JP2007114604A - Photosensitive composition and color filter - Google Patents

Abstract

It is possible to form a hardened portion (color filter) having a high sensitivity, excellent developability, and a sharp and smooth surface with high hardness and suppressed pixel defects even with a small exposure amount.
Photosensitivity comprising an acrylic copolymer containing a copolymer unit having a polyfunctional unsaturated double bond having three or more functions together with a polyfunctional polymerizable compound having two or more functions, a photopolymerization initiator, and a colorant. It is a composition.
[Selection figure] None

Description

  The present invention relates to a photosensitive composition and a color filter suitable for producing a color filter used for a liquid crystal display element or a solid-state image sensor, and more particularly to a transmissive, reflective or transflective color liquid crystal display device, and color imaging. The present invention relates to a photosensitive composition suitable for producing a color filter used for a tube element or the like, and a color filter using the same.

  Conventionally, when producing a color filter using a colored resin composition having photosensitivity, this colored resin composition is applied onto a substrate and dried, and then the dried coating film is exposed to a desired pattern. It can be produced by performing a development process to form a pixel pattern on the substrate.

However, when the exposure amount is small, pixel defects such as undercut, peeling, and chipping are likely to occur in the pixel portion during development, and the surface of the pixel portion is rough and it is difficult to obtain smoothness. Conversely, the exposure amount is large. In some cases, undissolved substances and development residues tend to be generated in non-pixel portions (uncured portions). Therefore, the range of the appropriate exposure amount in which both the pixel portion (cured portion) and the non-pixel portion can be provided as pixels having no defect is very narrow. In some cases, an exposure region that satisfies both can be obtained. There was no case.
In particular, in recent years, the manufacturing tact time tends to be shortened, and a problem has arisen that it is not possible to cope with the reduction in exposure amount accompanying the shortening.

  As one of means for enhancing the curability by exposure, there is a method of introducing a polymerizable double bond into the side chain of the alkali-soluble resin. In this case, the introduction of the polymerizable double bond into the side chain is accompanied by difficulty in synthesis, and from the viewpoint of curing, it is usual that only one polymerizable double bond is required per copolymerized unit. It was.

  However, recently, the demand for liquid crystal display elements (LCD) for TV applications is increasing, and the size of the substrate is increasing. In the manufacturing process of the color filter, if it is attempted to match the tact time of a conventional process, the exposure time is substantially shortened and the desired degree of curing cannot be obtained. Therefore, the sensitivity and curing performance that have been conventionally required are not always sufficient, and there is a strong demand for further increasing the sensitivity and improving the curability of photosensitive compositions used for color filter applications.

  As a technique related to the above, an epoxy compound having an ethylenically unsaturated double bond is added to a polymer having a carboxyl group, and an isocyanate having an ethylenically unsaturated double bond is added to the hydroxyl group generated by the addition reaction. A photopolymerizable composition using a binder resin (polymer) having two double bonds in the side chain after an addition reaction is disclosed (for example, see Patent Document 1). Although this composition is said to be excellent in curability and solubility in an alkaline developer, the photosensitivity and curing performance when the substrate is enlarged while maintaining the tact time during color filter production, that is, the exposure amount is high. The decrease in photosensitivity and curing performance in the case of decreasing cannot always be covered.

In addition to the above, a colored photosensitive composition containing a photosensitive resin having a carbon-carbon unsaturated bond (for example, see Patent Document 2), and a (meth) acryloyloxyalkyl isocyanate compound via a carboxyl group or a hydroxyl group. There is also a disclosure relating to a photosensitive resin composition containing a copolymer resin having a partially reacted product as a structural unit (see, for example, Patent Document 3), but in either case, the photosensitivity and curability are insufficient. .
JP 2002-14468 A JP-A-4-369653 JP 2000-298337 A

  As described above, although various studies have been made on the technology in which the resin component has an unsaturated site, as described above, until the examination to ensure the sensitivity when the exposure time is shortened more than before due to the market trend Therefore, when a color filter is produced while maintaining the tact time as the size of the substrate increases, the present situation is that sufficient sensitivity and curing degree cannot be obtained.

  The present invention has been made in view of the above, and has a high-sensitivity cured portion having high sensitivity, excellent developability, low exposure (that is, short tact time), high hardness, and reduced pixel defects. It is an object to provide a photosensitive composition that can be formed with a smooth surface, and a smooth color filter that has a good shape with few pixel defects such as pixel defects and pixel peeling, and to achieve the object. To do.

Specific means for achieving the above object are as follows.
<1> In the photosensitive composition containing an acrylic copolymer, a polyfunctional polymerizable compound having two or more functions, a photopolymerization initiator, and a colorant, the acrylic copolymer is a polyfunctional polyfunctional compound having three or more functions. The photosensitive composition is a copolymer containing a copolymer unit having a saturated double bond.
<2> The copolymer unit has a structure in which the polyunsaturated double bond is added to a side chain by addition reaction of a (meth) acryloylalkyl isocyanate compound having a polyunsaturated double bond via a hydroxyl group. It is a photosensitive composition as described in said <1> which is a unit.

<3> The acrylic copolymer has a copolymerization ratio of the copolymerized unit of 1 to 50 mol%, an acid value of 5 to 200 mgKOH / g, and a weight average molecular weight of 5,000 to 50,000. It is a photosensitive composition as described in <1> or <2>.
<4> The acrylic copolymer includes at least one type of structural unit represented by the following general formula (1) 0 to 50 mol% and at least one type of structural unit represented by the following general formula (2) 20 to 80 mol. % Is the photosensitive composition according to any one of <1> to <3>.

In the general formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ² represents an aromatic carbocycle, and R ³ represents an alkyl group or an aralkyl group.

  <5> A color filter comprising the photosensitive composition according to any one of <1> to <4>.

  According to the present invention, it is possible to form a hardened portion having a high shape and a smooth surface with high sensitivity and excellent developability, and with a small amount of exposure (that is, a short tact time) and a high hardness and suppressed pixel defects. It is possible to provide a photosensitive composition that can be formed, and a smooth color filter that has less pixel defects such as pixel chipping and pixel peeling and has a good shape.

  Hereinafter, the photosensitive composition of the present invention and a color filter using the photosensitive composition will be described in detail.

The photosensitive composition of the present invention comprises an acrylic copolymer containing a copolymer unit having a trifunctional or higher polyunsaturated double bond, a bifunctional or higher polyfunctional polymerizable compound, a polymerization initiator, It contains at least a colorant, and is generally composed of a solvent, and can be composed of other components as required.
Hereinafter, each component which comprises the photosensitive composition of this invention is explained in full detail.

-Acrylic copolymer-
The photosensitive composition of the present invention is a copolymer containing a copolymer unit having a polyunsaturated double bond having three or more functions as an acrylic copolymer (hereinafter referred to as “copolymer according to the present invention”). May contain at least one kind).

In the present invention, a structure including a copolymer unit having a polyunsaturated double bond having a tri- or higher functionality is used, and a short tact time is maintained while maintaining developability while suppressing generation of undissolved substances and development residues. Even when the exposure amount during pattern exposure is reduced by using time, photocuring can be performed well, and during development, film peeling or chipping of the cured region occurs, or even if a pattern is obtained, the curing reaction does not occur. It can be effectively avoided that the vicinity of the substrate of the pattern does not reach the inside of the film and is overhanged (undercut), or the pattern surface after development is partially dissolved and roughened.
In the present invention, it is possible to form a rectangular or forward-tapered cured portion with high hardness and reduced pixel defects by pattern exposure with a small exposure amount, and the surface of the cured portion can be configured smoothly. . This is particularly effective for producing a color filter capable of displaying a sharp and vivid image, for example.

  Examples of the copolymer containing a copolymer unit having a trifunctional or higher polyunsaturated double bond include, for example, methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, methyl acrylate, ethyl acrylate, 50 to 90 mol% of at least one acrylic acid ester or methacrylic acid ester such as butyl acrylate, benzyl methacrylate or benzyl acrylate as a monomer component, and at least one acid component monomer such as methacrylic acid or acrylic acid to 5 to 5% A copolymer having a structure in which 2-isocyanatotrimethylolethane triacrylate is added to a copolymer containing 20 mol% and 5 to 20 mol% of hydroxyethyl acrylate and / or hydroxyethyl methacrylate as a monomer component. A polymer etc. are mentioned.

  Among the copolymers according to the present invention, a (meth) acryloylalkyl isocyanate compound having a polyunsaturated double bond via a hydroxyl group in the molecule as a copolymer unit constituting the copolymer is trifunctional or higher. A polymer containing a structural unit to which a polyunsaturated double bond is added as a side chain by addition reaction is preferable.

  The copolymer according to the present invention includes, for example, a monomer having a polyunsaturated double bond with respect to the synthesized copolymer after a desired copolymer is synthesized by copolymerizing a plurality of monomers. The presence of a component, preferably a (meth) acryloylalkylisocyanate compound having a polyunsaturated double bond, causes an addition reaction to form 3 polyunsaturated double bonds in the constituent units constituting the copolymer. It can be obtained by adding more functional groups.

  Among them, as a constituent unit constituting the copolymer, it contains 0 to 50 mol% of at least one constituent unit represented by the following general formula (1), and at least one constituent unit represented by the following general formula (2). An acrylic copolymer containing 20 to 80 mol% of one kind is preferable.

In the general formulas (1) and (2), R ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
Examples of the alkyl group having 1 to 5 carbon atoms represented by R ¹ include a methyl group, an ethyl group, a butyl group, an isobutyl group, a t-butyl group, and an amyl group. Among these, an alkyl group having 1 to 3 carbon atoms is preferable, and a methyl group and an ethyl group are particularly preferable.

In the general formula (1), R ² represents an aromatic carbon ring, aromatic carbocyclic ring having 6 to 14 carbon atoms are preferred. Examples thereof include a benzene ring and a naphthalene ring. Among them, an aromatic carbocyclic ring having 6 to 10 carbon atoms is preferable, and a benzene ring is particularly preferable.

In the general formula (2), R ³ represents an alkyl group or an aralkyl group.
The alkyl group represented by R ³ is preferably an alkyl group having 1 to 8 carbon atoms, and examples thereof include a methyl group, an ethyl group, a butyl group, an isobutyl group, a t-butyl group, an amyl group, and a hexyl group. . Among these, an alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group, an ethyl group, a butyl group, and an isobutyl group are particularly preferable.

The aralkyl group represented by R ³ is preferably an aralkyl group having 7 to 12 carbon atoms, and examples thereof include a benzyl group and a methylnaphthyl group. Among them, an aralkyl group having 7 to 11 carbon atoms is preferable, and a benzyl group is particularly preferable.

Among the above, in the present invention, in the general formula (1), R ¹ is a hydrogen atom and R ² is a phenyl group. In the general formula (2), R ¹ is a methyl group, An embodiment in which R ³ is a benzyl group is preferred.

  Specific examples of the structural unit represented by the general formula (1) or (2) are listed below. However, the present invention is not limited to these.

  In the acrylic copolymer according to the present invention, the copolymerization ratio of the copolymer units having a trifunctional or higher polyunsaturated double bond is preferably 1 to 50 mol%. As this copolymerization ratio, the range of 10-30 mol% is more preferable.

  The acid value of the acrylic copolymer according to the present invention is preferably in the range of 5 to 200 mgKOH / g. Furthermore, the range of 10-150 mgKOH / g is more preferable, and the range of 10-90 mgKOH / g is particularly preferable.

  Furthermore, the weight average molecular weight of the acrylic copolymer according to the present invention is preferably 5,000 to 50,000. Furthermore, the range of 7,000 to 30,000 is more preferable, and the range of 8,000 to 20,000 is particularly preferable.

  As content in the photosensitive composition of the acryl-type copolymer containing the copolymer unit which has a polyunsaturated double bond more than trifunctional, with respect to the total solid (mass) of this composition, 5-50 mass% is preferable and 20-30 mass% is more preferable. When the content is within the above range, the uncured region can ensure developability while suppressing the generation of undissolved substances and development residues during the development process, and the cured region has high hardness with a small exposure amount. As a result, it is possible to form a sharply hardened portion in which the occurrence of pixel defects is suppressed and with a smooth surface.

-Polyfunctional polymerizable compound having at least two functions-
The photosensitive composition of the present invention contains at least one bifunctional or higher polyfunctional polymerizable compound (hereinafter also simply referred to as “polymerizable compound”). As the polymerizable compound, a compound having at least two addition-polymerizable ethylenically unsaturated groups and having a boiling point of 100 ° C. or higher under normal pressure is preferable.

Examples of the compound having at least two addition-polymerizable ethylenically unsaturated groups and having a boiling point of 100 ° C. or higher at normal pressure include, for example, polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neo Pentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether After adding ethylene oxide or propylene oxide to polyfunctional alcohols such as tri (acryloyloxyethyl) isocyanurate, glycerin and trimethylolethane Converted into poly (meth) acrylate of pentaerythritol or dipentaerythritol, urethane acrylates described in JP-B-48-41708, JP-B-50-6034, JP-A-51-37193, Polyester acrylates described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, and epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid Examples include functional acrylates and methacrylates.
Furthermore, what is introduce | transduced as a photocurable monomer and an oligomer by Japan Adhesive Association magazine Vol.20, No.7 (p.300-308) can be used. Among these, tetrafunctional or higher acrylate compounds are more preferable.

  Further, a compound obtained by adding ethylene oxide or propylene oxide to the polyfunctional alcohol and then (meth) acrylated is described in JP-A-10-62986 as general formulas (1) and (2) together with specific examples thereof. These can also be used as polymerizable compounds.

Of the above, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and a structure in which these acryloyl groups are connected via ethylene glycol and propylene glycol residues are preferred. These oligomer types can also be used.
These polymerizable compounds can be used in combination of two or more, in addition to being used alone.

  The content of the bifunctional or higher polyfunctional polymerizable compound in the photosensitive composition is preferably 20 to 200 mass%, more preferably 50 to 120 mass%, based on the total solid content of the photosensitive composition. %. When the amount of the polyfunctional polymerizable compound is within the above range, it is effective in terms of photosensitivity and curability.

-Photopolymerization initiator-
The photosensitive composition of the present invention contains at least one photopolymerization initiator. This photopolymerization initiator is contained together with the above-mentioned bifunctional or higher polyfunctional polymerizable compound, and a high degree of curing can be obtained and the curability can be controlled as desired.

  Examples of the photopolymerization initiator include halomethyloxadiazole described in JP-A-57-6096; halomethyl-s-triazine described in JP-B-59-1281, JP-A-53-133428, and the like. Isoactive halogen compounds; aromatic carbonyl compounds such as ketals, acetals, or benzoin alkyl ethers described in US Pat. No. 4,318,879, European Patent Publication EP-88050A; aromatics such as benzophenones described in US Pat. No. 4,1994,420 Ketone compounds; (thio) xanthones or acridine compounds described in Fr-2456541; compounds such as coumarins or lophine dimers described in JP-A-10-62986; sulfonium organics described in JP-A-8-015521 Use boron complex etc. Kill.

  Photoinitiators include acetophenone, ketal, benzophenone, benzoin, benzoyl, xanthone, triazine, halomethyloxadiazole, acridine, coumarins, lophine dimers, biimidazole Photopolymerization initiators such as systems are preferred.

  Examples of the acetophenone-based photopolymerization initiator include 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, p-dimethylaminoacetophenone, Preferable examples include 4′-isopropyl-2-hydroxy-2-methyl-propiophenone.

  Preferable examples of the ketal photopolymerization initiator include benzyldimethyl ketal and benzyl-β-methoxyethyl acetal.

  Examples of the benzophenone-based photopolymerization initiator include benzophenone, 4,4 ′-(bisdimethylamino) benzophenone, 4,4 ′-(bisdiethylamino) benzophenone, 4,4′-dichlorobenzophenone, 1-hydroxy- Cyclohexyl-phenyl-ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-tolyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone A preferred example is 1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1.

  Preferred examples of the benzoin-based or benzoyl-based photopolymerization initiator include benzoin isopropyl ether, benzoin isobutyl ether, benzoin methyl ether, methyl o-benzoyl bezoate, and the like.

  Preferable examples of the xanthone photopolymerization initiator include diethylthioxanthone, diisopropylthioxanthone, monoisopropylthioxanthone, chlorothioxanthone, and the like.

  Examples of the triazine photopolymerization initiator include 2,4-bis (trichloromethyl) -6-p-methoxyphenyl-s-triazine, 2,4-bis (trichloromethyl) -6-p-methoxystyryl. -S-triazine, 2,4-bis (trichloromethyl) -6- (1-p-dimethylaminophenyl) -1,3-butadienyl-s-triazine, 2,4-bis (trichloromethyl) -6-biphenyl -S-triazine, 2,4-bis (trichloromethyl) -6- (p-methylbiphenyl) -s-triazine, p-hydroxyethoxystyryl-2,6-di (trichloromethyl) -s-triazine, methoxystyryl -2,6-di (trichloromethyl-s-triazine, 3,4-dimethoxystyryl-2,6-di (trichloromethyl) -s- Liazine, 4-Benzoxolane-2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN, N- (diethoxycarbonylamino) -phenyl) -2,6-di (Chloromethyl) -s-triazine, 4- (pN, N- (diethoxycarbonylamino) -phenyl) -2,6-di (chloromethyl) -s-triazine and the like can be preferably exemplified.

  Examples of the halomethyloxadiazole-based photopolymerization initiator include 2-trichloromethyl-5-styryl-1,3,4-oxodiazole, 2-trichloromethyl-5- (cyanostyryl) -1, 3,4-oxodiazole, 2-trichloromethyl-5- (naphth-1-yl) -1,3,4-oxodiazole, 2-trichloromethyl-5- (4-styryl) styryl-1,3 Preferred examples include 1,4-oxodiazole.

  Preferred examples of the acridine-based photopolymerization initiator include 9-phenylacridine, 1,7-bis (9-acridinyl) heptane, and the like.

  Examples of the coumarin-based photopolymerization initiator include 3-methyl-5-amino-((s-triazin-2-yl) amino) -3-phenylcoumarin, 3-chloro-5-diethylamino-(( Preferred examples include s-triazin-2-yl) amino) -3-phenylcoumarin, 3-butyl-5-dimethylamino-((s-triazin-2-yl) amino) -3-phenylcoumarin, and the like. .

  Examples of the lophine dimer-based photopolymerization initiator include 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer and 2- (o-methoxyphenyl) -4,5-diphenylimidazolyl dimer. And 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer and the like.

  Preferable examples of the biimidazole-based photopolymerization initiator include 2-mercaptobenzimidazole and 2,2′-benzothiazolyl disulfide.

  In addition to the above, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, O-benzoyl-4 ′-(benzmercapto) benzoyl-hexyl-ketoxime, 2,4,6-trimethylphenyl Examples thereof include carbonyl-diphenyl phosphonyl oxide and hexafluorophospho-trialkylphenyl phosphonium salt.

In this invention, it is not limited to the above photoinitiator, Other well-known things can also be used. For example, vicinal polykettle aldonyl compounds disclosed in US Pat. No. 2,367,660, disclosed in US Pat. Nos. 2,367,661 and 2,367,670. α-carbonyl compounds, acyloin ethers disclosed in US Pat. No. 2,448,828, aromatics substituted with α-hydrocarbons disclosed in US Pat. No. 2,722,512 Group acyloin compounds, polynuclear quinone compounds disclosed in US Pat. Nos. 3,046,127 and 2,951,758, triallyl disclosed in US Pat. No. 3,549,367 Combination of imidazole dimer / p-aminophenyl ketone, benzothiazole compound / trihalomethy disclosed in Japanese Patent Publication No. 51-48516 And ru-s-triazine compounds.
Moreover, these photoinitiators can also be used together.

  As content in the photosensitive composition of a photoinitiator, 0.1-10.0 mass% is preferable with respect to the total solid of this composition, More preferably, it is 0.5-5.0 mass. %. When the content of the photopolymerization initiator is in the above range, the polymerization and curing can be performed satisfactorily and a high film strength can be obtained.

-Colorant-
The photosensitive composition of the present invention contains at least one colorant. As the colorant, conventionally known various dyes and pigments can be used alone or in admixture of two or more.

  As the pigment, various conventionally known inorganic pigments or organic pigments can be used. Further, considering that it is preferable to have a high transmittance, whether it is an inorganic pigment or an organic pigment, it is preferable to select a finer one as much as possible, and considering the handling properties, the average particle diameter of the pigment is 0.01. -0.1 micrometer is preferable and 0.01-0.05 micrometer is more preferable.

  Examples of inorganic pigments include metal compounds represented by metal oxides, metal complex salts, and the like. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, etc. And metal oxides of the above metals.

As an organic pigment, for example,
CIPigment Yellow 11, 24, 31, 53, 83, 93, 99, 108, 109, 110, 138, 139, 147, 150, 151, 154, 155, 167, 180, 185, 199;
CIPigment Orange 36, 38, 43, 71;
CIPigment Red 81, 105, 122, 149, 150, 155, 171, 175, 176, 177, 209, 220, 224, 242, 254, 255, 264, 270;
CIPigment Violet 19, 23, 32, 39;
CIPigment Blue 1, 2, 15, 15: 1, 15: 3, 15: 6, 16, 22, 60, 66;
CIPigment Green 7, 36, 37;
CIPigment Brown 25, 28;
CIPigment Black 1, 7;
And carbon black.

  In the present invention, those having a basic N atom in the structural formula of the pigment can be preferably used. A pigment having a basic N atom exhibits good dispersibility in the composition. Although the cause is not fully elucidated, it is presumed that the good affinity between the photosensitive polymerization component and the pigment has an influence.

  Examples of the pigment include the following. However, the present invention is not limited to these.

CIPigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185;
CIPigment Orange 36, 71;
CIPigment Red 122, 150, 171, 175, 177, 209, 224, 242, 254, 255, 264;
CIPigment Violet 19, 23, 32;
CIPigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66;
CIPigment Black 1;

The organic pigments can be used in combination of a plurality of types in order to increase color purity, in addition to the use of one type alone. Specific examples of combinations are shown below.
For example, as a red pigment, an anthraquinone pigment, a perylene pigment, a diketopyrrolopyrrole pigment alone or at least one of them, a disazo yellow pigment, an isoindoline yellow pigment, a quinophthalone yellow pigment, or a perylene red pigment And the like can be used. For example, as an anthraquinone pigment, C.I. I. Pigment Red 177, and perylene pigments include C.I. I. Pigment red 155, C.I. I. Pigment Red 224, and diketopyrrolopyrrole pigments include C.I. I. Pigment Red 254, and C.I. I. Mixing with Pigment Yellow 139 is preferred. The mass ratio of the red pigment to the yellow pigment is preferably 100: 5 to 100: 50. If it is less than 100: 5, it may be difficult to suppress the light transmittance of 400 to 500 nm and the color purity may not be increased. If it exceeds 100: 51, the dominant wavelength becomes shorter than the NTSC target hue. Deviation from may increase. In particular, the mass ratio is optimally in the range of 100: 10 to 100: 30. In addition, in the case of the combination of red pigments, it can adjust according to chromaticity.

  As the green pigment, a halogenated phthalocyanine pigment can be used alone, or a mixture thereof with a disazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment, or an isoindoline yellow pigment. For example, C.I. I. Pigment Green 7, 36, 37 and C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 180 or C.I. I. Mixing with Pigment Yellow 185 is preferred. The mass ratio of the green pigment to the yellow pigment is preferably 100: 5 to 100: 150. If the mass ratio is less than 100: 5, it may be difficult to suppress the light transmittance of 400 to 450 nm and the color purity may not be increased. If the mass ratio exceeds 100: 150, the dominant wavelength becomes longer. The deviation from the NTSC target hue may increase. The mass ratio is particularly preferably in the range of 100: 30 to 100: 120.

  As the blue pigment, a phthalocyanine pigment can be used alone, or a mixture of this with a dioxazine purple pigment can be used. For example, C.I. I. Pigment blue 15: 6 and C.I. I. Mixing with pigment violet 23 is preferred. The mass ratio of the blue pigment to the violet pigment is preferably 100: 0 to 100: 30, more preferably 100: 10 or less.

  Further, examples of the pigment for forming the black matrix include carbon, titanium carbon, iron oxide, titanium oxide, and the like. One kind can be used alone, or a plurality of kinds can be used in combination. A combination of carbon and titanium carbon is preferred. Moreover, as mass ratio at the time of combining carbon and titanium carbon, the range of 100: 0 to 100: 60 is preferable. If it is 100: 61 or more, the dispersion stability may decrease.

  There is no restriction | limiting in particular as said dye, A conventionally well-known dye can be used for a color filter use conventionally. When a dye is used as the colorant, a photosensitive curable colored resin composition can be obtained by uniformly dissolving the dye in the composition.

  Examples of the dye include JP-A 64-90403, JP-A 64-91102, JP-A-1-94301, JP-A-6-11614, Tokuho 2592207, U.S. Pat. 808,501, US Pat. No. 5,667,920, US Pat. No. 5,059,500, JP-A-5-333207, JP-A-6-35183, JP JP-A-6-51115, JP-A-6-194828, JP-A-8-2111599, JP-A-4-249549, JP-A-10-123316, JP-A-11-302283, JP-A-7- No. 286107, JP-A No. 2001-4823, JP-A No. 8-15522, JP-A No. 8-29771, JP-A No. 8-146215, JP-A-11-343437, JP-A-8-62416, JP-A-2002-14220, JP-A-2002-14221, JP-A-2002-14222, JP-A-2002-14223, JP-A-8. Examples thereof include the dyes described in JP-A No. 302224, JP-A-8-73758, JP-A-8-179120, JP-A-8-151531, and the like.

  The chemical structure includes pyrazole azo, anilino azo, triphenyl methane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, Examples include xanthene, phthalocyanine, benzopyran, and indigo dyes.

  In the case of a resist system that performs water or alkali development, acidic dyes and / or derivatives thereof are preferred from the viewpoint of completely removing the binder and / or dye in the photo-uncured part by development.

  In addition, direct dyes, basic dyes, mordant dyes, acid mordant dyes, azoic dyes, disperse dyes, oil-soluble dyes, food dyes, and / or derivatives thereof are also useful.

The acidic dye is not particularly limited as long as it has an acidic group such as sulfonic acid or carboxylic acid, but is soluble in an organic solvent or a developer, salt-forming with a basic compound, absorbance, It is selected in consideration of all required performance such as interaction with other components, light resistance, heat resistance and the like.
Specific examples of acid dyes are given below. However, the present invention is not limited to these.

For example, acid alizarin violet N;
acid black 1, 2, 24, 48;
acid blue 1,7,9,15,18,23,25,27,29,40,45,62,70,74,80,83,86,87,90,92,103,112,113,120, 129, 138, 147, 158, 171, 182, 192, 243, 324: 1;
acid chroma violet K;
acid Fuchsin;
acid green 1,3,5,9,16,25,27,50;
acid orange 6, 7, 8, 10, 12, 50, 51, 52, 56, 63, 74, 95;
acid red 1,4,8,14,17,18,26,27,29,31,34,35,37,42,44,50,51,52,57,66,73,80,87,88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 183, 198, 211, 215, 216, 217, 249, 252 257, 260, 266, 274;
acid violet 6B, 7, 9, 17, 19;
acid yellow 1,3,7,9,11,17,23,25,29,34,36,42,54,72,73,76,79,98,99,111,112,114,116,184 243;
Food Yellow 3;
And derivatives of these dyes.

  Among the above, acid black 24; acid blue 23, 25, 29, 62, 80, 86, 87, 92, 138, 158, 182, 243, 324: 1; acid orange 8, 51, 56, 63, 74; acid red 1,4,8,34,37,42,52,57,80,97,114,143,145,151,183,217; acid violet 7; acid yellow 17, 25, 29, 34, 42, 72, 76, 99, 111, 112, 114, 116, 184, 243; acid green 25, and the like, and derivatives of these dyes are preferred.

  In addition to the above, azo, xanthene, and phthalocyanine acid dyes are also preferable. I. Solvent Blue 44, 38; I. Solvent orange 45; Rhodamine B, Rhodamine 110 and other acid dyes and derivatives of these dyes are also preferably used.

  Although content in the photosensitive composition of a coloring agent is not specifically limited, Preferably, it is 30-60 mass% with respect to the total solid of this composition. When the amount of the colorant is within the above range, an appropriate chromaticity can be obtained as a color filter, a film with good photocurability and high hardness can be formed, and a development latitude at the time of alkali development is ensured. This is also effective.

  When the pigment is used as the colorant, a conventionally known pigment dispersant or surfactant can be added for the purpose of improving the dispersibility of the pigment. As the pigment dispersant and the surfactant, many kinds of compounds can be used. For example, a phthalocyanine derivative (commercial product: EFKA-745, manufactured by Efka), Solsperse 5000 (manufactured by Geneca); organosiloxane polymer Cations such as KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid (co) polymer polyflow No. 75, No. 90, No. 95 (manufactured by Kyoeisha Yushi Chemical Co., Ltd.), W001 (manufactured by Yusho) Surfactants: polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fat Nonionic surfactants such as esters; Anionic surfactants such as W004, W005, W017 (manufactured by Yusho); EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401 Polymer dispersants such as EFKA Polymer 450 (manufactured by Morishita Sangyo Co., Ltd.), Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 (San Nopco); Solsperse 3000, 5000 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000, etc. Various Solsperse dispersants (manufactured by Geneca); Adeka Pluronic L31, F38, L42, L44, L61 , Same L64, same 68, same L72, same P95, same F77, same P84, same F87, same P94, same L101, same P103, same F108, same L121, same P-123 (manufactured by Asahi Denka) and Isonet S-20 (Sanyo Kasei) For example).

-Solvent-
The photosensitive composition of the present invention can generally be prepared using a solvent.
Examples of the solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, and lactic acid. 3 such as ethyl, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate -Oxypropionic acid alkyl esters; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, 2-oxypropion Ethyl, propyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-oxy-2- Methyl methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, Methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate and the like; ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether Ter, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, etc .; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc .; aromatic hydrocarbons such as toluene, xylene and the like.

Among these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate Butyl carbitol acetate, propylene glycol methyl ether acetate and the like are preferable.
You may use a solvent in combination of 2 or more types besides using independently.

-Other ingredients-
In the photosensitive composition of the present invention, if necessary, a fluorine organic compound, a thermal polymerization inhibitor, other fillers, a polymer compound other than the acrylic copolymer, a surfactant other than the above, an adhesion promoter Various additives such as an agent, an antioxidant, an ultraviolet absorber, and an aggregation inhibitor can be contained.

<Fluorine organic compounds>
The photosensitive composition of the present invention contains at least one fluorine-based organic compound, so that the liquid properties (particularly fluidity) as a coating liquid when prepared in a liquid state can be improved. Liquidity can be improved. That is, the interfacial tension between the substrate and the coating liquid is reduced to improve the wettability to the substrate and the coating property to the substrate is improved, so that a thin film of about several μm is formed with a small amount of liquid. Is preferable in that a coating film having a uniform thickness with small thickness unevenness can be obtained.

  3-40 mass% is suitable for the fluorine content rate of a fluorine-type organic compound, More preferably, it is 5-30 mass%, Most preferably, it is 7-25 mass%. When the fluorine content of the fluorine-based organic compound is in the above range, it is effective in terms of coating thickness uniformity and liquid-saving properties, and the solubility in the composition is also good.

  Examples of the fluorinated organic compound include MegaFuck F171, F172, F173, F177, F141, F142, F143, F144, R30, and F437 (above, Dainippon Ink and Chemicals, Inc.) Manufactured), FLORARD FC430, FC431, FC171 (above, manufactured by Sumitomo 3M), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, and KH-40 (manufactured by Asahi Glass Co., Ltd.).

  In particular, the fluorine-based organic compound is effective in application of slits, which tends to cause coating unevenness, thickness unevenness, and liquid breakage on the coating surface when the coating film becomes thin.

  The addition amount of the fluorinated organic compound is preferably 0.001 to 2.0 mass%, more preferably 0.005 to 1.0 mass%, based on the total amount of the solution of the photosensitive composition.

<Thermal polymerization inhibitor>
Examples of the thermal polymerization inhibitor include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t- Butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2-mercaptobenzimidazole, and the like are useful.

<Various additives>
Specific examples of additives other than the above include fillers such as glass and alumina; itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, acidic cellulose Derivatives, polymers with hydroxyl groups, acid anhydrides added, alcohol-soluble nylons, alkali-soluble resins such as phenoxy resins formed from bisphenol A and epichlorohydrin; nonionic, kachin, anionic, etc. interfaces Activators, specifically phthalocyanine derivatives (commercially available products: EFKA-745, manufactured by Morishita Sangyo); organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid-based (co) polymer polyflow No. 75 , No. 90, No. 95 (manufactured by Kyoeisha Yushi Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.) and other cationic interfaces Reducing agent: polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (BASF) Nonionic surfactants such as Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1, etc. manufactured by the company; W004 , W005, W017 (manufactured by Yusho Co., Ltd.), etc .; EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, Polymer dispersing agents such as FKA polymer 401, EFKA polymer 450 (manufactured by Morishita Sangyo Co., Ltd.), Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 (San Nopco); Solsperse 3000, 5,000, 9000, 12000, 13240, 13240, 13940, 17000, 24000, 26000, 28000, etc., various Solsperse dispersants (manufactured by Geneca); Adeka Pluronic L31, F38, L42, L44 , L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (manufactured by Asahi Denka) And Isonet S-20 (manufactured by Sanyo Chemical Co., Ltd.); 2- (3-t-butyl It may be mentioned and aggregation inhibitor such as sodium polyacrylate; 5-methyl-2-hydroxyphenyl) -5-chloro-benzotriazole, ultraviolet absorbers such as alkoxy benzophenone.

  In order to promote alkali solubility of the uncured part and further improve the developability, it is effective to add an organic carboxylic acid, preferably a low molecular weight organic carboxylic acid having a molecular weight of 1000 or less. Specifically, for example, aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid; oxalic acid, malonic acid, succinic acid, Aliphatic dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid; Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, camphoric acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, Aromatic polycarboxylic acids such as trimesic acid, melophanoic acid, pyromellitic acid; phenylacetic acid Hydratropic acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetic acid, coumaric acid, other carboxylic acids such as umbellic acid.

  The photosensitive composition of the present invention comprises the acrylic copolymer described above, a bifunctional or higher polyfunctional polymerizable compound, a photopolymerization initiator, a colorant, and other components mixed with a solvent as necessary. It can be prepared by undergoing a dispersion mixing process using various mixers and dispersers. The step of dispersing and mixing is preferably composed of kneading and dispersing followed by fine dispersion treatment, but it is also possible to omit the kneading and dispersion and perform only fine dispersion treatment.

The color filter of the present invention is constituted by using the above-described photosensitive composition of the present invention, and can be suitably formed by a photolithography method.
In addition, the photosensitive composition of the present invention has high sensitivity, and its cured product (including a color filter) is excellent in transparency (light transmittance). In particular, the inside of a coating film for a color filter. Therefore, even if the content of the colorant is high, it is possible to reduce the possibility of peeling of a film that becomes a pixel during development or deformation of the pattern profile. Therefore, a color filter having a high colorant content and excellent color characteristics such as contrast can be obtained.
In the photosensitive composition, by containing the copolymer (acrylic copolymer) according to the present invention, in the case of a red organic pigment, the solid content is 30 to 50% by mass, preferably 35 to 45% by mass. % In the case of a green organic pigment, 35 to 55% by weight, preferably 40 to 50% by weight in the solid content, and in the case of a blue organic pigment, 25 to 45% by weight in the solid content, preferably 30-40 mass% can be contained, respectively.
Further, a cured film having high hardness can be formed with a short tact time, and it is excellent in alkali developability. In addition to being suitable for production of a color filter, it can be developed for various uses.

  In the photosensitive composition of the present invention, preferably, the dispersant is added so that the viscosity of the colorant after the dispersion treatment is relatively high (10,000 mPa · s or more, preferably 100,000 mPa · s or more). And then kneading and dispersing, then adding the acrylic copolymer according to the present invention and finely dispersing, and the viscosity after differential acid treatment is relatively low (1,000 mPa · s or less, preferably 100 mPa · s or less). The following is performed).

  In the kneading and dispersing treatment, it is preferable to use a twin roll, a triple roll, a ball mill, a tron mill, a disper, a kneader, a kneader, a homogenizer, a blender, a single-screw or a twin-screw extruder, etc. while giving a strong shearing force. scatter. Then, a solvent and an acrylic copolymer are added, and beads (glass with a particle diameter of 0.1 to 1 mm, zirconia, etc.) are mainly used by using a vertical or horizontal sand grinder, pin mill, slit mill, ultrasonic disperser, etc. ) For fine dispersion. Here, the kneading and dispersing treatment can be omitted. In that case, beads are dispersed with a pigment, a dispersant or a surface treatment agent, an acrylic copolymer and a solvent. The details of kneading and dispersing are described in “Paint Flow and Pigment Dispersion” by T.C. Patton (published by John Wiley and Sons, 1964).

  The color filter can be preferably produced by applying the above-described photosensitive composition of the present invention on a substrate and forming an image by a photolithography method. In the case of photolithography, the photosensitive composition of the present invention is applied onto the substrate directly or via another layer by spin coating, slit coating, cast coating, roll coating or the like (preferably using a slit coater). Applied by slit coating), dried (pre-baked) to form a coating film of the photosensitive composition, exposed through a predetermined mask pattern, only the coating film portion irradiated with light is cured, and an alkaline developer By developing and removing the uncured portion, a pattern consisting of a colored pattern image (that is, two or more colors such as single color, or three colors or four colors) is formed, and a color filter is formed. Obtainable. As radiation irradiated at this time, ultraviolet rays such as g-line, h-line and i-line are particularly preferably used.

  Drying (prebaking) of the coating film made of the photosensitive composition of the present invention coated on the substrate can be carried out at a temperature of 50 to 140 ° C. for 10 to 300 seconds using a hot plate, oven or the like. .

  Examples of the substrate include non-alkali glass, soda glass, Pyrex (registered trademark) glass, quartz glass, and the like in which a transparent conductive film is attached to these substrates, and solid-state imaging devices. Examples include a photoelectric conversion element substrate used in (image sensor such as CCD) and the like, for example, a silicon substrate. Furthermore, a plastic substrate is also possible. On these substrates, usually, black stripes for isolating each pixel are formed. The plastic substrate preferably has a gas barrier layer and / or a solvent resistant layer on the surface thereof.

  In general, the thickness (dry film thickness) of the coating film when the photosensitive composition of the present invention is applied on a substrate is preferably 0.3 to 5.0 μm, preferably 0.5 to 3.5 μm. And most preferably 1.0 to 2.5 μm.

The development process can be performed by using an alkaline developer and dissolving the uncured portion in the developer without dissolving the photocured portion. Any alkali developer can be used as long as it dissolves the film of the photosensitive composition in the uncured portion while not dissolving the cured portion. The development temperature is usually 20 to 30 ° C., and the development time is preferably 20 to 90 seconds.
In general, after the development treatment, excess developer is washed and removed, dried, and then heated (post-baked) at a temperature of 50 to 240 ° C.

  By repeating the steps as described above for each color in sequence for a desired hue, it is possible to obtain a cured film (including a color filter) colored with high quality and low cost with less process difficulties. it can.

As described above, the alkaline developer can be selected without limitation as long as it has a composition that dissolves the uncured portion of the photosensitive composition of the present invention but does not dissolve the cured portion. A combination of various organic solvents and an alkaline aqueous solution can be used.
Examples of the organic solvent include the solvents described above that can be used for preparing the photosensitive composition of the present invention.

  Examples of alkaline aqueous solutions include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethyl. Concentration of an alkaline compound such as ammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene is 0.001 to 10% by mass, preferably 0.01 to 1 An alkaline aqueous solution prepared by dissolving to a mass% can be used. In the case of using an alkaline developer, washing (rinsing) with water is generally performed after the development processing.

  The post-baking is heating after development processing for complete curing, and is usually performed at about 200 to 220 ° C. (hard baking). Post-baking is performed continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulation dryer), or a high-frequency heater so as to satisfy the above conditions for the coating film after development processing. Can be done.

  The photosensitive composition of the present invention has been described mainly with respect to the use for producing a color filter, but can also be applied to the production of a black matrix provided between colored pixels constituting a color filter. The black matrix exposes and develops the photosensitive composition of the present invention prepared using a black colorant such as carbon black or titanium black as a colorant, and further post-bake as necessary to cure the film. It can be produced by promoting.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. Unless otherwise specified, “part” and “%” are based on mass.

-Synthesis of alkali-soluble resin-
(1) Synthesis of copolymer B-1 (BzMA copolymer having a double bond in the side chain) 78.1 parts of benzyl methacrylate (BzMA), 5.4 parts of methacrylic acid, and 2-hydroxyethyl methacrylate 16 .5 parts was put into a reaction vessel, and 100 parts of propylene glycol monomethyl ether acetate and 5 parts of azobisisobutyronitrile were further added to this solution and uniformly dissolved, and the polymerization reaction was carried out at 95 ° C. for 5 hours. And a copolymer solution was obtained. Subsequently, 31.5 parts of 2-isocyanate trimethylolethane triacrylate and 31.5 parts of propylene glycol monomethyl ether acetate were added to the obtained copolymer solution, and the reaction was performed at 80 ° C. for 3 hours. A solution of trifunctional copolymer B-1 was obtained. The progress of the reaction was confirmed by measuring the infrared absorption spectrum and confirming the peak disappearance of the isocyanate group at 2200 cm ⁻¹ .
The obtained solution had a solid content of 49.4%, a viscosity of 1258 mPa · s (25 ° C.), an acid value of 13.0 mg KOH / g, and a weight average molecular weight by GPC of 9,500. It was.

(2) Synthesis of copolymer B-2 (MMA copolymer having double bond in side chain) 67.0 parts of methyl methacrylate (MMA), 8.1 parts of methacrylic acid, and 2-hydroxyethyl methacrylate 24 .9 parts was placed in a reaction vessel, and 100 parts of propylene glycol monomethyl ether acetate and 7.5 parts of azobisisobutyronitrile were further added to this solution and uniformly dissolved, and polymerization was carried out at 95 ° C. for 5 hours. The reaction was carried out to obtain a copolymer solution. Subsequently, 47.5 parts of 2-isocyanate trimethylolethane triacrylate and 47.5 parts of propylene glycol monomethyl ether acetate were added to the obtained copolymer solution, and the reaction was performed at 80 ° C. for 3 hours. A solution of trifunctional copolymer B-2 was obtained. The progress of the reaction was confirmed by measuring the infrared absorption spectrum and confirming the peak disappearance of the isocyanate group at 2200 cm ⁻¹ .
The obtained solution had a solid content of 50.1%, a viscosity of 1035 mPa · s (25 ° C.), an acid value of 17.5 mg KOH / g, and a weight average molecular weight by GPC of 10,300. It was.

(3) Synthesis of copolymer B-3 (an alkali-soluble copolymer having a monovalent double bond in the side chain) 96.1 parts of benzyl methacrylate, 6.6 parts of methacrylic acid, and 2-hydroxyethyl methacrylate 20.3 parts was put into a reaction vessel, and 120 parts of propylene glycol monomethyl ether acetate and 6.2 parts of azobisisobutyronitrile were further added to this, and the solution was dissolved uniformly at 95 ° C. over 5 hours. A polymerization reaction was performed to obtain a copolymer solution. Subsequently, 16.9 parts of 2-isocyanate ethyl acrylate and 16.9 parts of propylene glycol monomethyl ether acetate were added to the obtained copolymer solution, and the reaction was performed at 80 ° C. for 3 hours. A solution of B-3 was obtained. The progress of the reaction was confirmed by measuring the infrared absorption spectrum and confirming the peak disappearance of the isocyanate group at 2200 cm ⁻¹ .
The obtained solution had a solid content of 49.1%, a viscosity of 985 mPa · s (25 ° C.), an acid value of 25.2 mgKOH / g, and a weight average molecular weight by GPC of 10,500. It was.

(4) Synthesis of copolymer B-4 (an alkali-soluble copolymer having a bivalent double bond in the side chain) <1. Introduction of unsaturated group into copolymer>
Styrene / α-methylstyrene / methacrylic acid (= 49/9/42 [molar ratio]) copolymer (weight average molecular weight 12,000) 50 parts, p-methoxyphenol 0.1 part, tetraethylammonium chloride 1 part, And 110 parts of propylene glycol monomethyl ether acetate are put in a reaction vessel, and further, 22.5 parts of (3,4-epoxy-cyclohexyl) methyl acrylate is added dropwise thereto, and a polymerization reaction is performed at 90 ° C. for 32 hours, A copolymer solution was obtained. The progress of the reaction was confirmed by measuring the infrared absorption spectrum and confirming the peak disappearance of the isocyanate group at 2200 cm ⁻¹ . The obtained solution had a solid content of 40.1%, the acid value of the copolymer was 85 mgKOH / g, and the weight average molecular weight by GPC was 18,000.

<2. Introduction of secondary unsaturated group into copolymer>
Subsequently, 36 parts of the copolymer solution obtained above, 0.002 part of octyltin dilaurate and 10 parts of propylene glycol monomethyl ether acetate were put in a reaction vessel, and 6.2 parts of methacryloyloxyethyl isocyanate was further added thereto. The solution was added dropwise, and the polymerization reaction was carried out at 70 ° C. for 7 hours to obtain a solution of copolymer B-4.
The obtained solution had a solid content of 39.8%, the acid value of the copolymer was 60 mgKOH / g, and the weight average molecular weight by GPC was 29,000.

-Preparation of pigment dispersion-
(1) Preparation of Pigment Dispersion Liquid P-1 A mixture liquid obtained by mixing the compounds having the following composition was dispersed by a bead disperser using zirconia beads having an average particle diameter of 0.3 mm to obtain a pigment dispersion liquid P-1. Was prepared.
-Copolymer B-1 16.2 parts-C.I. I. Pigment Green 36 ... 18.0 parts · DISPER BYK-161 ... 2.0 parts (by Big Chemie Co., Ltd .; dispersant)
・ Propylene glycol monomethyl ether acetate: 43.8 parts

(2) Preparation of Pigment Dispersion P-2 A mixture obtained by mixing the compounds having the following composition was dispersed by a bead disperser using zirconia beads having an average particle diameter of 0.3 mm to obtain a pigment dispersion P-2. Was prepared.
-Copolymer B-2 ... 13.2 parts-C.I. I. Pigment Green 36 ... 15.0 parts · DISPER BYK-161 ... 1.7 parts (manufactured by Big Chemie Co., Ltd .; dispersant)
・ Propylene glycol monomethyl ether acetate 36.7 parts

(3) Preparation of Pigment Dispersion P-3 A mixture obtained by mixing the compounds having the following composition was dispersed by a bead disperser using zirconia beads having an average particle diameter of 0.3 mm to obtain a pigment dispersion P-3. Was prepared.
・ Methyl methacrylate / methacrylic acid copolymer: 8.0 parts (= 90/10 [molar ratio])
・ C. I. Pigment Green 36 ... 18.0 parts · DISPER BYK-161 ... 2.0 parts (by Big Chemie Co., Ltd .; dispersant)
・ Propylene glycol monomethyl ether acetate: 52.0 parts

(4) Preparation of Pigment Dispersion Liquid P-4 A mixture liquid obtained by mixing the compounds having the following composition was dispersed by a bead disperser using zirconia beads having an average particle diameter of 0.3 mm to obtain a pigment dispersion liquid P-4. Was prepared.
Benzyl methacrylate / methacrylic acid copolymer: 12.0 parts (= 90/10 [molar ratio])
・ C. I. Pigment Green 36 ... 36.0 parts · DISPER BYK-161 ... 3.0 parts (by Big Chemie Co., Ltd .; dispersant)
・ Propylene glycol monomethyl ether acetate: 78.0 parts

(5) Preparation of Pigment Dispersion Liquid P-5 A mixture liquid obtained by mixing the compounds having the following composition was dispersed with a bead disperser using zirconia beads having an average particle diameter of 0.3 mm to obtain a pigment dispersion liquid P-5. Was prepared.
-Copolymer B-3 ... 27.5 parts-C.I. I. Pigment Green 36 ... 30.0 parts · DISPER BYK-161 ... 3.2 parts (by Big Chemie Co., Ltd .; dispersant)
・ Propylene glycol monomethyl ether acetate: 72.7 parts

(6) Preparation of Pigment Dispersion Liquid P-6 A mixture liquid obtained by mixing the compounds having the following composition was dispersed with a bead disperser using zirconia beads having an average particle diameter of 0.3 mm to obtain a pigment dispersion liquid P-6. Was prepared.
-Copolymer B-4 ... 33.5 parts-C.I. I. Pigment Green 36 ... 30.0 parts · DISPER BYK-161 ... 3.2 parts (by Big Chemie Co., Ltd .; dispersant)
・ Propylene glycol monomethyl ether acetate: 66.2 parts

Example 1
The compound of the following composition was mixed and stirred to prepare a photosensitive colored resin composition CR-1 of the present invention which was uniformly and colored green.
Pigment dispersion P-1 125.1 parts Dipentaerythritol hexaacrylate 20.0 parts Irgacure 369 3.0 parts (Ciba Specialty Chemicals Co., Ltd.)
-Copolymer B-1 ... 13.3 parts-Propylene glycol monomethyl ether acetate ... 205.4 parts

(Example 2)
The compound of the following composition was mixed and stirred to prepare a photosensitive colored resin composition CR-2 of the present invention that was uniformly and colored green.
Pigment dispersion P-2 150.1 parts Dipentaerythritol hexaacrylate 30.0 parts Irgacure 369 4.5 parts (Ciba Specialty Chemicals Co., Ltd.)
-Copolymer B-1 ... 20.0 parts-Propylene glycol monomethyl ether acetate ... 308.1 parts

(Example 3)
Compounds of the following composition were mixed and stirred to prepare a photosensitive colored resin composition CR-3 of the present invention that was uniformly and colored green.
Pigment dispersion P-2 225.2 parts Dipentaerythritol hexaacrylate 36.0 parts Irgacure 369 5.4 parts (Ciba Specialty Chemicals Co., Ltd.)
-Copolymer B-2 ... 23.6 parts-Propylene glycol monomethyl ether acetate ... 370.0 parts

Example 4
A compound having the following composition was mixed and stirred to prepare a photosensitive colored resin composition CR-4 of the present invention which was uniformly and colored green.
Pigment dispersion P-1 50.0 parts Dipentaerythritol hexaacrylate 8.0 parts Irgacure 369 1.2 parts (Ciba Specialty Chemicals Co., Ltd.)
・ Methyl methacrylate / methacrylic acid copolymer: 2.6 parts (= 90/10 [molar ratio])
・ Propylene glycol monomethyl ether acetate: 84.9 parts

(Example 5)
A compound having the following composition was mixed and stirred to prepare a photosensitive colored resin composition CR-5 of the present invention which was uniformly and colored green.
・ Pigment dispersion P-3 250.0 parts Dipentaerythritol hexaacrylate 40.0 parts Irgacure 369 5.8 parts (Ciba Specialty Chemicals Co., Ltd.)
-Copolymer B-1 26.5 parts-Propylene glycol monomethyl ether acetate 410.0 parts

(Comparative Example 1)
Compounds of the following composition were mixed and stirred to prepare a comparative photosensitive colored resin composition CR-6 colored uniformly and green.
-Pigment dispersion P-3 ... 100.0 parts-Dipentaerythritol hexaacrylate ... 16.0 parts-Irgacure 369 ... 2.5 parts (Ciba Specialty Chemicals Co., Ltd.)
・ Methyl methacrylate / methacrylic acid copolymer: 5.3 parts (= 90/10 [molar ratio])
・ Propylene glycol monomethyl ether acetate: 168.5 parts

(Comparative Example 2)
A compound of the following composition was mixed and stirred to prepare a comparative photosensitive colored resin composition CR-7 colored uniformly and green.
-Pigment dispersion P-4 ... 125.1 parts-Dipentaerythritol hexaacrylate ... 20.0 parts-Irgacure 369 ... 3.0 parts (Ciba Specialty Chemicals Co., Ltd.)
Benzyl methacrylate / methacrylic acid copolymer: 6.6 parts (= 90/10 [molar ratio])
・ Propylene glycol monomethyl ether acetate: 211.0 parts

(Comparative Example 3)
Compounds of the following composition were mixed and stirred to prepare a comparative photosensitive colored resin composition CR-8 that was uniformly green.
Pigment dispersion P-5 204.1 parts Dipentaerythritol hexaacrylate 40.8 parts Irgacure 369 6.2 parts (Ciba Specialty Chemicals Co., Ltd.)
Copolymer B-3 27.2 parts Propylene glycol monomethyl ether acetate 420.0 parts

(Comparative Example 4)
Compounds of the following composition were mixed and stirred to prepare a comparative photosensitive colored resin composition CR-9 colored uniformly and green.
-Pigment dispersion P-6 ... 187.7 parts-Dipentaerythritol hexaacrylate ... 30.2 parts-Irgacure 369 ... 4.5 parts (manufactured by Ciba Specialty Chemicals Co., Ltd.)
-Copolymer B-4 ... 19.9 parts-Propylene glycol monomethyl ether acetate ... 308.1 parts

(Pixel formation and evaluation)
For the photosensitive colored resin compositions obtained in the above Examples and Comparative Examples, pixels are formed as follows, and pixel chipping and peeling, pixel surface smoothness, and pixel cross-sectional shape are evaluated. did.

Each of the photosensitive compositions was applied onto a glass substrate for producing a color filter by a spin coater, then placed on a hot plate at 100 ° C. so that the glass substrate was in contact, and dried for 2 minutes. A 2.0 μm green film was formed. Then, for each green film, through a mask that is depicted a predetermined pattern to a super-high pressure mercury lamp of ^{2.5kW, 25mJ / cm 2, 50mJ} / cm 2, 75mJ / cm 2, 100mJ / cm 2, and 150mJ Irradiation was performed with exposure doses of / cm ² and 200 mJ / cm ² . After irradiation, development processing was performed at 30 ° C. for 40 seconds using a 10% diluted solution of developer CD (manufactured by Fuji Film Electronics Materials Co., Ltd.), followed by rinsing with pure water to obtain a green pixel. After rinsing, the following measurements and evaluations were performed.

Next, each of the obtained green pixels was measured and evaluated by the following method. The results of measurement and evaluation are shown in Tables 1 to 3 below.
-1. Evaluation of pixel chipping and peeling-
Each green pixel after rinsing was observed with a microscope and evaluated.

-2. Evaluation of surface smoothness of pixels
The surface of the green pixel on the glass substrate was measured using an atomic force microscope AFM (manufactured by Digital Instruments Co., Ltd.), and the smoothness was evaluated using the obtained measurement value (Å) as an index.
A measured value shows that smoothness is favorable in it being 50 or less.

-3. Evaluation of pixel cross-sectional shape (pattern profile)
First, the length of the pixel pattern after rinsing is measured by the length measuring SEM (S-7800H, manufactured by Hitachi, Ltd.) in the above green pixel formation process, and the same width as the pattern mask width (here 2 μm width) The pattern that will be selected. Next, the selected pattern is divided so that one pattern cross section can be observed to prepare a sample, and the shape of the divided cross section of the sample is observed using an SEM (S-7800H, manufactured by Hitachi, Ltd.) I took a photo.

As shown in Tables 1 to 3, in the examples, even when the exposure amount is small, there is no occurrence of pixel defects such as partial chipping or peeling of the pixels due to development processing, and the shape is good and the shape is good. A color filter with a smooth surface could be obtained. Moreover, the uncured part which is a non-image part was free from undissolved substances and development residues, and exhibited good developability.
On the other hand, in the comparative example, it was not possible to obtain a pixel having a good shape without pixel chipping or peeling, and the produced color filter was inferior to the surface property and the cross-sectional pattern file.

Claims (5)

In the photosensitive composition containing an acrylic copolymer, a polyfunctional polymerizable compound having two or more functions, a photopolymerization initiator, and a colorant,
The photosensitive composition, wherein the acrylic copolymer is a copolymer including a copolymer unit having a trifunctional or higher polyunsaturated double bond.   The copolymer unit is a structural unit in which the polyunsaturated double bond is imparted to a side chain by addition reaction of a (meth) acryloylalkyl isocyanate compound having a polyunsaturated double bond via a hydroxyl group. The photosensitive composition according to claim 1.   The acrylic copolymer has a copolymerization ratio of the copolymerized units of 1 to 50 mol%, an acid value of 5 to 200 mgKOH / g, and a weight average molecular weight of 5,000 to 50,000. 3. The photosensitive composition according to 1 or 2. The acrylic copolymer contains 0 to 50 mol% of at least one structural unit represented by the following general formula (1) and 20 to 80 mol% of at least one structural unit represented by the following general formula (2). The photosensitive composition according to any one of claims 1 to 3.

[Wherein, R ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ² represents an aromatic carbocycle, and R ³ represents an alkyl group or an aralkyl group. ]   A color filter comprising the photosensitive composition according to claim 1.