensitivity and developability, and is produced by applying a photosensitive polymer composition of a color pattern having excellent solvent resistance. Therefore, it has an excellent coloring pattern with little color change.

<Video display component>

The image display element of the present invention has the display element of the above color filter As a specific example, a solid-state imaging element such as a liquid crystal display element, an organic EL display element, a CCD element, or a CMOS element can be given. When the image display element is manufactured, it can be carried out in accordance with a usual method in addition to the above-described color filter. For example, when manufacturing a liquid crystal display element, the color filter is formed on a substrate, and an electrode, a spacer, or the like is formed in order. Then, an electrode or the like can be formed on the other substrate, and both of them can be bonded together, and a predetermined amount of liquid crystal can be injected and sealed.

[Examples]

Hereinafter, the present invention will be described in detail with reference to the embodiments, but the present invention is not limited by these examples. Moreover, in this embodiment, the parts and percentages are based on mass unless otherwise specified. Further, the measurement methods of the acid value, the unsaturated group equivalent weight and the weight average molecular weight are as follows.

(1) Acid value: The acid value of the curable polymer (A) measured in accordance with JIS K6901 5.3, which means the amount of potassium hydroxide required to neutralize the acidic component contained in 1 g of the curable polymer (A). number.

(2) Unsaturated Group Equivalent The molecular weight per mole of the polymerizable unsaturated bond is calculated based on the amount of the monomer used.

(3) The molecular weight per mole of the blocked isocyanate group-terminated isocyanate group, and the calculated value based on the amount of the monomer used.

(4) The so-called weight average molecular weight (Mw) means a standard polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC) under the following conditions.

Pipe column: Shodex (registered trademark) LF-804+LF-804 (Showa Electric Co., Ltd.)

Column temperature: 40 ° C

Sample: 0.2% tetrahydrofuran solution of copolymer

Developing solvent: tetrahydrofuran

Detector: Differential Refractometer (Shodex RI-71S) (made by Showa Denko Co., Ltd.)

Flow rate: 1mL/min

Example 1

To a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, 162.2 g of propylene glycol monomethyl ether acetate was added, and the mixture was stirred while being replaced with nitrogen, and the temperature was raised to 120 °C.

Next, 4.7 g (0.05 mol) of norbornene, 53.0 g (0.45 mTorr) of vinyl toluene, 32.4 g (0.45 mTorr) of acrylic acid, and methacryloxyloxy group B represented by the above formula (3) 10.3 g of tert-butylperoxy-2-ethylhexanoic acid was added to the monomer mixture of the reaction product of the isocyanate and propylene glycol monomethyl ether (dissociation temperature 160 ° C) 12.25 g (0.05 mol) The ester (polymerization initiator, manufactured by Nippon Oil Co., Ltd., Perbutyl O) was dropped from the dropping funnel over 2 hours into the flask. After completion of the dropwise addition, the mixture was further stirred at 120 ° C for 2 hours to carry out a copolymerization reaction to form an addition copolymer (curable polymer precursor). Then, the inside of the flask was replaced with air, and 22.5 g (0.16 mol) of glycidyl methacrylate, 0.4 g of triphenylphosphine (catalyst), and 0.4 g of methylhydroquinone were placed in the above-mentioned addition copolymer solution. , continue at 110 ° C for 10 hours In the reaction, a polymerizable unsaturated bond is introduced into the side chain of the polymer by a reaction between a carboxyl group derived from acrylic acid and an epoxy group of glycidyl methacrylate to obtain a curable polymer (A). The polymer had an acid value of 131.5 mgKOH/g, an unsaturated group equivalent of 851 g/mol, a blocked isocyanate equivalent of 2,700 g/mol, and a weight average molecular weight of 10,500.

Next, 82.0 g of propylene glycol monomethyl ether was added to the reaction solution to prepare a polymer solution having a polymer component concentration of 34% of the curable polymer (A). This was taken as sample 1.

Example 2

In a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, 232.8 g of propylene glycol monomethyl ether acetate was added, and the mixture was stirred while being replaced with nitrogen, and the temperature was raised to 120 °C. Next, it is composed of 6.09 g (0.06 mol) of norbornene, 68.33 g (0.58 mol) of vinyl toluene, 82.0 g (0.58 mol) of glycidyl methacrylate, and the formula (3). A monomer mixture composed of a reaction product of a propylene oxyethyl isocyanate and a propylene glycol monomethyl ether (dissociation temperature: 160 ° C) of 15.88 g (0.06 mol) was added with 13.3 g of a third butyl peroxy group. 2-ethylhexanoate (polymerization initiator, manufactured by Nippon Oil Co., Ltd., Perbutyl O), and the resultant was dropped from the dropping funnel over 2 hours into the flask. After completion of the dropwise addition, the mixture was further stirred at 120 ° C for 2 hours to carry out a copolymerization reaction to form an addition copolymer. Then, the inside of the flask was replaced with air, and 42.0 g (0.58 mol) of acrylic acid, 0.5 g of triphenylphosphine (catalyst), and 0.5 g of methylhydroquinone were placed in the above-mentioned addition copolymer solution, and subjected to 10 at 110 ° C. Hour continues The reaction introduces a polymerizable unsaturated bond into the side chain of the polymer by the reaction of an epoxy group derived from glycidyl methacrylate with a carboxyl group of acrylic acid, and further adds 48.0 g of tetrahydrophthalic anhydride (0.29 mol). The reaction was continued at 110 ° C for 3 hours to react a hydroxyl group formed by the cleavage of the epoxy group with an anhydride group of tetrahydrophthalic anhydride. The polymerizable polymer (B) thus obtained had an acid value of 92.5 mgKOH/g, an unsaturated group equivalent of 392 g/mol, a blocked isocyanate equivalent of 4,100 g/mol, and a weight average molecular weight of 12,000.

Next, 106.53 g of propylene glycol monomethyl ether was added to the reaction solution to prepare a polymer solution having a polymer concentration of 44.5% of the polymerizable polymer (B). This was taken as sample 2.

Example 3

In place of the reaction product of methacryloxyethyl isocyanate and propylene glycol monomethyl ether represented by the above formula (3), 12.25 g (0.05 mol), 2-isocyanide represented by the above formula (2) is used. A polymerizable polymer (C) was obtained in the same manner as in Example 1 except that the reaction product of the acid group ethyl methacrylate and ε-caprolactam was obtained at a dissociation temperature of 160 ° C., 13.4 g (0.05 mol). The polymer had an acid value of 130.2 mgKOH/g, an unsaturated group equivalent of 859 g/mol, a blocked isocyanate equivalent of 2,700 g/mol, and a weight average molecular weight of 15,900.

Next, 106.53 g of propylene glycol monomethyl ether was added to the reaction solution to prepare a polymer solution having a polymer component concentration of 34% of the polymerizable polymer (C). This was taken as sample 3.

Example 4

In place of the reaction product of methacryloxyethyl isocyanate and propylene glycol monomethyl ether represented by the above formula (3), 15.88 g (0.06 mol), 2-isocyanide represented by the above formula (2) is used. A polymerizable polymer (D) was obtained in the same manner as in Example 2 except that the reaction product of the acid group ethyl methacrylate and ε-caprolide was 17.37 g (0.06 mol). The polymer had an acid value of 92.5 mgKOH/g, an unsaturated group equivalent of 392 g/mol, a blocked isocyanate equivalent of 4,100 g/mol, and a weight average molecular weight of 18,000.

Next, 106.53 g of propylene glycol monomethyl ether was added to the reaction solution to prepare a polymer solution having a polymer concentration of 44.5% of the polymerizable polymer (D). This was taken as sample 4.

Comparative example 1

Except that the reaction product of methacryloxyethyl isocyanate and propylene glycol monomethyl ether represented by the above formula (3) was not used, 15.88 g (0.06 mol), and the amount of vinyl toluene used was 76.48 g ( A polymerizable polymer (E) was obtained in the same manner as in Example 2 except for 0.65 mol. The polymer had an acid value of 138.5 mgKOH/g, an unsaturated group equivalent of 800 g/mol, and a weight average molecular weight of 9,000.

Next, 103.3 g of propylene glycol monomethyl ether was added to the reaction solution to prepare a polymer solution having a polymer concentration of 35% of the polymerizable polymer (E). This was taken as sample 5.

Comparative example 2

In addition to the use of the reaction product of the reaction of 2-isocyanatoethyl methacrylate and ε-caprolactam represented by the above formula (2), 13.4 g (0.05 mol), and the amount of vinyl toluene used. A polymerizable polymer (F) was obtained in the same manner as in Example 3 except that it was 59.0 g (0.5 mol). The polymer had a polymer acid value of 142.2 mgKOH/g, an unsaturated group equivalent of 800 g/mol, and a weight average molecular weight of 10,000.

Next, 106.53 g of propylene glycol monomethyl ether was added to the reaction solution to prepare a polymer solution having a polymer concentration of 44.5% of the polymerizable polymer (F). This was taken as sample 6.

Example 5 and Comparative Example 3 <Preparation of photosensitive polymer composition (pigment type)>

In a stainless steel container filled with 180 parts of zirconia beads having a diameter of 0.5 mm, 3610 parts of CI pigment green, 33.75 parts of propylene glycol monomethyl ether acetate, and a dispersing agent (Disperbyk-161 manufactured by BYK Chemical Co., Ltd.) were charged. 6.25 parts were prepared by mixing with a paint shaker for 3 hours to prepare a green pigment dispersion.

Using this green pigment dispersion, it was mixed with other compounding ingredients shown in Table 1 (i.e., a curable polymer, a reactive diluent, a photopolymerization initiator, and a solvent) to prepare a photosensitive polymer composition shown in Table 2. (Composition No. 1 to 6). The mixing ratio of the respective components is shown in Table 1. Furthermore, the amount of the hardenable polymer in Table 1 does not contain a solvent for polymerization. The amount of the solvent prepared by the solution is added to the solvent as a compounding component.

Example 6 and Comparative Example 4 <Evaluation of color resist (pigment type)>

The performance when the photosensitive polymer composition obtained in Example 5 was used as a color resist (pigment type) was evaluated as follows.

(1) Formation by pattern of color resist

The prepared color resist (pigment type) was spin-coated on a 5 cm square glass substrate (alkali-free glass substrate) to have a thickness of 2.5 μm after exposure, and then the solvent was volatilized by heating at 90 ° C for 3 minutes. Next, a mask of a predetermined pattern was placed at a distance of 100 μm from the coating film, and the coating film was exposed (the exposure amount was 150 mJ/cm ² ) through the mask, and the exposed portion was photocured. Next, an aqueous solution containing 0.1% by mass of sodium carbonate was sprayed at a temperature of 23 ° C at a pressure of 0.3 MPa, and the unexposed portion was dissolved and developed, and then baked at 230 ° C for 30 minutes to form a designation. The pattern.

(2) Evaluation of patterns formed by color resists

With respect to the pattern formed as described above, alkali developability and sensitivity were evaluated as follows.

(2-1) Alkali imaging

The alkali imaging property was confirmed by the residue and development morphology after alkali development. The residue after alkali development was confirmed by observing the pattern after alkali development using a Hitachi high-tech electron microscope S-3400. The evaluation criteria are as follows.

○: no residue

×: There is residue

(2-2) Sensitivity

The above-described alkali development using a spray was carried out for 30 seconds, and the amount of reduction in the thickness of the pattern before and after the alkali development was measured to determine whether the sensitivity was good or not. Since the thickness reduction of this pattern is less, it can be said that the better the sensitivity, so the evaluation criteria are as follows.

○: less than 0.20 μm

×: 0.20 μm or more

(3) Evaluation of solvent resistance

On a 5 cm square glass substrate (alkali-free glass substrate), a polymer composition of the type after removing the pigment from the above color resist was spin-coated, and the thickness after exposure was 2.5 μm, followed by heating at 90 ° C. The solvent was volatilized for 3 minutes. Second. The coating film was exposed to light having a wavelength of 365 nm, and the exposed portion was subjected to spectral hardening, and placed in a drier having a baking temperature of 180 ° C, 200 ° C, and 230 ° C for 1 hour to form a cured coating film. 200 mL of n-methyl-2-pyrrolidone was placed in a 500 mL-capped glass vial, and the test piece with the hardened coating film was immersed therein, and then a spectrophotometer UV-1650PC (manufactured by Shimadzu Corporation) was used. The color change after one hour of passing at 23 ° C was measured, and the solvent resistance was evaluated based on the results. The basis for this evaluation is as follows.

○: △E* ab is less than 0.3

×: ΔE* ab is 0.3 or more

Table 2 shows the results of evaluation of the above-mentioned alkali developability, sensitivity, and solvent resistance.

As can be seen from the results of Table 2, the color resists (experiment numbers 5-1 to 5-4) of the photosensitive polymer compositions of Examples 1 to 4 were used, and the alkali developability and sensitivity were good, and solvent resistance was given. Excellent pattern, with respect to the color resist of the photosensitive polymer composition of Comparative Examples 1 to 2 (experiment number 5-5 to 5-6), alkali imaging or poor sensitivity, baking temperature When the temperature is as low as 180 ° C and 200 ° C, the solvent resistance is insufficient.

Example 7 and Comparative Example 5 <Preparation of photosensitive polymer composition (dye type)>

According to the compounding component and the mixing ratio shown in Table 3, a photosensitive polymer composition (dye type) containing a dye (acid green 3) was prepared. again The amount of the curable polymer in Table 3 does not include a solvent, and the amount of the solvent used for the preparation of the polymer solution is added to the solvent as a compounding component.

Example 8 and Comparative Example 6 <Evaluation of color resist (dye type)>

The performance when the photosensitive polymer composition obtained in Example 7 was used as a color resist (dye type) was evaluated by the same method as in Example 8. The results are shown in Table 4.

As is clear from the results of Table 4, the color resists (experiment numbers 7-1 to 7-4) using the photosensitive polymer compositions of Examples 1 to 4 were excellent in alkali developability and sensitivity, and solvent resistance. Excellent, with respect to the color resist of the photosensitive polymer composition of Comparative Examples 1 and 2 (experiment number 7-5 to 7-6), the alkali developability or sensitivity is poor, and the baking temperature is as 180. When the temperature is low at °C and 200 °C, the solvent resistance is also poor.

Comparative Example 7

A polymerizable polymer (G) was obtained in the same manner as in Example 1 except that the modification reaction without glycidyl methacrylate was carried out. The polymer had an acid value of 324.0 mg KOH/g, a blocked isocyanate equivalent of 2,300 g/mol, and a weight average molecular weight of 9,000. Second, dissolve in the reaction 52.2 g of propylene glycol monomethyl ether was added to the solution to prepare a polymer solution having a polymer component concentration of 35.0% of the polymerizable polymer (G). The photosensitive polymer composition (dye type) was prepared in the same manner as in Example 7 except that the polymer solution was used, and the performance as a color resist was evaluated. As a result, the sensitivity and the solvent resistance were insufficient as compared with the examples of the present invention. .

[Industry use possibility]

As apparent from the above results, according to the present invention, it is possible to provide a curable polymer which is excellent in sensitivity or developability when used as a photosensitive material, and at the same time, even if the baking temperature at the time of pattern formation is lowered, A hard coat film having sufficient solvent resistance is formed. In addition, by using the curable polymer, it is excellent in sensitivity, developability, and solvent resistance, and is suitable as a photosensitive polymer composition for a color filter resist. Further, by using the photosensitive polymer composition, a color filter excellent in solvent resistance and high in reliability can be obtained.

Claims (18)

A curable polymer characterized by containing an acid group, a polymerizable unsaturated group, and a blocked isocyanate group in a molecule, and having a weight average molecular weight of 1,000 to 50,000 in terms of polystyrene; Any one of: (I) for copolymerizing (a) a blocked isocyanato group-containing monomer, (b) an unsaturated acid monomer, and (d) another monomer as desired; a copolymer formed by reacting (c) with an unsaturated monomer having an acid group and a reactive functional group, and a modified polymer having a polymerizable unsaturated bond introduced into the side chain; (II) for making (a) a blocked isocyanate group monomer, (c) an unsaturated monomer having an acid group and a reactive functional group, and a copolymer copolymerized with (d) another monomer as desired, and (e) A modified polymer in which a unsaturated monobasic acid and (f) a polybasic acid or an anhydride thereof are reacted to introduce a polymerizable unsaturated bond and an acid group in a side chain. The curable polymer of claim 1, which has an acid value of 20 to 300 KOHmg/g, an unsaturated group equivalent of 100 to 4,000 g/mol, and a blocked isocyanate group equivalent of 400 to 6,000 g/mol. The hardenable polymer according to claim 1 or 2, wherein the hardenable polymer is a polymerization unit having a terminal isocyanato group-containing monomer having an ethylenically unsaturated bond in the main chain, and has a side chain Polymerizable unsaturated group. A sclerosing polymer according to claim 1 or 2, wherein the acid group is a carboxyl group or an acid anhydride group. The hardenable polymer of claim 1 or 2, wherein the blocked isocyanate group has a dissociation temperature of from 100 to 200 °C. The sclerosing polymer of claim 1, wherein the single system containing a blocked isocyanate group is a terminal body formed of an isocyanato group-containing (meth) acrylate and a blocking agent. The sclerosing polymer of claim 6, wherein the blocking agent is an internal amide compound or an alcohol compound. The hardenable polymer of claim 1, wherein (d) the other single system is at least one selected from the group consisting of an aromatic vinyl compound and a cyclic olefin. A polymer composition containing the curable polymer (A) and the solvent (B) according to any one of claims 1 to 8. The polymer composition of claim 9, which further comprises a reactive diluent (C). The polymer composition of claim 10, which further contains a photopolymerization initiator (D) and is photosensitive. The polymer composition of claim 11, which further contains a colorant (E). The polymer composition of claim 12, wherein the colorant (E) is a dye. A photosensitive material for a color filter, which is composed of the polymer composition according to any one of claims 9 to 13. A color filter formed using a photosensitive material such as the color filter of claim 14. A method of manufacturing a color filter, which is characterized by The color filter is coated on the substrate with a photosensitive material, exposed by a mask, and formed into a pattern by alkali development, and then baked at a temperature of 210 ° C or lower. A method of producing a color filter according to claim 16, wherein the coloring agent (E) is a dye. An image display element having a color filter as in claim 15.