JP6157193B2 - (Meth) acrylate polymer, composition containing the polymer and use thereof - Google Patents

Description

  The present invention relates to a novel curable (meth) acrylate-based polymer having an acid group and a polymerizable unsaturated bond in the side chain, a method for producing the polymer, and uses of the polymer, and more specifically, a photosensitive material for a color filter. Curable (meth) acrylate polymer suitable as a method, a method for producing the curable (meth) acrylate polymer, a polymer composition containing the curable (meth) acrylate polymer, and photopolymerization initiating the polymer composition The present invention relates to a photosensitive polymer composition containing an agent, a color filter formed from the photosensitive polymer composition, and an image display element comprising the color filter.

  In recent years, photosensitive polymer compositions curable with active energy rays such as ultraviolet rays and electron beams have been widely used in the fields of various coatings, printing, paints, adhesives and the like from the viewpoint of resource saving and energy saving. In the field of electronic materials such as printed wiring boards, photosensitive polymer compositions that can be cured by active energy rays are used for solder resists, color filter resists, and the like.

  The color filter generally includes a transparent substrate such as a glass substrate, red (R), green (G) and blue (B) pixels formed on the transparent substrate, a black matrix formed at the pixel boundary, It is comprised from the protective film formed on a pixel and a black matrix. A 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 for forming a pixel and a black matrix (hereinafter, the pixel and the black matrix are referred to as “colored pattern”), various manufacturing methods have been proposed. Among them, a pigment / dye dispersion method created by a photolithography method using a photosensitive polymer composition as a resist and repeating coating, exposure, development and baking is excellent in durability such as light resistance and heat resistance, Since it gives a colored pattern with few defects such as pinholes, it is the current mainstream.

  Generally, the photosensitive polymer composition used in the photolithography method contains an alkali-soluble resin, a reactive diluent, a photopolymerization initiator, a colorant, and a solvent. Various types of polymers have been conventionally developed as alkali-soluble resins. Recently, photosensitive polymer compositions using polymers having a low glass transition temperature (Tg) have been developed. For example, Patent Document 1 includes a monomer unit derived from an N-substituted maleimide compound, has a carboxyl group and an ethylenically unsaturated double bond, and has a Tg of 20 ° C. or lower, preferably −50 ° C. or higher. A photosensitive material for a color filter using a polymer of the above is disclosed (see claim 1 and paragraph 0038). The polymer can be synthesized by reacting a copolymer of N-substituted maleimide and unsaturated carboxylic acid with an ethylenically unsaturated compound having a functional group reactive with a carboxy group such as an epoxy group ( (See paragraph 0011).

  In Patent Document 1, when such a low Tg polymer is used, the alkali-soluble resin has sufficient flexibility, and adhesion with the base material is improved, so that peeling or chipping during alkali development is prevented. It can be prevented (see paragraph 0038). However, since this curable polymer contains maleimide polymer units, there is a problem of yellowish discoloration (yellowing) caused by nitrogen atoms contained in the molecule.

  Patent Document 2 includes a monomer having a Tg of 20 ° C. or lower when it is a homopolymer in a proportion of 30% by mass or more, preferably 50% by mass or more based on the total monomers, and has a double bond equivalent. A color filter photosensitive material using 550 or more polymers is disclosed. This polymer has a large double bond equivalent, so that the crosslink density of the thin film decreases, the hardness and elastic modulus of the thin film decrease, and since the Tg is low, the polymer main chain skeleton becomes flexible, It is described that the internal stress at the time of filter firing can be reduced, and as a result, the phase difference of the obtained color filter is reduced (see paragraph 0030).

  In Patent Document 2, it is recommended to use a (meth) acrylate having an alkyl group having 4 to 20 carbon atoms as a monomer for lowering the Tg of the polymer. Specific examples of the polymer using such a monomer As a modified product obtained by adding glycidyl methacrylate to an addition copolymer of dodecyl methacrylate / n-butyl methacrylate / methacrylic acid, glycidyl methacrylate was added to an addition copolymer of 2-ethylhexyl methacrylate / n-butyl methacrylate / methacrylic acid. Modified products, modified products obtained by adding glycidyl methacrylate to an addition copolymer of tricyclodecanyl methacrylate / n-butyl methacrylate / methacrylic acid (binder resin H, see paragraph 0117) and the like are described. However, Patent Document 2 describes that inclusion of a hydroxy group in a polymer increases the phase difference when a color filter is formed, which is undesirable (see paragraph 0025), and it is hoped that the number of hydroxy groups will be as small as possible. It was rare.

  Patent Document 3 is typified by alicyclic monomers such as tricyclodecanyl methacrylate and norbornene and ethoxylated o-phenylphenol (meth) acrylate (that is, 2-phenylphenoxyethyl (meth) acrylate). A photosensitive material for a color filter using a modified polymer in which an acid group and a polymerizable unsaturated bond are introduced into a copolymer of an alkylene oxide-derived structure and an aryl residue-containing (meth) acrylate is disclosed. In Patent Document 3, as a method for introducing an acid group and a polymerizable unsaturated bond, (1) an unsaturated monobasic acid is copolymerized in advance and an unsaturated group having an epoxy group and a part of the acid group in the molecule. (2) An unsaturated monomer having an epoxy group is copolymerized in advance, the epoxy group in the molecule is cleaved with an unsaturated monobasic acid, and a polybasic acid anhydride is added to the produced hydroxy group. The method of making it react is illustrated. It is described that any method can obtain equivalent performance (see Example 3 and other examples). However, this material exhibits excellent characteristics in terms of sensitivity, developability, heat decomposability, and heat yellowing, but it cannot be said that the adhesion to the substrate or the flexibility of the coating film is sufficient, and coloring When a dye is used as a material, a phenomenon that the original clearness of the dye is often insufficient may be caused.

JP 2012-32772 A JP 2012-203361 A WO2012 / 141000 Publication

  The present invention was developed under the background art as described above, and its main purpose is sensitivity, developability, solvent resistance, substrate when used as a material for a photosensitive polymer composition. Another object of the present invention is to provide a curable polymer excellent in adhesion to the dye and dispersibility of the dye and a method for producing the same. Another object is to provide a polymer composition capable of forming a coating film excellent in sensitivity, developability, solvent resistance, adhesion to a substrate, and dye dispersibility. Furthermore, another object is to provide a photosensitive polymer composition suitable as a material for a color filter, which can form a pattern excellent in solvent resistance, adhesion to a substrate, and dispersibility of a dye. Is to provide a stable color filter, and to provide an image display device including the color filter.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have used and obtained two specific types of monomers as monomer components constituting the main chain of the curable polymer. When an acid group, a hydroxy group and an unsaturated double bond coexist in the side chain of the addition copolymer, a curable polymer excellent in sensitivity, developability, solvent resistance, adhesion to the substrate and dispersibility of the dye is obtained. The inventors have found that it can be obtained efficiently and have completed the present invention.

Thus, according to the present invention, the first invention has a (meth) acrylate monomer (a) of 5 to 40 mol%, an epoxy group or a carboxy group, which has a glass transition temperature of 10 ° C. or less when a homopolymer is formed. By subjecting the addition copolymer of (meth) acrylic monomer (b) 30 to 85 mol% and other radical polymerizable monomer (c) 0 to 35 mol% to the following modification reaction (I) or (II) Curability having an acid group, a hydroxy group and a polymerizable unsaturated bond in the obtained side chain, a glass transition temperature of 20 ° C. or less, and a polystyrene equivalent weight average molecular weight of 1,000 to 50,000. A polymer is provided.
Modification method of (I):
A method in which an epoxy group contained in a molecule of an addition copolymer is cleaved with a polymerizable unsaturated monobasic acid (d), and a hydroxy group generated by the cleavage is reacted with a polybasic acid or an anhydride thereof (e) .
Modification method of (II):
A method of reacting a carboxy group contained in a molecule of an addition copolymer with a (meth) acrylate monomer (f) having a functional group reactive with the carboxy group.

  As a second invention, (meth) acrylic monomer having 5 to 40 mol% of (meth) acrylate monomer (a) having a glass transition temperature of 10 ° C. or less when a homopolymer is formed, and (meth) acryl having epoxy group or carboxy group Monomer (b) 30-85 mol% and other radically polymerizable monomers (c) 0-35 mol% used as desired are radically polymerized, and then the resulting addition copolymer is subjected to the above (I) or (II ), A side chain has an acid group, a hydroxy group and a polymerizable unsaturated bond, has a glass transition temperature of 20 ° C. or less, and has a polystyrene equivalent weight average molecular weight of 1,000 to 1,000. A method of producing a curable polymer that is 50,000 is provided.

  Furthermore, as a third invention, a polymer composition containing the curable polymer (A), the solvent (B) and / or a reactive diluent (C) is provided, and further as the fourth invention, There is provided a photosensitive polymer composition containing a reactive polymer (A), a solvent (B), a reactive diluent (C), a photopolymerization initiator (D), and a colorant (E) optionally added. Furthermore, as a fifth invention, a color filter formed using the photosensitive polymer composition is provided, and as a sixth invention, an image display device including the color filter is provided.

  According to the present invention, when used as a photosensitive material, a curable polymer excellent in sensitivity, developability, solvent resistance, adhesion to a substrate and dye dispersibility can be efficiently obtained. In addition, the cured coating film formed from the photosensitive polymer composition of the present invention is excellent in sensitivity, developability, solvent resistance, adhesion to the substrate, and dispersibility of the dye. When used as a photosensitive material for a color filter, a color filter having a colored pattern excellent in solvent resistance, adhesion to a substrate and dispersibility of a dye can be obtained.

<Curable polymer>
As described above, when the curable polymer of the present invention is a homopolymer, the (meth) acrylate monomer (a) having a glass transition temperature of 10 ° C. or lower and the (meth) acrylic monomer having an epoxy group or a carboxy group are used. An acid group or a hydroxy group is added to the side chain obtained by performing the modification reaction (I) or (II) above on the addition copolymer of (b) and other radically polymerizable monomer (c) used as desired. And having a polymerizable unsaturated bond, a glass transition temperature of 20 ° C. or less, and a polystyrene equivalent weight average molecular weight of 1,000 to 50,000. Incidentally, in this specification, since the polymerizable unsaturated group which exists in a polymer molecule contributes to the crosslinking reaction between polymers, this polymer is called "curable polymer." In the present specification, (meth) acrylate means acrylate or methacrylate, and (meth) acrylic monomer means acrylic monomer or methacrylic monomer.

<Monomer used for addition copolymer>
The addition copolymer, which is a precursor of the curable polymer of the present invention, has a (meth) acrylate monomer (a) having a glass transition temperature of 10 ° C. or lower when a homopolymer is formed, and an epoxy group or a carboxy group. It is produced by radical copolymerization of (meth) acrylic monomer (b) and other radically polymerizable monomer (c) used as desired according to a conventional method. The (meth) acrylate monomer (a) does not include those corresponding to the (meth) acrylic monomer (b).

  In the present invention, as the first monomer component, a (meth) acrylate having a glass transition temperature of 10 ° C. or lower, preferably −100 to 0 ° C., particularly preferably −80 to −10 ° C. when a homopolymer is used. Monomer (a) is used. The lower this Tg, the lower the Tg of the resulting curable polymer, thereby improving the developability and adhesion to the substrate when used as a photosensitive material, resulting in improved pattern shape. The

  The glass transition temperature was measured in accordance with JIS-K7121 at a heating rate of 10 ° C./min in a nitrogen stream using DSC (differential scanning calorimetry, measuring instrument: Seiko DSC6200) for the solid content of the polymer. The midpoint glass transition temperature.

  Specific examples of the (meth) acrylate monomer (a) that gives a low Tg include n-pentyl methacrylate, isoamyl acrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, 2-ethylhexyl acrylate, n-octyl methacrylate, isodecyl methacrylate, Lauryl acrylate, lauryl methacrylate, methoxy-triethylene glycol acrylate, ethoxy-diethylene glycol acrylate, methoxy polyethylene glycol methacrylate, methoxy polyethylene glycol acrylate (trade name: AM-90G, manufactured by Shin-Nakamura Chemical Co., Ltd.), 2-hydroxyethyl acrylate, 2 -(Meth) acrylate having no aromatic ring such as hydroxypropyl acrylate (hereinafter referred to as monomer (a 1)); phenoxyethyl acrylate, phenoxy-polyethylene glycol acrylate (trade name: Light acrylate P-200A, manufactured by Kyoei Chemical Co., Ltd.), o-phenoxybenzyl acrylate, m-phenoxybenzyl acrylate, p-phenoxybenzyl And (meth) acrylate having an aromatic ring such as acrylate (hereinafter sometimes referred to as monomer (a-2)). These monomers may be used alone, but two or more types of monomers may be used in combination.

  Of these, (meth) acrylate monomers having a glass transition temperature (Tg) of −100 to 0 ° C., more preferably −80 to −10 ° C. when homopolymers are used are preferred. Even when the polymerization ratio is small, a low Tg curable polymer can be easily obtained. Moreover, since the curable polymer obtained has a low Tg, the developability and adhesion to the substrate when used as a photosensitive material are improved, and the pattern shape is further improved. On the other hand, it is not preferable to use a (meth) acrylate having a Tg of more than 10 ° C. when the homopolymer is used because the adhesiveness is lowered. Moreover, when Tg becomes too low, there exists a concern that solvent resistance falls.

  In the present invention, when the monomer (a-1), that is, (meth) acrylate having no aromatic ring is used as the (meth) acrylate monomer (a), a curable polymer excellent in dye dispersibility can be obtained. In addition, when the monomer (a-2), that is, (meth) acrylate having an aromatic ring is used, a curable polymer having excellent pigment dispersibility can be obtained. In general, even a photosensitive material that exhibits good performance in the pigment dispersion method is not necessarily sufficient when applied to the dye dispersion method, or vice versa. In the invention, when the monomer (a-1) and the monomer (a-2) are used in combination, a curable polymer exhibiting good performance can be obtained by any method. In this case, the use ratio of (a-1) and (a-2) is such that the molar ratio of (a-1) / (a-2) is 1/10 to 5/1, preferably 1/5 to 2 / 1, more preferably 1/3 to 1/1.

  In the present invention, the (meth) acrylic monomer (b) having an epoxy group or a carboxyl group is used as the second monomer component. Specific examples of the (meth) acrylic monomer having an epoxy group (hereinafter sometimes referred to as monomer (b-1)) include glycidyl (meth) acrylate, 2-glycidyloxyethyl (meth) acrylate, and alicyclic epoxy. 3,4-epoxycyclohexylmethyl (meth) acrylate and lactone adducts thereof (eg, Cyclomer A200, M100 manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxy Examples thereof include mono (meth) acrylic acid ester of cyclohexanecarboxylate, epoxidized product of dicyclopentenyl (meth) acrylate, epoxidized product of dicyclopentenyloxyethyl (meth) acrylate, and the like. Of these, glycidyl (meth) acrylate is preferably used from the standpoint of availability and reactivity.

  Specific examples of the (meth) acrylic monomer having a carboxyl group (hereinafter sometimes referred to as the monomer (b-2)) include (meth) acrylic acid and substituted products thereof such as α-bromo (meth). Acrylic acid, (beta) -furyl (meth) acrylic acid, etc. are mentioned. Among these, (meth) acrylic acid is most often used. The monomer (b-1) and the monomer (b-2) may be used alone, or two or more monomers (b-1) or monomers (b-2) may be used in combination. However, when the monomer (b-1) and the monomer (b-2) are used in combination, there is a concern of causing a side reaction due to the epoxy group and the carboxy group in the copolymerization reaction.

  In the present invention, in addition to these essential monomer components, other radical polymerizable monomers (c) can be used in combination as required. Specific examples of preferable other monomer (c) include a polymerizable monomer having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms (hereinafter referred to as c-1), a norbornene monomer (hereinafter referred to as c-2), and Examples thereof include lower alkyl methacrylate (c-3) having 1 to 3 carbon atoms. In the monomer (c-1), the bridged cyclic hydrocarbon means one having a structure represented by the following formula (1) or (2) represented by adamantane or norbornane, The hydrocarbon group refers to a group corresponding to the remaining part of the structure excluding a part of hydrogen.

(In the formula (1), A ¹ and B ¹ each represent a linear or branched alkylene group (including a cyclic group), R ⁴ represents a hydrogen atom or a methyl group, and A ¹ and B ¹ are the same. Or may be different, and the branches of A ¹ and B ¹ may be connected to form a ring.)

(In the formula (2), A ² , B ² and L each represent a linear or branched alkylene group (including a cyclic group), and R ⁵ represents a hydrogen atom or a methyl group. A ² and B ² , L may be the same or different, and the branches of A ² , B ² , and L may be connected to form a ring.)

  The monomer (c-1) is preferably a (meth) acrylate having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms, and has a structure represented by adamantyl (meth) acrylate or the following formula (3) ( More preferred is (meth) acrylate.

(In Formula (3), R ^{6 to} R ⁸ each represent a hydrogen atom or a methyl group. R ⁹ and R ¹⁰ are each a hydrogen atom or a methyl group, or are linked to each other to form a saturated or unsaturated ring. The ring is preferably a 5-membered ring or a 6-membered ring. * Represents a bond connected to the (meth) acrylate group.)

  Examples of the polymerizable monomer (c-1) include dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate and the like. Among these, dicyclopentanyl methacrylate is more preferable from the viewpoint of heat decomposition resistance and heat discoloration. These can be used alone or in combination of two or more.

  Further, the norbornene monomer (c-2) is represented by the following formula (4).

(X and Y in Formula (4) each independently represent a hydrogen atom, a linear or branched hydrocarbon group having 1 to 4 carbon atoms, and R ¹ and R ² are each independently A hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent or an alkyloxycarbonyl group, which may have a cyclic structure connecting R ¹ and R ^2. )

When X and Y are linear or branched hydrocarbon groups having 1 to 4 carbon atoms, specific examples thereof include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl. Group, t-butyl group and the like. When R ¹ and R ² are optionally substituted hydrocarbon groups having 1 to 20 carbon atoms, examples of R ¹ and R ² include a methyl group, an ethyl group, an n-propyl group, Linear or branched alkyl group such as isopropyl group, n-butyl group, isobutyl group, t-butyl group, t-amyl group, stearyl group, lauryl group, 2-ethylhexyl group; aryl group such as phenyl; cyclohexyl group , T-butylcyclohexyl group, dicyclopentadienyl group, tricyclodecanyl group, isobornyl group, adamantyl group, 2-methyl-2-adamantyl group and the like, and specific examples of substituents Examples thereof include alkoxy groups such as methoxy group and ethoxy group, and aryl groups such as phenyl group. Furthermore, when R ¹ and R ² are alkyloxycarbonyl groups, a methoxycarbonyl group, an ethoxycarbonyl group and the like can be mentioned.

Examples of the norbornene monomer (c-2) include norbornene (bicyclo [2.2.1] hept-2-ene), 5-methylbicyclo [2.2.1] hept-2-ene, and 5-ethyl. Bicyclo [2.2.1] hept-2-ene, 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 ] dec-8-ene, tricyclo [5.2.1.0 ^2,6 ] dec-3 -Ene, tricyclo [4.4.0.1 ^2,5 ] undec-3-ene, tricyclo [6.2.1.0 ^1,8 ] undec-9-ene, tricyclo [6.2.1.0 ^1,8 ] undec-4-ene, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 . 0 ^1,6 ] dodec-3-ene, 8-methyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 . 0 ^1,6 ] dodec-3-ene, 8-ethylidenetetracyclo [4.4.0.1 ^2,5 . 1 ^7,12 ] dodec-3-ene, 8-ethylidenetetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 . 0 ^1,6 ] dodec-3-ene, pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13] pentadeca-4-ene, pentacyclo [7.4.0.1 ^2,5. 1 ^9,12 . 0 ^8,13] pentadeca-3-ene, 5- methoxycarbonyl bicyclo [2.2.1] hept-2-ene, 5-ethoxycarbonyl-bicyclo [2.2.1] hept-2-ene, 5-methyl Examples include -5-methoxycarbonylbicyclo [2.2.1] hept-2-ene and 5-methyl-5-ethoxycarbonylbicyclo [2.2.1] hept-2-ene. Among these, norbornene and dicyclopentadiene are preferable from the viewpoints of heat decomposition resistance and heat discoloration. These can be used alone or in combination of two or more.

  Lower alkyl methacrylate (c-3) is an alkyl methacrylate having an alkyl group having 1 to 3 carbon atoms, and specific examples thereof include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate and the like. . These can be used alone or in combination of two or more. Among them, methyl methacrylate is used for prizes.

Other specific examples include styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-methoxystyrene, m -Aromatic vinyl compounds such as methoxystyrene, p-methoxystyrene, p-nitrostyrene, p-cyanostyrene, p-acetylaminostyrene;
Conjugated diene compounds such as butadiene, isoprene and chloroprene;

n-butyl (meth) acrylate, sec-butyl (meth) acrylate, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, benzyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, Methylcyclohexyl (meth) acrylate, ethylcyclohexyl (meth) acrylate, rosin (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 1,1,1-trifluoroethyl (meth) acrylate, perfluoroethyl (meth) acrylate, Perfluoro-n-propyl (meth) acrylate, perfluoro-iso-propyl (meth) acrylate, 3- (N, N-dimethylamino) propyl (meth) acrylate, triphenylmethyl (Meth) acrylate, phenyl (meth) acrylate, cumyl (meth) acrylate, 4-phenoxyphenyl (meth) acrylate, biphenyloxyethyl (meth) acrylate, naphthalene (meth) acrylate, anthracene (meth) acrylate, (meth) acroyl (Meth) acrylic acid such as a reaction product of oxyethyl isocyanate (ie 2-isocyanatoethyl (meth) acrylate) and ε-caprolactam, a reaction product of (meth) acryloyloxyethyl isocyanate and propylene glycol monomethyl ether Ester compounds;

(Meth) acrylic acid amide, (meth) acrylic acid N, N-dimethylamide, (meth) acrylic acid N, N-diethylamide, (meth) acrylic acid N, N-dipropylamide, (meth) acrylic acid N, (Meth) acrylic amides such as N-di-isopropylamide, (meth) acrylic acid anthracenyl amide;
Vinyl compounds such as (meth) acrylic acid anilide, (meth) acrylonitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinyl pyrrolidone, vinyl pyridine, vinyl acetate, vinyl toluene;
Unsaturated dicarboxylic acid diester compounds such as diethyl citraconic acid, diethyl maleate, diethyl fumarate, diethyl itaconate;
Monomaleimide compounds such as N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, N- (4-hydroxyphenyl) maleimide;
Etc. These can be used alone or in combination of two or more.

  Among these, those containing no nitrogen atom in the molecule are preferably used from the viewpoint of yellowing resistance. In particular, when the above (c-1) and / or (c-2) is used in a proportion of 2 to 10 mol%, the heat decomposition resistance and the heat discoloration are improved. Further, when the lower alkyl methacrylate (c-3) is used in a proportion of 10 to 35 mol%, the transparency is greatly improved. Further, a reaction product of (meth) acryloyloxyethyl isocyanate (that is, 2-isocyanatoethyl (meth) acrylate) and ε-caprolactam, a reaction product of (meth) acryloyloxyethyl isocyanate and propylene glycol monomethyl ether When a monomer having a blocked isocyanate group such as is used, the solvent resistance is improved.

  The proportion of (meth) acrylate monomer (a), (meth) acrylic monomer (b) and other radical polymerizable monomer (c) used in the production of the addition copolymer is such that (meth) acrylate monomer (a) 5 to 40 mol%, preferably 10 to 35 mol%, more preferably 15 to 35 mol%, and (meth) acrylic monomer (b) is 30 to 85 mol%, preferably 35 to 80 mol% More preferably, it is 40 to 75 mol%, and the other radical polymerizable monomer (c) is 0 to 35 mol%, preferably 0 to 30 mol%, more preferably 2 to 30 mol%.

  When the amount of the (meth) acrylate monomer (a) is excessively small, it becomes difficult to obtain a curable polymer having a low Tg, and as a result, the adhesion to the substrate tends to be insufficient, and the dispersibility with dyes and pigments. May not be enough. Conversely, if the amount is excessively large, the sensitivity and solvent resistance may be reduced. Further, when the amount of the (meth) acrylic monomer (b) is excessively small, it becomes difficult to introduce a desired amount of unsaturated bonds into the side chain of the polymer, and in particular, the (meth) acrylic monomer (b-1) is used. In some cases, it becomes difficult to introduce a desired amount of acid groups. On the other hand, if the amount is excessively large, adhesion and dispersibility with dyes and pigments may not be sufficient.

  In the production of the addition copolymer, the other radical polymerizable monomer (c) is not necessarily essential, but by using the monomer (c) in combination, the heat resistance and the pigment dispersibility can be appropriately improved. In particular, when (c-1) and / or (c-2) is used as the other radical polymerizable monomer (c), the heat resistance and yellowing resistance are improved. preferable.

  The copolymerization reaction of the (meth) acrylate monomer (a), the (meth) acrylic monomer (b) and other radically polymerizable monomer (c) used as desired is a polymerization solvent according to a radical polymerization method known in the art. In the presence or absence of. For example, these monomers may be dissolved in a solvent as required, and then a polymerization initiator may be added to the solution, and a polymerization reaction may be performed at 50 to 130 ° C. for 1 to 20 hours.

Solvents that can be used for the copolymerization reaction are not particularly limited, and examples thereof include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, and diethylene glycol. Mono-n-butyl 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-n- Propyl ether, dipropylene glycol mono-n-butyl ether Le, tripropylene glycol monomethyl ether, and tripropylene glycol monoethyl ether (poly) alkylene glycol monoalkyl ether compound;
(Poly) alkylene glycol monoalkyl ether acetate compounds such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate;

Other ether compounds such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran;
Ketone compounds such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone;
Methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-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-methoxybutyl Propionate, ethyl acetate, n-butyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl acetate, i-amyl acetate, n-butyl propionate, ethyl butyrate , N-propyl butyrate, i-propyl butyrate, n-butyl butyrate Le, methyl pyruvate, ethyl pyruvate, pyruvate n- propyl, methyl acetoacetate, ethyl acetoacetate, ester compounds such as ethyl 2-oxobutyrate;
Aromatic hydrocarbon compounds such as toluene and xylene;
And carboxylic acid amide compounds such as N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, and the like. These solvents can be used alone or in admixture of two or more.

  Among these, (poly) alkylene glycol monoalkyl ether solvents such as propylene glycol monomethyl ether and (poly) alkylene glycol monoalkyl ether acetate solvents such as propylene glycol monomethyl ether acetate, that is, glycol ether solvents are preferable.

  Although the usage-amount of a polymerization solvent is not specifically limited, When the sum total of the preparation amount of a monomer is 100 mass parts, it is generally 30-1,000 mass parts, Preferably it is 50-800 mass parts. In particular, when the amount of the solvent used is 1,000 parts by mass or less, a decrease in the molecular weight of the copolymer due to chain transfer action can be suppressed, and the viscosity of the copolymer can be controlled within an appropriate range. Further, by setting the blending amount of the solvent to 30 parts by mass or more, an abnormal polymerization reaction can be prevented, the polymerization reaction can be stably performed, and the coloring and gelation of the copolymer can also be prevented. .

  In addition, the polymerization initiator that can be used for the copolymerization reaction is not particularly limited, and examples thereof include azobisisobutyronitrile, azobisisovaleronitrile, benzoyl peroxide, t-butylperoxy-2- Examples include ethyl hexanoate. These can be used alone or in combination of two or more. The amount of the polymerization initiator used is generally 0.5 to 20 parts by mass, preferably 1 to 10 parts by mass when the total amount of monomers charged is 100 parts by mass.

<Manufacture of curable polymer>
In the present invention, the side chain contains an acid group, a hydroxy group by performing the following modification reaction (I) or (II) using an epoxy group or a carboxy group contained in the molecule of the addition copolymer thus produced. A curable polymer having a group and a polymerizable unsaturated bond, having a glass transition temperature of 20 ° C. or lower, and having a polystyrene-equivalent weight average molecular weight of 1,000 to 50,000 can be obtained.
Modification method of (I):
A method in which an epoxy group contained in a molecule of an addition copolymer is cleaved with a polymerizable unsaturated monobasic acid (d), and a hydroxy group generated by the cleavage is reacted with a polybasic acid or an anhydride thereof (e) .
Modification method of (II):
A method of reacting a carboxy group contained in a molecule of an addition copolymer with a (meth) acrylate monomer (f) having a functional group reactive with the carboxy group.

<Modification method of (I)>
The polymerizable unsaturated monobasic acid (d) used in this modification reaction may be any one having a polymerizable unsaturated bond and an acid group, and examples thereof include unsaturated carboxylic acids, unsaturated sulfonic acids, unsaturated phosphones. An acid etc. are illustrated. Specific examples of preferred unsaturated monobasic acids include (meth) acrylic acid, α-bromo (meth) acrylic acid, β-furyl (meth) acrylic acid, crotonic acid, propiolic acid, cinnamic acid, α-cyanocinnamic acid Unsaturated carboxylic acids such as monomethyl maleate, monoethyl maleate, monoisopropyl maleate, monomethyl fumarate, monoethyl itaconate; 2-acrylamido-2-methylpropanesulfonic acid, tert-butylacrylamidesulfonic acid, p-styrenesulfone Unsaturated sulfonic acids such as acids; unsaturated phosphonic acids such as vinylphosphonic acids; and the like. These unsaturated monobasic acids may be used alone or in combination of two or more. Among these, unsaturated carboxylic acid is preferable from the viewpoint of reactivity and availability, and (meth) acrylic acid is most often used.

  The amount of the polymerizable unsaturated monobasic acid (d) used for the modification reaction can be appropriately selected according to the value of the unsaturated group equivalent of the target curable polymer. Usually, the amount is 0.90 to 1 mol, preferably 0.95 to 1 mol, per mol of epoxy group contained in the addition copolymer. If the amount of the polymerizable unsaturated monobasic acid (e) used is excessively small, side reactions may occur in the subsequent reaction.

  This denaturation reaction can be carried out according to a conventional method. For example, both components may be added to the reaction solvent, and a catalyst may be further added. For example, the reaction may be performed at 50 to 150 ° C., preferably 80 to 130 ° C. In this modification reaction, there is no particular problem even if the solvent used in the copolymerization reaction is included. Therefore, the modification reaction can be performed without removing the solvent after the copolymerization reaction is completed.

  In carrying out this modification reaction, a polymerization inhibitor is added as necessary to prevent gelation. Although it does not specifically limit as a polymerization inhibitor, For example, hydroquinone, methyl hydroquinone, hydroquinone monomethyl ether, etc. are mentioned. The catalyst is not particularly limited, and examples thereof include tertiary amines such as triethylamine, quaternary ammonium salts such as triethylbenzylammonium chloride, phosphorus compounds such as triphenylphosphine, and chelate compounds of chromium. Can be mentioned.

  At the same time as the epoxy group of the addition copolymer is cleaved by the first modification reaction as described above, an unsaturated bond derived from the polymerizable unsaturated monobasic acid (d) is introduced into the side chain of the polymer. , A hydroxy group derived from an epoxy group is generated. In the present invention, an acid group is introduced into the polymer by a second modification reaction in which this hydroxy group reacts with a polybasic acid or its anhydride (e).

  The polybasic acid or its anhydride (e) used may be either a saturated or unsaturated polybasic acid or its anhydride. Specific examples include malonic acid, succinic acid, succinic anhydride, glutaric acid, adipine Acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, methyltetrahydrophthalic acid, methyltetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, Citraconic acid, citraconic anhydride, 5-rubornene-2,3-dicarboxylic acid, 5-rubornene-2,3-dicarboxylic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, phthalic anhydride, etc. Tribasic acids such as dibasic acid or anhydride, trimellitic acid, trimellitic anhydride or the like Anhydride, pyromellitic acid, etc. tetracarboxylic acid or its anhydride such as pyromellitic acid anhydride are exemplified. Of these, dicarboxylic acid anhydride is preferably used.

  The amount of the hydroxy group and polybasic acid or anhydride (e) used in the second modification reaction can be appropriately selected according to the acid value of the target curable polymer. Usually, the amount is 0.01 to 0.9 mol, preferably 0.02 to 0.85 mol, per mol of the hydroxy group produced in the first modification reaction. If the amount of the hydroxy group and polybasic acid or anhydride (e) used is too small, the developability may be insufficient, and if too large, development residue may be generated and the sensitivity may be lowered.

  The second denaturation reaction can also be performed according to a conventional method. For example, after performing the first modification reaction, a polybasic acid or its anhydride (e) is added to the reaction system, and the reaction may be performed at, for example, 50 to 150 ° C., preferably 80 to 130 ° C. The reaction time may be appropriately selected, but is usually 0.05 to 10 hours, preferably 0.1 to 7 hours.

<Modification method of (II)>
Specific examples of the (meth) acrylate compound (f) having a functional group reactive with a carboxy group used in the modification reaction of (II) have a functional group such as an epoxy group, a hydroxy group, an amino group, and a vinyl ether group. Specific examples thereof include glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate having alicyclic epoxy, and lactone adducts thereof (for example, Daicel Chemical Industries, Ltd.) Cyclomer A200, M100), 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate mono (meth) acrylate, epoxidized dicyclopentenyl (meth) acrylate, dicyclopentenyloxy Ethyl (meth) acrylate Radical polymerizable compounds having an epoxy group such as epoxidized products; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 2 -Radical polymerizable compounds having a hydroxy group such as phenoxy-2-hydroxypropyl (meth) acrylate, 2- (meth) acryloyloxy-2-hydroxypropyl phthalate, allyl alcohol; 4- radicals having an amino group such as aminostyrene Polymerizable compounds; Radical polymerizable compounds having a vinyl ether group such as 2-vinyloxyethoxyethyl (meth) (meth) acrylate. Among these, a radically polymerizable compound having an epoxy group, particularly glycidyl (meth) acrylate is preferably used.

  The reaction of the addition copolymer and the (meth) acrylate compound (f) can be carried out according to a conventional method. For example, both components may be added to the reaction solvent, a polymerization inhibitor and a catalyst may be further added, and the reaction may be performed at, for example, 50 to 150 ° C., preferably 80 to 130 ° C. Further, as in the case of the modification method (I), the modification reaction can be carried out without removing the solvent after completion of the addition copolymerization reaction. If necessary, a polymerization inhibitor is used to prevent gelation. May be added.

  The amount of the (meth) acrylate compound (f) used in the modification reaction can be appropriately selected according to the unsaturated group equivalent and the acid value of the target curable polymer. Usually, the amount is 0.05 to 0.8 mol, preferably 0.1 to 0.7 mol, per mol of the carboxy group contained in the addition copolymer. When the amount of the (meth) acrylate compound (f) used is too small, the unsaturated group equivalent becomes too large, and the sensitivity and solvent resistance performance tend to be lowered.

<Curable polymer>
In the present invention, by subjecting the addition copolymer to the modification method (I) or (II), the glass transition temperature (Tg) is 20 ° C. or lower, preferably −50 to 10 ° C., more preferably −30. A curable polymer having a polystyrene equivalent weight average molecular weight of 1,000 to 50,000, preferably 3,000 to 40,000 can be obtained. When Tg exceeds 20 ° C., the adhesion to the substrate is not sufficient, and conversely, when Tg is excessively low, the formed coating film becomes too soft or the physical properties when cured tend to be insufficient. Further, if the weight average molecular weight is less than 1,000, chipping of a colored pattern is likely to occur after alkali development when used as a photosensitive polymer composition. Conversely, if the molecular weight exceeds 50,000, the development time is increased. May become too long and lack practicality.

  In the present invention, 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 10 to 300 KOHmg / g, preferably 20 to 200 KOHmg / g. Range. When the acid value is less than 10 KOHmg / g, the alkali developability as a photosensitive polymer may be lowered. On the other hand, when the acid value exceeds 300 KOHmg / g, the exposed portion (photocured portion) is easily dissolved in the alkali developer, and the pattern shape may be insufficient.

  The hydroxyl value (JIS K0070) of the curable polymer is usually in the range of 70 to 300 KOHmg / g, preferably 85 to 250 KOHmg / g. If the hydroxyl value is less than 70 KOHmg / g, adhesion and developability may be deteriorated. On the other hand, when the hydroxyl value exceeds 300 KOHmg / g, the solvent resistance may be insufficient.

  Furthermore, the unsaturated group equivalent of the curable polymer is not particularly limited, but is usually in the range of 100 to 4,000 g / mol, preferably 200 to 2,000 g / mol, and more preferably 300 to 500 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 developability. Conversely, when the unsaturated group equivalent is 4,000 g / mol or less, the sensitivity is more improved. It is effective in raising. The unsaturated bond equivalent is the mass of the polymer per 1 mol of unsaturated bonds in the polymer, and can be determined by dividing the mass of the polymer by the amount of unsaturated bonds in the polymer (g / Mol). In the present invention, the unsaturated bond equivalent is a theoretical value calculated from the amount of raw materials used for introducing unsaturated bonds.

<Polymer composition>
In the present invention, in addition to the curable polymer (A component, hereinafter may be referred to as A), a solvent (B component, hereinafter may be referred to as B) and / or a reactive diluent (C component, hereinafter referred to as B). (Sometimes referred to as C). The solvent (B) is not particularly limited as long as it is an inert solvent that does not react with the curable polymer (A), and is the same category as the solvent used in the production of the curable polymer (A) (copolymerization reaction). Things can be used. Specific examples thereof are as described above. Preferably, (poly) alkylene glycol monoalkyl ether solvents such as propylene glycol monomethyl ether and (poly) alkylene glycol monoalkyl ether acetate solvents such as propylene glycol monomethyl ether acetate, That is, a glycol ether solvent is used.

  The polymer composition of the present invention can be prepared by appropriately mixing the desired solvent (B) with the curable polymer (A) isolated from the polymerization system, but the curable polymer (A) is not necessarily polymerized. The solvent contained at the end of the copolymerization reaction can be used as it is, and a desired solvent can be further added as necessary. Moreover, the solvent contained in the other component used when preparing a polymer composition can also be used as a component of a 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 when used in combination with the curable polymer (A), the film strength of the coating film formed and the adhesion to the substrate are as follows. Can be improved. Moreover, it can also be set as the composition which contains a curable polymer (A) and a reactive diluent (C) without containing a solvent (B) if desired.

  Monofunctional monomers used as reactive diluents include (meth) acrylamide, methylol (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (meth) acrylamide, butoxymethoxymethyl (meth) ) Acrylamide, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4 -Hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (meth) acryloyloxy-2-hydroxypropyl phthalate, glycerin mono ( Acrylate), tetrahydrofurfuryl (meth) acrylate, glycidyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, phthalic acid (Meth) acrylate compounds such as half (meth) acrylate of derivatives; aromatic vinyl compounds such as styrene, α-methylstyrene, α-chloromethylstyrene, vinyltoluene; carboxylic acid esters such as vinyl acetate and vinyl propionate Can be mentioned. Moreover, these can be used individually or in combination of 2 or more types.

  On the other hand, as the polyfunctional monomer, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol Di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexane glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerol di (meth) acrylate, pentaerythritol di (meth) Acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, , 2-bis (4- (meth) acryloxydiethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane, 2-hydroxy-3- (meth) acryloyloxypropyl ( (Meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diglycidyl phthalate di (meth) acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly (meth) acrylate, Urethane (meth) acrylate (ie, tolylene diisocyanate), trimethylhexamethylene diisocyanate and hexamethylene diisocyanate, etc. and 2-bidoxyethyl (meth) acrylate (Meth) acrylate compounds such as tri (meth) acrylate of tris (hydroxyethyl) isocyanurate; aromatic vinyl compounds such as divinylbenzene, diallylphthalate and diallylbenzenephosphonate; dicarboxylic acid ester compounds such as divinyl adipate; Examples include allyl cyanurate, methylene bis (meth) acrylamide, (meth) acrylamide methylene ether, and a condensate of polyhydric alcohol and N-methylol (meth) acrylamide. Moreover, these can be used individually or in combination of 2 or more types.

  The blending amounts of the curable polymer (A), the solvent (B), and the reactive diluent (C) in the polymer composition may be appropriately selected according to the purpose of use. C) When the total of the components is 100 parts by mass, the curable polymer (A) is 10 to 100 parts by mass, the solvent (B) is 0 to 1,000 parts by mass, and the reactive diluent (C) is 0 to 90 parts. The curable polymer (A) is preferably 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. 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. If the blending amount is within this range, it becomes a polymer composition having an appropriate viscosity and can be used to prepare a photosensitive polymer composition described later, as well as various coatings, adhesives, binders for printing ink, etc. It can also be used.

<Photosensitive polymer composition>
In the present invention, the curable polymer (A), the solvent (B), the reactive diluent (C), the photopolymerization initiator (D component, hereinafter may be referred to as D), and optionally the colorant (E A photosensitive polymer composition comprising a component, hereinafter sometimes referred to as E). Although it does not specifically limit as a photoinitiator (D), For example, Benzoin compounds, such as a benzoin, a benzoin methyl ether, a benzoin ethyl ether, a benzoin butyl ether; Acetophenone, 2, 2- dimethoxy-2-phenyl acetophenone, 1, 1 -Dichloroacetophenone, 4- (1-t-butyldioxy-1-methylethyl) acetophenone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 2-benzyl-2 -Acetophenone compounds such as dimethylamino-1- (4-morpholinophenyl) butanone-1; anthraquinone compounds such as 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone; xanthone, thio Xanthone compounds such as sandone, 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone; ketal compounds such as acetophenone dimethyl ketal and benzyldimethyl ketal; benzophenone, 4- (1-t-butyldioxy-1- Benzophenone compounds such as methylethyl) benzophenone and 3,3 ′, 4,4′-tetrakis (t-butyldioxycarbonyl) benzophenone; acylphosphine oxide compounds; These can be used alone or in combination of two or more.

  The blending amount of the photopolymerization initiator (D) in the photosensitive polymer composition is generally 0.1 to 30 parts by mass, preferably 0. 0 parts per 100 parts by mass in total of the component (A) and the component (C). It is 5-20 mass parts, More preferably, it is 1-15 mass parts. If it is the compounding quantity of this range, it will become the photosensitive polymer composition which has appropriate photocurability.

  The colorant (E) is not particularly limited as long as it dissolves or disperses in the solvent (B), and examples thereof include dyes and pigments. The dye has an acidic group such as carboxylic acid or sulfonic acid from the viewpoint of solubility in the solvent (B) or alkali developer, interaction with other components in the photosensitive polymer composition, heat resistance, and the like. It is preferable to use acid dyes, salts of acid dyes with nitrogen compounds, sulfonamides of acid dyes, and the like.

  Examples of such dyes include 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 chroma 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 red1, 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, 38, 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 yellow1, 3, 9, 11, 17, 23, 25, 29, 34, 36, 42, 54, 72, 73, 76, 79, 98, 99, 111, 112, 114, 116; food yellow3 and these Derivatives and the like. Among these, azo, xanthene, anthraquinone or phthalocyanine acid dyes are preferable. These can be used alone or in combination of two or more depending on the color of the target pixel.

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

  These can be used alone or in combination of two or more depending on the color of the target color filter. In addition, according to the color of the target color filter, it can also use combining said dye and a pigment. The blending amount of the colorant (E) is generally 5 to 80 parts by weight, preferably 5 to 70 parts by weight, more preferably 10 to 60 parts by weight with respect to 100 parts by weight as the total of the components (A) and (C). Part.

  When a pigment is used as the colorant (E), a known dispersant may be added to the photosensitive polymer composition from the viewpoint of improving the dispersibility of the pigment. As the dispersant, it is preferable to use a polymer dispersant excellent in dispersion stability over time. Examples of polymer dispersants include urethane dispersants, polyethyleneimine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene glycol diester dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified esters. System dispersants and the like. As such a polymer dispersant, commercially available under trade names such as EFKA (manufactured by EFKA Chemicals Beebuy (EFKA)), Disperbyk (manufactured by BYK Chemie), Disparon (manufactured by Enomoto Kasei Co., Ltd.), SOLPERSE (manufactured by GENEKA). You may use what is done. What is necessary is just to set the compounding quantity of a dispersing agent suitably according to kinds, such as a pigment 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 blending amount is generally 10 to 90 parts by mass of the curable polymer (A) and the solvent (B) when the total amount of the component (A) and the component (C) in the photosensitive polymer composition is 100 parts by mass. 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, the curable 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 colorant (E) is 5 to 70 parts by mass, and more preferably, the curable polymer (A) is 30 to 75 parts by mass. Parts, solvent (B) is 100 to 700 parts by weight, reactive diluent (C) is 25 to 70 parts by weight, photopolymerization initiator (D) is 1 to 15 parts by weight, and colorant (E) is 10 to 60 parts. Part by mass. Even 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). The above numerical range is applicable.

  In addition to the above components, the polymer composition and photosensitive polymer composition of the present invention may be added with known coupling agents, leveling agents, thermal polymerization inhibitors and the like in order to impart predetermined characteristics. An agent may be blended. The amount of these additives is not particularly limited as long as it does not impair the effects of the present invention.

  The photosensitive polymer composition of this invention can be manufactured by mixing said component using a well-known mixing apparatus. Further, if desired, after preparing a polymer composition containing the curable polymer (A) and the solvent (B), the reactive diluent (C), the photopolymerization initiator (D), and optional components. It is also possible to manufacture by mixing the colorant (E).

  The photosensitive polymer composition of the present invention is suitable as a resist used for producing various resists, in particular, color filters incorporated in organic EL displays, liquid crystal display devices, solid-state imaging devices such as CCDs and CMOSs, and the like. . Moreover, since the photosensitive polymer composition of the present invention gives a cured film excellent in heat resistance, solvent resistance, dispersibility of dyes and pigments, it can be used for various coatings, adhesives, binders for printing inks, and the like. You can also.

<Color filter>
Next, a color filter prepared using the photosensitive polymer composition of the present invention will be described. The color filter of the present invention has a colored 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 formed at the boundary between the pixels, and a protective film formed on the pixels and the black matrix. In this configuration, other configurations can be adopted except that the pixels and the black matrix (colored pattern) are formed using the above-described photosensitive polymer composition.

  Next, an embodiment of a color filter manufacturing method will be described. First, a colored pattern is formed on a substrate. Specifically, a black matrix and RGB pixels are sequentially formed on the substrate. The material of the base material is not particularly limited, and a glass substrate, a silicon substrate, a polycarbonate substrate, a polyester substrate, a polyamide substrate, a polyamideimide substrate, a polyimide substrate, an aluminum substrate, a printed wiring substrate, an array substrate, or the like is appropriately used. Can do.

  The colored pattern can be formed by a photolithography method. Specifically, after applying the above-mentioned photosensitive polymer composition onto a substrate to form a coating film, the coating film is exposed through a photomask having a predetermined pattern, and the exposed portion is photocured. And a predetermined pattern can be formed by developing after baking an unexposed part with aqueous alkali solution, and baking.

  A method for applying the photosensitive polymer composition is not particularly limited, and screen printing, roll coating, curtain coating, spray coating, spin coating, and the like can be used. Moreover, after application | coating of the photosensitive polymer composition, you may volatilize a solvent (B) by heating using heating means, such as a circulation type oven, an infrared heater, a hotplate, as needed. The heating conditions are not particularly limited, and may be set as appropriate according to the type of the photosensitive polymer composition to be used. In general, heating may be performed 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 active energy rays such as ultraviolet rays and excimer laser light through a negative mask. What is necessary is just to select the energy dose to irradiate suitably according to the composition of the photosensitive polymer composition, for example, it is preferable that it is 30-2000 mJ / cm < ² >. The light source used 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 used for development is not particularly limited, but an aqueous solution of sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide, potassium hydroxide, etc .; an aqueous solution of an amine compound such as ethylamine, diethylamine, dimethylethanolamine; Methylammonium, 3-methyl-4-amino-N, N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl- P-phenylenediamine such as N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline and their sulfates, hydrochlorides or p-toluenesulfonates An aqueous solution of a compound can be used. In addition, you may add an antifoamer and surfactant to these aqueous solutions as needed. Moreover, it is preferable to wash and dry after development with the above-mentioned alkaline aqueous solution.

  By baking the pattern formed by alkali development, the curing of the photosensitive polymer can be completed. The baking conditions are not particularly limited, and heat treatment may be performed according to the type of the photosensitive polymer composition to be used. For example, heating is performed at a temperature of 130 ° C. to 250 ° C. for 10 minutes to 4 hours, preferably 20 minutes to 2 hours.

  The steps of coating, exposing, developing and baking as described above are repeated by sequentially using a photosensitive polymer composition for black matrix and a photosensitive polymer composition for red, green and blue pixels. The coloring pattern can be formed. In addition, although the formation method of the coloring pattern by photocuring was demonstrated above, if the photosensitive polymer composition which mix | blended the hardening accelerator and the well-known epoxy resin was used instead of a photoinitiator (D), A desired coloring pattern can also be formed by applying the ink jet method and then heating. Next, a protective film is formed on the colored pattern (RGB pixels and black matrix). It does not specifically limit as a protective film, What is necessary is just to form using a well-known thing.

  The color filter produced in this way is manufactured using a photosensitive polymer composition that gives a colored pattern with excellent sensitivity, developability, solvent resistance, and dispersibility of dyes or pigments. With a colorful pattern.

<Image display element>
The image display element of the present invention is a display element having the above-described color filter, and specific examples thereof include liquid crystal display elements, organic EL display elements, solid-state imaging elements such as CCD elements and CMOS elements. In manufacturing such an image display element, a conventional method may be used except that the above-described color filter is used. For example, when manufacturing a liquid crystal display element, the color filter is formed on a substrate, and then electrodes, spacers, and the like are sequentially formed. Then, an electrode or the like may be formed on another substrate, and both may be bonded together to inject and seal a predetermined amount of liquid crystal.

EXAMPLES Hereinafter, although this invention is demonstrated in detail with reference to an Example, this invention is not limited by these Examples. In this example, all parts and percentages are based on mass unless otherwise specified. Moreover, the measuring method of glass transition temperature, an acid value, an unsaturated group equivalent, a hydroxyl value, and a weight average molecular weight is as follows.
(1) Glass transition temperature (Tg): A curable polymer solution is applied to a glass substrate, dried at 50 ° C. under reduced pressure for 24 hours, redissolved in acetone, and again dried at 50 ° C. under reduced pressure for 24 hours. By using DSC (differential scanning calorimeter method, measuring instrument: Seiko DSC6200), the solid content obtained by removing the volatile components by doing this is compliant with JIS-K7121 under a nitrogen stream at a heating rate of 10 ° C / min. And measured (midpoint glass transition point).
(2) Acid value: The acid value of the curable polymer measured in accordance with JIS K6901 5.3, and the number of mg of potassium hydroxide required to neutralize the acidic component contained in 1 g of the curable polymer. means.
(3) Unsaturated group equivalent: It is the mass of the polymer per mole of polymerizable unsaturated bonds, and is a calculated value calculated based on the amount of monomer used.
(4) Hydroxyl value: Hydroxyl value of a curable polymer measured according to JIS K0070, which is required to neutralize acetic acid bonded to a hydroxyl group when 1 g of the curable polymer is acetylated. It means the number of mg of potassium.
(5) Weight average molecular weight (Mw): Means a standard polystyrene equivalent weight average molecular weight measured under the following conditions using gel permeation chromatography (GPC).
Column: Shodex (registered trademark) LF-804 + LF-804 (manufactured by Showa Denko KK)
Column temperature: 40 ° C
Sample: 0.2% tetrahydrofuran solution of copolymer Development solvent: Tetrahydrofuran Detector: Differential refractometer (Showex RI-71S) (manufactured by Showa Denko KK)
Flow rate: 1mL / min

Example 1
To a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and a gas introduction tube, 262.0 g of propylene glycol monomethyl ether acetate was added and stirred while replacing with nitrogen, and the temperature was raised to 120 ° C.
Subsequently, 49.7 g (0.27 mol) of 2-ethylhexyl acrylate having a glass transition temperature of −70 ° C. when converted to a homopolymer, 99.4 g (0.7 mol) of glycidyl methacrylate, and dicyclopentanyl methacrylate What added 19.0 g of t-butylperoxy-2-ethylhexanoate (polymerization initiator, manufactured by NOF Corporation, perbutyl O) to a monomer mixture consisting of 6.6 g (0.03 mol) It dropped in the said flask over 2 hours from the dropping funnel. After completion of the dropping, the mixture was further stirred at 120 ° C. for 2 hours to carry out a copolymerization reaction, thereby producing an addition copolymer (a precursor of a curable polymer). Thereafter, the inside of the flask was replaced with air, and 50.4 g (0.7 mol) of acrylic acid, 0.6 g of triphenylphosphine (catalyst) and 0.2 g of methylhydroquinone were charged into the above addition copolymer solution. The reaction was continued at 110 ° C. for 10 hours, and the epoxy group was cleaved by the reaction of an epoxy group derived from glycidyl methacrylate and methacrylic acid, and at the same time, a polymerizable unsaturated bond was introduced into the side chain of the polymer. Next, 21.3 g (0.14 mol) of tetrahydrophthalic anhydride was added to the reaction system, and the reaction was continued at 110 ° C. for 3 hours. The hydroxyl group generated by the cleavage of the epoxy group and the anhydrous tetrahydrophthalic anhydride Physical groups were reacted to introduce a carboxy group into the side chain. The polymerizable polymer (A) thus obtained had a Tg of −10 ° C., an acid value of 32 KOH mg / g, an unsaturated group equivalent of 350 g / mol, and a weight average molecular weight of 6,400. there were. The hydroxyl value was 127 KOHmg / g.
Next, 107.5 g of propylene glycol monomethyl ether was added to the reaction solution to prepare a polymer solution having a solid content concentration of 40% of the curable polymer (A). This is designated as Sample 1.

Example 2
Instead of 49.7 g (0.27 mol) of 2-ethylhexyl acrylate, 130.1 g of methoxy polyethylene glycol acrylate (AM-90G manufactured by Shin-Nakamura Chemical Co., Ltd.) having a glass transition temperature of -71 ° C. when a homopolymer is obtained (0.27 mol) and curable polymer (B) in the same manner as in Example 1 except that 19.0 g of t-butylperoxy-2-ethylhexanoate was changed to 28.8 g. Got. The polymer had a Tg of −9 ° C., an acid value of 23 KOH mg / g, an unsaturated group equivalent of 480 g / mol, and a weight average molecular weight of 8,700. The hydroxyl value was 93 KOHmg / g. Next, propylene glycol monomethyl ether was added to the reaction solution to prepare a polymer solution having a solid content concentration of 40% of the curable polymer (B). This is designated as Sample 2.

Example 3
Instead of 49.7 g (0.27 mol) of 2-ethylhexyl acrylate, 94.0 g (0.37 mol) of m-phenoxybenzyl methacrylate having a glass transition temperature of -35 ° C. when used as a homopolymer is used. Glycidyl methacrylate 99.4 g (0.7 mol) to 85.2 g (0.6 mol), t-butylperoxy-2-ethylhexanoate to 22.7 g, acrylic acid 50.4 g (0 .7 mol) was changed to 43.2 g (0.6 mol) in the same manner as in Example 1 to obtain a curable polymer (C). The polymer had a Tg of −8 ° C., an acid value of 29 KOH mg / g, an unsaturated group equivalent of 460 g / mol, and a weight average molecular weight of 7,200. The hydroxyl value was 94 KOHmg / g. Next, propylene glycol monomethyl ether was added to the reaction solution to prepare a polymer solution having a solid content concentration of 40% of the curable polymer (B). This is designated as Sample 3.

Example 4
Instead of 49.7 g (0.27 mol) of 2-ethylhexyl acrylate, a mixture of 16.6 g (0.09 mol) of 2-ethylhexyl methacrylate and 45.7 g (0.18 mol) of m-phenoxybenzyl methacrylate is used. A curable polymer (D) was obtained in the same manner as in Example 1 except that the amount of t-butylperoxy-2-ethylhexanoate was changed to 20.5 g. The polymer had a Tg of −2 ° C., an acid value of 30 KOH mg / g, an unsaturated group equivalent of 370 g / mol, and a weight average molecular weight of 6,300. The hydroxyl value was 120 KOHmg / g. Next, propylene glycol monomethyl ether was added to the reaction solution to prepare a polymer solution having a solid content concentration of 40% of the curable polymer (D). This is designated as Sample 4.

Example 5
To a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and a gas introduction tube, 262.0 g of propylene glycol monomethyl ether acetate was added and stirred while replacing with nitrogen, and the temperature was raised to 120 ° C. Next, 64.4 g (0.35 mol) of 2-ethylhexyl acrylate, 71.0 g (0.5 mol) of glycidyl methacrylate and dicyclopentanyl methacrylate 6 having a glass transition temperature of −70 ° C. as a homopolymer. 18.8 g of t-butylperoxy-2-ethylhexanoate (polymerization initiator, NOF Corporation) was added to a monomer mixture consisting of .6 g (0.03 mol) and methyl methacrylate 12.0 (0.12 mol). The product to which Perbutyl O) was added was dropped into the flask over 2 hours from the dropping funnel. After completion of the dropping, the mixture was further stirred at 120 ° C. for 2 hours to carry out a copolymerization reaction, thereby producing an addition copolymer (a precursor of a curable polymer). Thereafter, the inside of the flask was replaced with air, and 36.0 g (0.5 mol) of acrylic acid, 0.6 g of triphenylphosphine (catalyst) and 0.2 g of methylhydroquinone were charged into the above addition copolymer solution. The reaction was continued for 10 hours at 110 ° C., and the epoxy group was cleaved by the reaction of the epoxy group derived from glycidyl methacrylate and acrylic acid, and at the same time, a polymerizable unsaturated bond was introduced into the side chain of the polymer. Next, 21.3 g (0.14 mol) of tetrahydrophthalic anhydride was added to the reaction system, and the reaction was continued at 110 ° C. for 3 hours. The hydroxyl group generated by the cleavage of the epoxy group and the anhydrous tetrahydrophthalic anhydride Physical groups were reacted to introduce a carboxy group into the side chain. The polymerizable polymer (A) thus obtained had a Tg of −20 ° C., an acid value of 34 KOH mg / g, an unsaturated group equivalent of 460 g / mol, and a weight average molecular weight of 7,100. there were. The hydroxyl value was 87 KOHmg / g. Next, propylene glycol monomethyl ether was added to the reaction solution to prepare a polymer solution having a solid content concentration of 40% of the curable polymer (E). This is designated as Sample 5.

Example 6
The amount of glycidyl methacrylate used is 49.7 g (0.35 mol), the amount of methyl methacrylate used is 27.0 (0.27 mol), and the amount of t-butylperoxy-2-ethylhexanoate is used. A curable polymer (F) was obtained in the same manner as in Example 5 except that 18.0 g and the amount of acrylic acid used was changed to 25.2 g (0.35 mol). The polymer had a Tg of −8 ° C., an acid value of 11 KOH mg / g, an unsaturated group equivalent of 560 g / mol, and a weight average molecular weight of 5,600. The hydroxyl value was 88 KOHmg / g. Next, propylene glycol monomethyl ether was added to the reaction solution to prepare a polymer solution having a solid content concentration of 40% of the curable polymer (F). This is designated as Sample 6.

Example 7
A curable polymer (G) was obtained in the same manner as in Example 1 except that the amount of tetrahydrophthalic anhydride used was changed to 44.1 g (0.29 mol). The polymer had a Tg of -11 ° C., an acid value of 60 KOH mg / g, an unsaturated group equivalent of 390 g / mol, and a weight average molecular weight of 7,000. The hydroxyl value was 85 KOHmg / g. Next, propylene glycol monomethyl ether was added to the reaction solution to prepare a polymer solution having a solid content concentration of 40% of the curable polymer (G). This is designated as Sample 7.

Example 8
The curable polymer (I) was prepared in the same manner as in Example 1 except that 14.0 g (0.14 mol) of succinic anhydride was used instead of 21.3 g (0.14 mol) of tetrahydrophthalic anhydride. Got. The polymer had a Tg of −12 ° C., an acid value of 33 KOH mg / g, an unsaturated group equivalent of 340 g / mol, and a weight average molecular weight of 6,100. The hydroxyl value was 131 KOHmg / g. Next, propylene glycol monomethyl ether was added to the reaction solution to prepare a polymer solution having a solid content concentration of 40% of the curable polymer (H). This is designated as Sample 8.

Example 9
The curable polymer (J) was prepared in the same manner as in Example 1 except that 2.8 g (0.03 mol) of norbornene was used instead of 6.6 g (0.03 mol) of dicyclopentanyl methacrylate. Obtained. The polymer had a Tg of −5 ° C., an acid value of 32 KOH mg / g, an unsaturated group equivalent of 350 g / mol, and a weight average molecular weight of 6,500. The hydroxyl value was 129 KOH mg / g. Next, propylene glycol monomethyl ether was added to the reaction solution to prepare a polymer solution having a solid content concentration of 40% of the curable polymer (I). This is designated as Sample 9.

Example 10
To a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and a gas introduction tube, 267.5 g of propylene glycol monomethyl ether acetate was added, stirred while replacing with nitrogen, and heated to 120 ° C. Next, a monomer mixture consisting of 6.6 g (0.03 mol) of dicyclopentenyl methacrylate, 49.7 g (0.27 mol) of 2-ethylhexyl acrylate and 50.4 g (0.7 mol) of acrylic acid was added to a monomer mixture. 2 g of t-butylperoxy-2-ethylhexanoate (polymerization initiator, manufactured by NOF Corporation, perbutyl O) was added dropwise into the flask over 2 hours from the dropping funnel. After completion of the dropping, the mixture was further stirred at 120 ° C. for 2 hours to carry out a copolymerization reaction, thereby producing an addition copolymer. Thereafter, the inside of the flask was replaced with air, and 56.8 g (0.4 mol) of glycidyl methacrylate, 0.6 g of triphenylphosphine (catalyst) and 0.2 g of methylhydroquinone were charged into the above addition copolymer solution. The reaction was continued at 110 ° C. for 10 hours, and a polymerizable unsaturated bond was introduced into the side chain of the polymer by the reaction of the carboxy group derived from acrylic acid and the epoxy group of glycidyl methacrylate to obtain a curable polymer (M). The polymer had a Tg of −5 ° C., an acid value of 92 KOH mg / g, an unsaturated group equivalent of 460 g / mol, and a weight average molecular weight of 10,000. The hydroxyl value was 123 KOHmg / g. Next, propylene glycol monomethyl ether was added to the reaction solution to prepare a polymer solution having a curable polymer (J) concentration of 40%. This is designated as Sample 10.

Comparative Example 1
Instead of 49.7 g (0.27 mol) of 2-ethylhexyl acrylate, 38.3 g (0.27 mol) of n-butyl methacrylate and use of t-butylperoxy-2-ethylhexanoate A curable polymer (K) was obtained in the same manner as in Example 1 except that the amount was changed to 17.6 g. The polymer had a Tg of 30 ° C., an acid value of 34 KOH mg / g, an unsaturated group equivalent of 330 g / mol, and a weight average molecular weight of 6,700. The hydroxyl value was 134 KOHmg / g. Next, propylene glycol monomethyl ether was added to the reaction solution to prepare a polymer solution having a solid content concentration of 40% of the curable polymer (K). This is designated as Sample 11.

Comparative Example 2
Use 72.4 g (0.27 mol) of phenylphenoxyethyl acrylate instead of 49.7 g (0.27 mol) of 2-ethylhexyl acrylate, and use of t-butylperoxy-2-ethylhexanoate A curable polymer (L) was obtained in the same manner as in Example 1 except that the amount was changed to 21.8 g. The polymer had a Tg of 22 ° C., an acid value of 29 KOH mg / g, an unsaturated group equivalent of 390 g / mol, and a weight average molecular weight of 6800. The hydroxyl value was 116 KOHmg / g. Next, propylene glycol monomethyl ether was added to the reaction solution to prepare a polymer solution having a solid content concentration of 40% of the curable polymer (L). This is designated as Sample 12.

  Table 1 shows the compositions and properties of the curable polymers obtained in Examples 1 to 10 and Comparative Examples 1 and 2.

Example 11
Using the samples 1 to 12 prepared in Examples 1 to 10 and Comparative Examples 1 and 2, a transparent photosensitive polymer composition (transparent resist) was prepared by the following formulation.
(Combination)
Samples 1 to 12 (polymer only) 25.0 parts by weight Trimethylolpropane triacrylate (reactive diluent) 3.0 parts by weight Irgacure 907 (photopolymerization initiator, manufactured by BASF Japan Ltd.) 0.2 parts by weight High Cure ABP (Photopolymerization initiator, manufactured by Kawaguchi Pharmaceutical Co., Ltd.) 0.1 parts by mass Propylene glycol monomethyl ether (solvent) 31.0 parts by mass In addition, the numbers (No. 1 to No. 12) of the photosensitive polymer composition are used. Correspond to the sample numbers (No. 1 to No. 12). Further, the mass of the sample does not include the solvent used for the preparation of the polymer solution, and the amount of the solvent contained in each sample is added to the solvent as a blending component.

<Evaluation of transparent resist>
Adhesion and transparency were evaluated by the methods shown below. The results are shown in Table 2.
Adhesion:
The prepared transparent resist is spin-coated on a 5 cm square glass substrate (non-alkali glass substrate) so that the final cured coating thickness is 2.5 μm, and then heated at 90 ° C. for 3 minutes. The solvent was volatilized. Next, the entire surface of the coating film was exposed (exposure amount 50 mJ / cm ² ), photocured, and then baked at 230 ° C. for 30 minutes to obtain a cured coating film. About this coating film, the cross cut test was done according to JISK5400, the peeling state of 100 cross cuts was observed visually, and the adhesiveness was evaluated on the following references | standards.
○: No separation was observed.
X: Exfoliation is observed in 10% or more of the whole transparency:
The coating film formed on the glass substrate was further left in a dryer at 230 ° C. for 1 hour, and the light transmittance at 400 nm of the coating film before and after the heat treatment was measured with a spectrophotometer. Transparency was evaluated.
◎: Change rate of transmittance is 0.5% or less ○: Change rate of transmittance is 1% or less ×: Change rate of transmittance is 1% or more

  From the results shown in Table 2, the transparent resist of the present invention is excellent in transparency and adhesion, and in particular, the transparent resist (No. 5 and 6) copolymerized with methyl methacrylate as the monomer (c) is more excellent. It turns out that it has transparency. On the other hand, the transparent resists (No. 11 and 12) using a curable polymer having a glass transition temperature exceeding 10 ° C. had insufficient adhesion.

Example 12
<Preparation of photosensitive polymer composition (dye type)>
Using the samples 1 to 12 prepared in Examples 1 to 10 and Comparative Examples 1 to 2, a photosensitive polymer composition (dye type) containing a dye (acid green 3) by mixing the following components according to the following composition: Prepared.
In addition, the number (No.1-No.12) of the photosensitive polymer composition respond | corresponds to the sample number (No.1-No.12) used. Further, the mass of the sample does not include the solvent used for the preparation of the polymer solution, and the amount of the solvent contained in each sample is added to the solvent as a blending component.

(Composition) Mass parts Samples 1 to 12 (polymer only) 32.5
Trimethylolpropane triacrylate (reactive diluent) 15.6
Irgacure 907 (photopolymerization initiator, manufactured by BASF Japan) 1.3
acid green 3 5.2
Propylene glycol monomethyl ether (solvent) 45.4

<Evaluation of color resist (dye type)>
The alkali developability, sensitivity, and solvent resistance were evaluated by the following methods. The results are shown in Table 2.
(1) Pattern formation by color resist After spin coating the prepared color resist (dye type) on a 5 cm square glass substrate (non-alkali glass substrate) so that the thickness after exposure is 2.5 μm, The solvent was volatilized by heating at 90 ° C. for 3 minutes. Next, a photomask having a predetermined pattern was disposed at a distance of 100 μm from the coating film, and the coating film was exposed through this photomask (exposure amount 150 mJ / cm ² ), and the exposed portion was photocured. Next, an unexposed part is dissolved and developed by spraying an aqueous solution containing 0.1% by mass of sodium carbonate at a temperature of 23 ° C. and a pressure of 0.2 MPa, and then baking is performed at 230 ° C. for 30 minutes. A predetermined pattern was formed.

(2) Evaluation of pattern formed from color resist About the pattern formed as mentioned above, alkali developability, sensitivity, and adhesiveness were evaluated as follows.
(2-1) Alkali developability Alkali developability was confirmed by the residue after alkali development and the development form. The residue after alkali development was confirmed by observing the pattern after alkali development using an electron microscope S-3400 manufactured by Hitachi High-Technologies Corporation. The criteria for this evaluation are as follows.
◯: No residue ×: Residue (2-2) Sensitivity The quality of the sensitivity was determined by performing alkali development using the above spray for 30 seconds and measuring the decrease in pattern thickness before and after alkali development. Since it can be said that the sensitivity of this pattern thickness is better as the amount of decrease is smaller, the criteria for this evaluation were as follows.
○: Less than 0.15 μm Δ: 0.15 μm or more and less than 0.20 μm ×: 0.20 μm or more (2-3) Adhesiveness,
The size of the minimum pattern capable of pattern formation was observed with an optical microscope, and the adhesion was evaluated according to the following criteria. In addition, a fine pattern can be formed, so that adhesiveness is favorable.
○: Minimum pattern size is less than 10 μm ×: Minimum pattern size is 10 μm or more

(3) Evaluation of solvent resistance On a 5 cm square glass substrate (non-alkali glass substrate), the above color resist was spin-coated so that the thickness after exposure was 2.5 μm, and then at 90 ° C. for 3 minutes. The solvent was evaporated by heating. Next, the coating film was exposed to light having a wavelength of 365 nm, the exposed portion was photocured, and then left in a drier at a baking temperature of 230 ° C. for 30 minutes to form a cured coating film. 200 mL of n-methyl-2-pyrrolidone is put into a glass bottle with a capacity of 500 mL, and the test piece with the cured coating film is immersed therein, and then the color change after 1 hour at 23 ° C. is measured with a spectrophotometer UV. Measurement was performed with -1650 PC (manufactured by Shimadzu Corporation), and solvent resistance was evaluated based on the result. The criteria for this evaluation are as follows.
○: ΔE ^* ab is less than 0.25 Δ: ΔE ^* ab is 0.25 or more and less than 0.3 ×: ΔE ^* ab is 0.3 or more

  As can be seen from the results in Table 2, the color resists (No. 1 to 10) using the photosensitive polymer composition (dye type) of the present invention are excellent in alkali developability, sensitivity, solvent resistance and adhesion. Performance. However, the color resist (No. 6) using a curable polymer having an unsaturated group equivalent of 560 g / mol tends to decrease sensitivity and solvent resistance. On the other hand, the color resist (No. 11-12) using the photosensitive polymer composition of Comparative Examples 1-2 is inferior to alkali developability and adhesiveness.

Example 13
<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, C.I. 10 parts of I Pigment Green 36, 33.75 parts of propylene glycol monomethyl ether acetate, and 6.25 parts of dispersant (Disperbyk-161 manufactured by Big Chemie Japan Co., Ltd.) are added and dispersed by mixing for 3 hours in a paint shaker. By doing so, a green pigment dispersion was prepared.
Using this green pigment dispersion, a photosensitive polymer composition (pigment type) containing a green pigment was prepared by the following formulation. In addition, the number (No.1-No.12) of the photosensitive polymer composition respond | corresponds to the sample number (No.1-No.12) used. Further, the mass of the sample does not include the solvent used for the preparation of the polymer solution, and the amount is added to the solvent as a blending component.

(Composition) Mass parts Samples 1 to 12 (polymer only) 8.03
Trimethylolpropane triacrylate (reactive diluent) 6.5
Irgacure 907 (photopolymerization initiator, manufactured by BASF Japan) 1.66
High Cure ABP (photopolymerization initiator, manufactured by Kawaguchi Pharmaceutical) 0.83
Green pigment dispersion 50.0
Propylene glycol monomethyl ether (solvent) 52.6

<Evaluation of color resist (pigment type)>
In the same manner as in Example 12 (dye type), alkali developability, sensitivity, and solvent resistance were evaluated, and pigment dispersibility was evaluated by the following method. The results are shown in Table 2.
Pigment dispersibility:
In the above formulation, a green resin composition excluding the photopolymerization initiator was prepared, and the viscosity was measured with an E-type viscometer immediately after preparation and after standing in a constant temperature bath at 40 ° C. for 7 days. The quality of dispersion was evaluated.
A (Very good dispersibility): Viscosity change rate of less than 15% B (Dispersibility is good): Viscosity change rate of 15% or more and less than 20% Δ (Dispersibility is slightly insufficient): Viscosity change rate of 20% or more 25 Less than% x (Inferior in dispersibility): Viscosity change rate of 25% or more

  As can be seen from the results in Table 2, the color resists (Nos. 1 to 10) using the photosensitive polymer composition (pigment type) of the present invention are excellent in alkali developability, sensitivity, solvent resistance and adhesion. When the curable polymer using the (meth) acrylate monomer (a-2) having an aromatic ring is used (No. 3 and No. 4), the pigment dispersibility is remarkably excellent. I understand that. On the other hand, the color resist (No. 11-12) using the photosensitive polymer composition of Comparative Examples 1-2 is inferior to alkali developability and adhesiveness.

Example 14
<Preparation of photosensitive polymer composition (mixture type of dye / pigment)>
A photosensitive polymer composition (dye / pigment type) was prepared by the following composition using 40 parts of a green pigment dispersion prepared in the same manner as in Example 13 and 2 parts of a dye (acid green 3). In addition, the number (No.1-No.12) of the photosensitive polymer composition respond | corresponds to the sample number (No.1-No.12) used. Moreover, the quantity of the curable polymer does not contain a solvent, and the quantity of the solvent contained in each sample is added to the solvent as a blending component.

(Composition) Mass parts Samples 1 to 12 (polymer only) 19.0
Trimethylolpropane triacrylate (reactive diluent) 11.5
Irgacure 907 (photopolymerization initiator, manufactured by BASF Japan) 2.4
High Cure ABP (photopolymerization initiator, manufactured by Kawaguchi Pharmaceutical) 0.64
acid green 3 2.0
Green pigment dispersion 40.0
Propylene glycol monomethyl ether (solvent) 36.6

<Evaluation of photosensitive polymer composition (mixture type of dye / pigment)>
The performance when using the above photosensitive polymer composition as a color resist (dye / pigment mixed type) was evaluated in the same manner as in Example 14. The results are shown in Table 2.

  As can be seen from the results in Table 2, the color resists (No. 1 to 10) using the photosensitive polymer composition (dye / pigment type) of the present invention have alkali developability, sensitivity, solvent resistance and adhesion. In particular, when a curable polymer using the (meth) acrylate monomer (a-2) having an aromatic ring is used (No. 3 and No. 4), the pigment dispersibility is remarkable. It turns out that it is excellent. On the other hand, the color resist (No. 11-12) using the photosensitive polymer composition of Comparative Examples 1-2 is inferior to alkali developability and adhesiveness.

  According to the present invention, when used as a photosensitive material, a curable polymer excellent in sensitivity, developability, solvent resistance, adhesion to a substrate and dye dispersibility can be efficiently obtained. In addition, the cured coating film formed from the photosensitive polymer composition of the present invention is excellent in sensitivity, developability, solvent resistance, adhesion to the substrate, and dispersibility of the dye. When used as a photosensitive material for a color filter, a color filter having a colored pattern excellent in solvent resistance, adhesion to a substrate and dispersibility of a dye can be obtained.

Claims (13)

(Meth) acrylate monomer (a) having a glass transition temperature of 10 ° C. or less when made as a homopolymer (5) to 40 mol%, (meth) acrylic monomer having epoxy group or carboxy group (b) 30 to 85 mol% And other radical polymerizable monomers (c) [excluding N-substituted maleimide] The side obtained by subjecting 0 to 35 mol% of the addition copolymer to the following modification reaction (I) or (II) groups in the chain has a hydroxy group and a polymerizable unsaturated bond, the glass transition temperature is at 20 ° C. or less and a curable polymer weight average molecular weight in terms of polystyrene is 1,000 to 50,000 And
The (meth) acrylate monomer (a) is a (meth) acrylate (a-1) having no aromatic ring and / or a (meth) acrylate (a-2) having an aromatic ring, and at least one of (a) is A curable polymer, which is 2-ethylhexyl acrylate .
Modification method of (I):
A method of cleaving an epoxy group contained in a molecule of an addition copolymer with a polymerizable unsaturated monobasic acid (d), and reacting a polybasic acid or an anhydride thereof (e) with a hydroxy group formed by the cleavage .
Modification method of (II):
A method of reacting a carboxy group contained in a molecule of an addition copolymer with a (meth) acrylate monomer (f) having a functional group reactive with the carboxy group. The other radical polymerizable monomer (c) is a polymerizable monomer (c-1) having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms, a norbornene monomer (c-2), and 1 to 3 carbon atoms. The curable polymer according to claim 1, which is at least one monomer selected from lower alkyl methacrylate (c-3). The curable polymer according to claim 1, wherein the acid value is 10 to 300 KOH mg / g, the hydroxyl value is 70 to 300 KOH mg / g, and the unsaturated group equivalent is 100 to 4,000 g / mol. The curable polymer according to any one of claims 1 to 3, wherein the (meth) acrylic monomer (b) is a (meth) acrylic monomer (b-1) having an epoxy group, and the modification reaction is the method of (I). .   The curable polymer according to any one of claims 1 to 4, wherein the addition copolymer is a copolymer containing the radical polymerizable monomer (c) in a proportion of 2 to 30 mol%. The curable polymer according to any one of claims 1 to 5, wherein the (meth) acrylate monomer (a) has a glass transition temperature of -100 ° C to 0 ° C when it is a homopolymer. The curable polymer according to any one of claims 1 to 6 , wherein at least one of (meth) acrylate (a-2) is m-phenoxybenzyl acrylate. The curable polymer according to any one of claims 1 to 7 , wherein at least one of the other radical polymerizable monomers (c) is dicyclopentanyl methacrylate or methyl methacrylate. The polymer composition containing the curable polymer in any one of Claims 1-8 , a solvent, and / or a reactive diluent. Furthermore, the polymer composition of Claim 9 containing the photoinitiator and the coloring agent mix | blended arbitrarily. A photosensitive material for a color filter comprising the polymer composition according to claim 10 . A color filter formed using the photosensitive material for a color filter according to claim 11 . An image display device comprising the color filter according to claim 12 .