JP2008266627A - Pigment dispersion composition, photocurable composition, color filter and its production method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a pigment dispersion composition having excellent pigment dispersibility and dispersion stability, a photocurable composition containing the dispersion composition, a color filter obtainable a high contrast therefrom and its production method. <P>SOLUTION: The dispersion composition etc. contains at least a pigment, a solvent, a dispersant having a polyester chain in the molecule and a polymer containing a copolymerization unit deriving from a monomer expressed by formula (1). In the formula, R<SP>1</SP>is a hydrogen atom, or a substituted or unsubstituted alkyl group; R<SP>2</SP>is a single bond or a bivalent linking group; Y is -CO-, -C(=O)O-, -CONH-, -OC(=O)- or a phenylene group; and Z is a group having a nitrogen-containing heterocyclic structure. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a pigment dispersion composition, a photocurable composition containing the same, a color filter produced using the photocurable composition, and a method for producing the color filter.

  The color filter contains a pigment dispersion composition in which an organic pigment or an inorganic pigment is dispersed, a polyfunctional monomer, a photopolymerization initiator, an alkali-soluble resin, and other components to form a colored photosensitive composition. It is manufactured by forming a colored pattern by a photolithography method or the like.

  In recent years, color filters tend to be used not only for monitors but also for televisions (TVs) in liquid crystal display (LCD) applications. Along with this trend of expanding applications, color filters are required to have high color characteristics in terms of chromaticity and contrast. Similarly, color filters having high color characteristics are demanded for color filters for image sensors (solid-state imaging devices).

  In response to the above requirements, the pigment contained in the colored photosensitive composition is dispersed in a finer state (good dispersibility), and is dispersed in a stable state (good dispersion stability). Is required. If the dispersibility of the pigment is insufficient, fringes (jagged edges) and surface irregularities occur in the formed colored resist film, and the chromaticity and dimensional accuracy of the manufactured color filter are reduced, contrast is increased. There is a problem that it is significantly deteriorated. In addition, when the dispersion stability of the pigment is insufficient, in the color filter manufacturing process, in particular, the uniformity of the film thickness in the coating process of the colored photosensitive composition is reduced, or in the exposure process. There is a tendency that the sensitivity is lowered and the alkali solubility in the developing process is lowered. Furthermore, when the dispersion stability of the pigment is poor, there is also a problem that the constituent components of the colored photosensitive composition are aggregated with the passage of time, the viscosity is increased, and the pot life is extremely shortened. However, when the pigment particle size is reduced, the surface area of the pigment particles increases, so the cohesion between the pigment particles increases, and it is difficult to achieve both high level dispersibility and dispersion stability. There are many.

  In order to solve such problems, various pigment dispersants have been developed. Among these dispersants, a copolymer containing a macromonomer (an oligomer having an ethylenically unsaturated group at a terminal) is useful, and a copolymer containing the macromonomer (an oligomer having an ethylenically unsaturated group at a terminal) is useful. It is disclosed in the publication that a pigment dispersion having a small pigment particle size and excellent dispersion stability can be obtained by using a coalescence (see, for example, Patent Documents 1 and 2). However, since the copolymer containing the macromonomer described in the document does not have a functional group that promotes adsorption to the pigment, it does not function alone as a dispersant, and must be used in combination with another dispersant. There is a problem. In addition, when the copolymer containing the macromonomer is used as a dispersant, the thickening action seen in the polymer dispersant can be suppressed, but the dispersibility is reduced because the pigment is not sufficiently refined. There is a problem that it is not enough.

In order to improve the dispersion stability of the pigment, a graft polymer having a partial structure of an organic dye (for example, see Patent Document 3), a graft polymer having a nitrogen-containing heterocyclic ring (for example, see Patent Document 4), and a cyclic imide group A graft polymer (for example, see Patent Document 5) is disclosed. Further, it is disclosed that a resin having an N-substituted maleimide and a urethane-based dispersant (for example, see Patent Document 6) or a graft copolymer having a nitrogen atom (for example, see Patent Document 7) are used in combination. . However, a pigment dispersion composition that is excellent in pigment dispersibility, fluidity, etc. and is soluble in an alkaline aqueous solution, and a colored photosensitive composition containing the pigment dispersion composition have not yet been provided. .
JP-A-8-259876 JP-A-10-339949 JP 2003-26950 A JP 2003-26949 A JP 2003-277673 A JP 2006-58821 A JP 2006-45262 A

This invention makes it a subject to achieve the following objectives.
That is, an object of the present invention is to provide a pigment dispersion composition excellent in pigment dispersibility and dispersion stability, and excellent in pigment dispersibility and dispersion stability, cured by exposure to light transmittance. Another object of the present invention is to provide a photocurable composition capable of forming a film excellent in contrast.
Another object of the present invention is to provide a color filter capable of obtaining a high contrast and a method for producing such a color filter.

  As a result of intensive studies, the present inventors have found that the above problems can be solved by using a polymer having a specific structure having a nitrogen-containing heterocyclic structure in the molecule as a pigment dispersant, and the present invention is completed. It came to. That is, the means for solving the problems are as follows.

  <1> It contains at least a polymer including a pigment, a solvent, a dispersant having a polyester chain in the molecule, and a copolymer unit derived from a monomer represented by the following general formula (1). Pigment dispersion composition.

In general formula (1), R ¹ represents a hydrogen atom or a substituted or unsubstituted alkyl group. R ² represents a single bond or a divalent linking group. Y represents -CO-, -C (= O) O-, -CONH-, -OC (= O)-, or a phenylene group. Z represents a group having a nitrogen-containing heterocyclic structure.

<2> The pigment dispersion according to <1>, wherein the polymer is a graft copolymer including a copolymer unit derived from a polymerizable oligomer having an ethylenically unsaturated bond at a terminal. Composition.
<3> The pigment dispersion composition according to <1> or <2>, wherein the polymer is a polymer further including a copolymer unit derived from a monomer having an acid group.
<4> Z <1> is characterized in that Z in the general formula (1) is a group having a nitrogen-containing heterocyclic structure having 6 or more carbon atoms. A pigment dispersion composition.

<5> A photocurable composition comprising the pigment dispersion composition according to any one of <1> to <4>, a photopolymerizable compound, and a photopolymerization initiator.
<6> Furthermore, alkali-soluble resin is contained, The photocurable composition as described in said <5> characterized by the above-mentioned.

<7> The photocurable composition according to <5> or <6>, wherein the photocurable composition is for a color filter.
<8> A color filter comprising a colored pattern formed using the photocurable composition for a color filter according to <7> on a substrate.

  <9> A photosensitive film forming step of forming a photosensitive film by applying the photocurable composition for a color filter according to the above <7> directly or through another layer to form a photosensitive film, and the formed photosensitivity And a colored pattern forming step of forming a colored pattern by sequentially performing pattern exposure and development on the conductive film.

According to the present invention, a pigment dispersion composition having high pigment dispersibility and dispersion stability, and a film excellent in dispersibility and dispersion stability of the pigment, cured by exposure, and excellent in light transmittance and contrast. The photocurable composition which can form can be provided.
Moreover, according to this invention, the color filter which can obtain high contrast, and the manufacturing method of such a color filter can be provided.

  Hereinafter, the pigment dispersion composition, the photocurable composition, the color filter, and the method for producing the color filter of the present invention will be described in detail.

[Pigment dispersion composition]
The pigment dispersion composition of the present invention comprises at least a pigment, a solvent, a dispersant having a polyester chain in the molecule, and a copolymer (including a copolymer unit derived from a monomer represented by the following general formula (1) ( Hereinafter, it is referred to as “specific polymer” as appropriate)).
That is, the pigment dispersion composition of the present invention is characterized in that a specific polymer and a dispersant having a polyester chain in the molecule are used in combination.

  The pigment dispersion composition of the present invention having the above configuration can exhibit high pigment dispersibility and dispersion stability.

[Polymer containing copolymerized units derived from monomer represented by general formula (1)]
The polymer (specific polymer) containing a copolymer unit derived from the monomer represented by the general formula (1), which is one of characteristic components in the pigment dispersion composition of the present invention, will be described in detail. .
The specific polymer is capable of functioning as a pigment dispersant in the pigment dispersion composition.

  First, the monomer represented by the general formula (1) and items related thereto will be described in detail.

In general formula (1), R ¹ represents a hydrogen atom or a substituted or unsubstituted alkyl group. R ² represents a single bond or a divalent linking group. Y represents -CO-, -C (= O) O-, -CONH-, -OC (= O)-, or a phenylene group. Z represents a group having a nitrogen-containing heterocyclic structure.

In general formula (1), R ¹ represents a hydrogen atom or a substituted or unsubstituted alkyl group. R ² represents a single bond or a divalent linking group. Y represents -CO-, -C (= O) O-, -CONH-, -OC (= O)-, or a phenylene group. Z represents a group having a nitrogen-containing heterocyclic structure.

In general formula (1), R ¹ represents a hydrogen atom or a substituted or unsubstituted alkyl group. As this alkyl group, a C1-C12 alkyl group is preferable, a C1-C8 alkyl group is more preferable, and a C1-C4 alkyl group is especially preferable.

When the alkyl group represented by R ¹ has a substituent, examples of the substituent include a hydroxy group and an alkoxy group (preferably having 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms). A methoxy group, an ethoxy group, a cyclohexyloxy group, etc. are mentioned.

Specific examples of the preferred alkyl group represented by R ¹ include, for example, methyl group, ethyl group, propyl group, n-butyl group, i-butyl group, t-butyl group, n-hexyl group, cyclohexyl group, 2 -Hydroxyethyl group, 3-hydroxypropyl group, 2-hydroxypropyl group, 2-methoxyethyl group can be mentioned.

R ¹ is most preferably a hydrogen atom or a methyl group.

In general formula (1), R ² represents a single bond or a divalent linking group. The divalent linking group is preferably a substituted or unsubstituted alkylene group. The alkylene group is preferably an alkylene group having 1 to 12 carbon atoms, more preferably an alkylene group having 1 to 12 carbon atoms, still more preferably an alkylene group having 1 to 8 carbon atoms, and an alkylene group having 1 to 4 carbon atoms. Particularly preferred.

The alkylene group represented by R ² may be one in which two or more are connected via a hetero atom (for example, an oxygen atom, a nitrogen atom, or a sulfur atom).

Specific examples of the preferable alkylene group represented by R ² include a methylene group, an ethylene group, a propylene group, a trimethylene group, and a tetramethylene group.

When the preferable alkylene group represented by R ² has a substituent, examples of the substituent include a hydroxy group.

Examples of the divalent linking group represented by R ² include —O—, —S—, —C (═O) O—, —CONH—, —C (═O) S at the terminal of the alkylene group. A heteroatom or a heteroatom selected from-, -NHCONH-, -NHC (= O) O-, -NHC (= O) S-, -OC (= O)-, -OCONH-, and -NHCO- It may have a partial structure and be linked to Z via the heteroatom or a partial structure containing a heteroatom.

  In general formula (1), Z represents a group having a nitrogen-containing heterocyclic structure. Specific examples of the nitrogen-containing heterocyclic structure include, for example, pyridine ring, pyrazine ring, pyrimidine ring, pyrrole ring, imidazole ring, triazole ring, tetrazole ring, indole ring, quinoline ring, acridine ring, phenothiazine ring, and phenoxazine ring. , An acridone ring, an anthraquinone ring, a benzimidazole structure, a benztriazole structure, a benzthiazole structure, a cyclic amide structure, a cyclic urea structure, and a cyclic imide structure. These nitrogen-containing heterocyclic structures may have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, an aliphatic ester group, an aromatic ester group, an alkoxycarbonyl group, Etc.

  Z is more preferably a group having a nitrogen-containing heterocyclic structure having 6 or more carbon atoms, and particularly preferably a group having a nitrogen-containing heterocyclic structure having 6 to 12 carbon atoms. Specific examples of the nitrogen-containing heterocyclic structure having 6 or more carbon atoms include phenothiazine ring, phenoxazine ring, acridone ring, anthraquinone ring, benzimidazole structure, benztriazole structure, benzthiazole structure, cyclic amide structure, and cyclic urea structure. And a cyclic imide structure are preferable, and a structure represented by the following general formula (2), (3) or (4) is particularly preferable.

In the general formula (2), X represents a single bond, an alkylene group (for example, a methylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, etc.), -O-, -S-, -NR ^A- , and It is one selected from the group consisting of —C (═O) —. Here, R ^A represents a hydrogen atom or an alkyl group. When R ^A represents an alkyl group, the alkyl group is preferably an alkyl group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, or an n-propyl group. I-propyl group, n-butyl group, t-butyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, n-octadecyl group and the like.

  Among the above, as X in the general formula (2), a single bond, a methylene group, —O—, or —C (═O) — is preferable, and —C (═O) — is particularly preferable.

In General Formula (4), Y and Z each independently represent —N═, —NH—, —N (R ^B ) —, —S—, or —O—. R ^B represents an alkyl group, and when R ^B represents an alkyl group, the alkyl group is preferably an alkyl group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, for example, a methyl group , Ethyl group, n-propyl group, i-propyl group, n-butyl group, t-butyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, n-octadecyl group and the like.
Among the above, as Y and Z in the general formula (4), —N═, —NH—, and —N (R ^B ) — are particularly preferable. Examples of the combination of Y and Z include a combination in which one of Y and Z is —N═ and the other is —NH—, and an imidazolyl group.

  In general formula (2), (3), or (4), ring A, ring B, ring C, and ring D each independently represent an aromatic ring. Examples of the aromatic ring include a benzene ring, naphthalene ring, indene ring, azulene ring, fluorene ring, anthracene ring, pyridine ring, pyrazine ring, pyrimidine ring, pyrrole ring, imidazole ring, indole ring, quinoline ring, acridine ring, Examples include phenothiazine ring, phenoxazine ring, acridone ring, anthraquinone ring, among others, benzene ring, naphthalene ring, anthracene ring, pyridine ring, phenoxazine ring, acridine ring, phenothiazine ring, phenoxazine ring, acridone ring, anthraquinone ring. Are preferable, and a benzene ring, a naphthalene ring, and a pyridine ring are particularly preferable.

  Specifically, examples of the ring A and ring B in the general formula (2) include a benzene ring, a naphthalene ring, a pyridine ring, a pyrazine ring, and the like. Examples of the ring C in the general formula (3) include a benzene ring, a naphthalene ring, a pyridine ring, and a pyrazine ring. Examples of the ring C in the general formula (4) include a benzene ring, a naphthalene ring, a pyridine ring, a pyrazine ring, and the like.

  Among the structures represented by the general formula (2), (3) or (4), a benzene ring and a naphthalene ring are more preferable from the viewpoint of dispersibility and stability over time of the dispersion, and the general formula (2) or In (4), a benzene ring is more preferable, and in the general formula (3), a naphthalene ring is more preferable.

  Although the preferable specific example (exemplary compound M-1 to M-27) of the monomer represented by General formula (1) is given to the following, this invention is not restrict | limited to these.

  The specific polymer may include only one type of copolymer unit derived from the monomer represented by the general formula (1), or may include two or more types.

  In the specific polymer, the content of the copolymer unit derived from the monomer represented by the general formula (1) is not particularly limited, but when the total structural unit contained in the polymer is 100% by mass In addition, the copolymer unit derived from the monomer represented by the general formula (1) is preferably contained in an amount of 5% by mass or more, and more preferably 10 to 50% by mass.

  That is, from the viewpoint of the dispersibility and dispersion stability of the pigment contained in the pigment dispersion composition, and the contrast of the color filter obtained by applying the pigment dispersion composition, the simple formula represented by the general formula (1) is used. The content of the copolymer unit derived from the monomer is preferably 5% by mass or more. From the viewpoint of developability when producing a color filter from a photocurable composition containing a pigment dispersion composition, the content of copolymer units derived from the monomer represented by the general formula (1) Is preferably 50% by mass or less.

  The specific polymer is a graft containing a copolymer unit derived from the monomer represented by the general formula (1) and a copolymer unit derived from a polymerizable oligomer having an ethylenically unsaturated double bond at the terminal. A copolymer is particularly preferred. The specific polymer further contains copolymer units derived from a polymerizable oligomer having an ethylenically unsaturated double bond at the terminal, so that it has excellent dispersibility (low viscosity and high contrast) and stability over time (low viscosity) The pigment dispersion composition is excellent in the following.

  Such a polymerizable oligomer having an ethylenically unsaturated double bond at the terminal is also called a macromonomer because it is a compound having a predetermined molecular weight. In the following description, the “polymerizable oligomer having an ethylenically unsaturated bond at the terminal” in the present invention may be appropriately referred to as “polymerizable oligomer” or “macromonomer”.

  The polymerizable oligomer optionally used in the present invention comprises a polymer chain part and a part of a polymerizable functional group having an ethylenically unsaturated double bond at its terminal. It is preferable from the viewpoint of obtaining a desired graft polymer that such a group having an ethylenically unsaturated double bond is present only at one end of the polymer chain. As the group having an ethylenically unsaturated double bond, a (meth) acryloyl group and a vinyl group are preferable, and a (meth) acryloyl group is particularly preferable.

The macromonomer preferably has a polystyrene-equivalent number average molecular weight (Mn) in the range of 1000 to 10,000, and particularly preferably in the range of 2000 to 9000.
If it is less than 1000, dispersibility, dispersion stability, and contrast are low, and if it exceeds 10,000, developability deteriorates.

  That is, from the viewpoint of the dispersibility and dispersion stability of the pigment contained in the pigment dispersion composition and the contrast of the color filter obtained by applying the pigment dispersion composition, the number average molecular weight (Mn) of the macromonomer is It is preferable that it is 1000 or more. From the viewpoint of developability when producing a color filter from a photocurable composition containing a pigment dispersion composition, the number average molecular weight (Mn) of the macromonomer is preferably 10,000 or less.

  The polymer chain portion in the macromonomer is a homopolymer or copolymer formed from at least one monomer selected from the group consisting of alkyl (meth) acrylate, styrene and derivatives thereof, acrylonitrile, vinyl acetate, and butadiene, or , Polyethylene oxide, polypropylene oxide, or polycaprolactone.

  The polymerizable oligomer is preferably an oligomer represented by the following general formula (5).

In General Formula (5), R ¹¹ and R ¹³ each independently represent a hydrogen atom or a methyl group.
R ¹² represents a linking group containing an alkylene group having 1 to ¹² carbon atoms, and the linking group may be an alkylene group having 1 to 12 carbon atoms, or a plurality of the alkylene groups may be ester bonds or ethers. It may be linked via a bond, an amide bond or the like. The alkylene group for R ¹² is preferably an alkylene group having 2 to 4 carbon atoms. The alkylene group for R ¹² may further have a substituent (for example, a hydroxyl group).

Y ¹¹ represents a phenyl group having no substituent, a phenyl group having one alkyl group having 1 to 4 carbon atoms, or —COOR ¹⁴ . Here, R ¹⁴ represents an alkyl group having 1 to 6 carbon atoms, a phenyl group, or an arylalkyl group having 7 to 10 carbon atoms. Y ¹¹ is preferably a phenyl group or —COOR ¹⁴ . Here, R ¹⁴ represents an alkyl group having 1 to 12 carbon atoms.
q represents an integer of 20 to 200.

  In the present invention, preferred examples of the polymerizable oligomer (macromonomer) that can be used for the synthesis of the specific polymer include polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and poly-i-butyl (meth). A polymer in which a (meth) acryloyl group is bonded to one molecular end of acrylate or polystyrene can be exemplified. As such polymerizable oligomers available on the market, one-end methacryloylated polystyrene oligomer (Mn = 6000, trade name: AS-6, manufactured by Toagosei Chemical Co., Ltd.), one-end methacryloylated polymethyl methacrylate oligomer ( Mn = 6000, trade name: AA-6, manufactured by Toa Gosei Chemical Co., Ltd.) and one-terminal methacryloylated poly-n-butyl acrylate oligomer (Mn = 6000, trade name: AB-6, Toa Gosei Chemical Co., Ltd.) ) Made).

  The specific polymer may include only one type of copolymer unit derived from a polymerizable oligomer having an ethylenically unsaturated double bond at the terminal, or may include two or more types.

  The specific polymer preferably further contains a copolymer unit derived from a monomer having an acid group. When the specific polymer further contains a copolymer unit derived from a monomer having an acid group, when the pigment dispersion composition is applied to the photocurable composition, the development removability of the unexposed area is excellent.

  Monomers having an acid group include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid; maleic acid, maleic anhydride, fumaric acid, itaconic acid, anhydrous Unsaturated dicarboxylic acids such as itaconic acid, citraconic acid, citraconic anhydride and mesaconic acid or their anhydrides; trivalent or higher unsaturated polycarboxylic acids or their anhydrides; succinic acid mono (2-acryloyloxyethyl) ), Succinic acid mono (2-methacryloyloxyethyl), phthalic acid mono (2-acryloyloxyethyl), phthalic acid mono (2-methacryloyloxyethyl) monovalent polyvalent carboxylic acid mono [ (Meth) acryloyloxyalkyl] esters; ω-carboxy-polycaprolactone monoacrylate, ω-carboxy-polycaprolacto It can be mentioned mono (meth) acrylates such as both terminal carboxy polymers such monomethacrylate.

  The specific polymer may include only one type of copolymer unit derived from a monomer having an acid group, or may include two or more types.

  In the specific polymer, the content of the copolymer unit derived from the monomer having an acid group is preferably 10 to 200 mgKOH / g, particularly preferably 50 to 150 mgKOH / g. That is, from the viewpoint of dispersibility and dispersion stability of the pigment contained in the pigment dispersion composition, the content of the copolymer unit derived from the monomer having an acid group is preferably 10 mgKOH / g or more. In addition, from the viewpoint of developability when producing a color filter with a photocurable composition containing a pigment dispersion composition, the content of copolymer units derived from monomers having an acid group is 200 mgKOH / g or less. It is preferable that

  The specific polymer may further contain copolymer units derived from a copolymerizable vinyl monomer as long as the effect is not impaired.

  Although it does not restrict | limit especially as a vinyl monomer which can be used here, For example, (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, ( Preference is given to meth) acrylamides, vinyl ethers, esters of vinyl alcohol, styrenes, (meth) acrylonitrile and the like. Specific examples of such vinyl monomers include the following compounds. In addition, in this specification, when showing either or both of "acryl and methacryl", it may describe as "(meth) acryl".

  Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate. , Isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, (meth) acrylic acid 2- Ethylhexyl, t-octyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-Methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate 2- (2-methoxyethoxy) ethyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, (meth) acrylic acid Diethylene glycol monoethyl ether, (meth) acrylic acid triethylene glycol monomethyl ether, (meth) acrylic acid triethylene glycol monoethyl ether, (meth) acrylic acid polyethylene glycol monomethyl ether, (meth) acrylic acid polyethylene glycol monoethyl ether, ( Β-phenoxyethoxyethyl (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclo (meth) acrylate Pentenyloxyethyl, trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tribromophenyl (meth) acrylate And (meth) acrylic acid tribromophenyloxyethyl.

  Examples of crotonic acid esters include butyl crotonate and hexyl crotonate.

  Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate, and the like.

  Examples of maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.

  Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.

  Examples of itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

  (Meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and Nn-butyl. Acrylic (meth) amide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N -Diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholine, diacetone acrylamide, etc. are mentioned.

  Examples of vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and methoxyethyl vinyl ether.

  Examples of styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chloro styrene, dichloro styrene, bromo styrene, chloromethyl Examples thereof include styrene, hydroxystyrene protected with a group that can be deprotected by an acidic substance (for example, t-Boc and the like), methyl vinylbenzoate, and α-methylstyrene.

  The preferred molecular weight of the specific polymer is preferably in the range of 10,000 to 200,000 in terms of weight average molecular weight (Mw) and in the range of 4,000 to 100,000 in terms of number average molecular weight (Mn). In particular, the weight average molecular weight (Mw) is preferably in the range of 10,000 to 50,000, and the number average molecular weight (Mn) is preferably in the range of 4000 to 10,000.

  That is, from the viewpoint of the dispersibility and dispersion stability of the pigment contained in the pigment dispersion composition and the contrast of the color filter obtained by applying the pigment dispersion composition, the weight average molecular weight (Mw) of the specific polymer. Is preferably 10,000 or more. From the viewpoint of developability when producing a color filter from a photocurable composition containing a pigment dispersion composition, the weight average molecular weight (Mw) of the specific polymer is preferably 100,000 or less.

  The specific polymer is produced by a normal radical polymerization method using, for example, the monomer represented by the general formula (1), a polymerizable oligomer (macromonomer), and another radical polymerizable compound as a copolymerization component. can do. In general, a suspension polymerization method or a solution polymerization method is used. Examples of the solvent used for synthesizing such a specific polymer include ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, propanol, butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxy. Examples include ethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, toluene, ethyl acetate, methyl lactate, and ethyl lactate. It is done. These solvents may be used alone or in combination of two or more.

  Specific examples of the specific polymer include, but are not limited to, polymers 1 to 31 described in Examples described later.

  In the pigment dispersion composition of the present invention, the content of the specific polymer is preferably a mass ratio of pigment: specific polymer = 1: 0.1 to 1: 2, more preferably 1: 0.2 to 1. : 1, more preferably 1: 0.4 to 1: 0.7.

[Dispersant having a polyester chain in the molecule]
The pigment dispersion composition of the present invention contains a dispersant having a polyester chain in the molecule.
The structure of the polyester chain in the dispersant having a polyester chain in the molecule is preferably one having 3 or more repeating units, more preferably 5 or more, and still more preferably 5 or more and less than 20. is there.
The structure of the repeating unit in the polyester chain is preferably a structure in which a diol compound and a dicarboxylic acid compound are condensed or a structure in which a lactone ring is subjected to ring-opening polymerization. The diol compound and the dicarboxylic acid compound are each preferably a compound having 4 to 30 carbon atoms, and more preferably 4 to 20 carbon atoms. More preferably, it is an aliphatic compound having 4 to 20 carbon atoms from the viewpoint of adsorptivity with the pigment, that is, dispersibility. Moreover, as a lactone ring, a C4-C20 aliphatic lactone is preferable, More preferably, it is a C4-C6 thing. As the structure of the polyester chain, a structure in which a lactone ring is ring-opened and polymerized is preferable in terms of adsorptivity with the pigment, that is, dispersibility.
In addition, the molecular weight of the polyester chain is preferably 100 or more, more preferably 200 or more, and most preferably 200 or more and less than 2000 in terms of stability over time.
The polyester chain in the dispersant having a polyester chain in the molecule may be the main chain of the polymer compound constituting the dispersant or a side chain.
The dispersant having a polyester chain in the molecule is preferably a polymer compound having a non-polyester structure in the main chain and a polyester chain in the side chain from the viewpoint of adsorptivity with the pigment, that is, dispersibility.

  Specifically as a dispersant having a polyester chain in the molecule, for example, a compound obtained by reacting a polyalkyleneimine and a polyester compound described in JP-A No. 54-37082, JP-A No. 61-174939, and the like, A compound in which the side chain amino group of polyallylamine described in JP-A-9-169821 is modified with polyester, a graft polymer comprising a polyester-type macromonomer described in JP-A-9-171253 as a copolymerization component, Preferred examples include polyester polyol-added polyurethanes described in JP-A-60-166318.

  When these compounds contain a flexible polyester chain, the adsorptivity to the pigment increases, and the dispersibility can be improved by using in combination with the specific polymer. Further, in the case of forming a resist pattern by using the photocurable composition containing the pigment dispersion composition of the present invention as a resist solution (for example, when producing a colored pattern of a color filter), development in the development process Since the liquid permeability can be improved, a good resist pattern can be formed.

  A commercially available dispersant can also be used as a dispersant having a polyester chain in the molecule. For example, Solsperse 24000GR, 28000, 32000, 38500 (manufactured by Nippon Lubrizol Co., Ltd.), Azisper PB711, PN411, PA111, PB821, PB822 (manufactured by Ajinomoto Fine Techno), EFKA4047, 4050 (manufactured by Efka Additives Japan), Disperbyk-161, 162, 167, 168 (manufactured by Big Chemie Japan) may be mentioned.

  Among the dispersants having a polyester chain in the molecule, from the standpoint of adsorptivity with pigment, that is, dispersibility and stability over time, a compound obtained by reacting a polyalkyleneimine and a polyester compound, and a polyester type macromonomer And a compound obtained by reacting a polyalkyleneimine and a polyester compound is most preferable.

  The dispersant having a polyester chain in the molecule may be used alone or in combination of two or more.

  In the pigment dispersion composition, the dispersant having a polyester chain in the molecule is in the range of 1: 0.1 to 1:10 in terms of the mass ratio of the specific polymer: the dispersant having a polyester chain, from the viewpoint of stability over time. It is preferably used in the range of 1: 0.5 to 1: 5, more preferably in the range of 1: 0.5 to 1: 3.

[Pigment]
The pigment dispersion composition of the present invention contains a pigment.
As the pigment, conventionally known various inorganic pigments or organic pigments can be appropriately selected and used.
As for the particle size of the pigment, considering that the color filter in which the pigment dispersion composition of the present invention is suitably used preferably has a high transmittance, the particle size of the inorganic pigment or the organic pigment is preferably as large as possible. It is preferable to use a small one. In consideration of the handleability of the pigment dispersion composition and the photocurable composition containing the same, the average particle diameter of the pigment is preferably 0.01 to 0.1 μm, more preferably 0.01 to 0.05 μm.

  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 And metal oxides such as the above, and complex oxides of the above metals.

As an organic pigment, for example,
C. I. Pigment yellow 11,24,31,53,83,93,99,108,109,110,138,139,147,150,151,154,155,167,180,185,199;
C. I. Pigment orange 36, 38, 43, 71;
C. I. Pigment red 81,105,122,149,150,155,171,175,176,177,209,220,224,242,254,255,264,270;
C. I. Pigment violet 19, 23, 32, 37, 39;
C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 3, 15: 6, 16, 22, 60, 66;
C. I. Pigment green 7, 36, 37;
C. I. Pigment brown 25, 28;
C. I. Pigment black 1, 7;
Etc.

Although the pigment in this invention is not specifically limited, The following organic pigment is more preferable.
C. I. Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185
C. I. Pigment orange 36, 71,
C. I. Pigment Red 122, 150, 171, 175, 177, 209, 224, 242, 254, 255, 264
C. I. Pigment violet 19, 23, 37,
C. I. Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66,
C. I. Pigment Black 7.

  These organic pigments can be used alone or in various combinations to increase color purity. Specific examples of combinations are shown below.

  Examples of red pigments include anthraquinone pigments, perylene pigments, diketopyrrolopyrrole pigments alone or at least one of them, bisazo yellow pigments, isoindoline yellow pigments, quinophthalone yellow pigments or perylene red pigments. 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 becomes difficult to suppress the light transmittance of 400 nm to 500 nm, and the color purity may not be improved. On the other hand, when the ratio exceeds 100: 50, the dominant wavelength becomes shorter than the short wavelength, and the deviation from the NTSC target hue may increase. In particular, the mass ratio is optimally in the range of 100: 10 to 100: 30. In the case of a combination of red pigments, it can be adjusted in accordance with the chromaticity.

  As the green pigment, for example, a halogenated phthalocyanine pigment can be used alone, or a mixture thereof with a bisazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment, or an isoindoline yellow pigment can be used. 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 is difficult to suppress the light transmittance of 400 nm to 450 nm, and the color purity may not be increased. On the other hand, if the ratio exceeds 100: 150, the dominant wavelength becomes longer and the deviation from the NTSC target hue may become large. The mass ratio is particularly preferably in the range of 100: 30 to 100: 120.

  As the blue pigment, for example, a phthalocyanine pigment 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 and the purple pigment is preferably 100: 0 to 100: 50, more preferably 100: 5 to 100: 30.

  Examples of the pigment for black matrix include carbon, titanium black, iron oxide, titanium oxide alone or a mixture thereof, and a combination of carbon and titanium black is preferable. The mass ratio of carbon to titanium black is preferably in the range of 100: 0 to 100: 60. If it exceeds 100: 60, the dispersion stability may decrease.

  As content in the pigment dispersion composition of a pigment, 40-90 mass% is preferable with respect to the total solid (mass) of this composition, and 50-80 mass% is more preferable. When the content of the pigment is within such a range, the color density is sufficient and it is effective to ensure excellent color characteristics.

  In the pigment dispersion composition, the total content of the specific polymer and the dispersant having a polyester chain in the molecule is preferably 0.5 to 100% by mass, and preferably 3 to 70% by mass with respect to the mass of the pigment. Is more preferable.

  The total content of the specific polymer and the dispersant having a polyester chain in the molecule (pigment dispersant). Within the above range, a sufficient pigment dispersion effect can be obtained.

〔solvent〕
Examples of the solvent in the pigment dispersion composition of the present invention include 1-methoxy-2-propyl acetate, 1-methoxy-2-propanol, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, ethyl acetate, butyl acetate, ethyl lactate, and acetone. And solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, n-propanol, 2-propanol, n-butanol, cyclohexanol, ethylene glycol, diethylene glycol, toluene, and xylene.

  The content of the solvent in the pigment dispersion composition is appropriately selected according to the use of the pigment dispersion composition. When the pigment dispersion composition is used for the preparation of a photocurable composition to be described later, it should be contained so that the solid content concentration including the pigment and the pigment dispersant is 5 to 50% by mass from the viewpoint of handleability. Can do.

-Preparation of pigment dispersion composition-
The preparation mode of the pigment dispersion composition of the present invention is not particularly limited. For example, the pigment, the pigment dispersant, and the solvent are mixed using a vertical or horizontal sand grinder, a pin mill, a slit mill, an ultrasonic disperser, or the like. It can be obtained by performing fine dispersion treatment with beads made of glass, zirconia or the like having a particle diameter of 0.01 to 1 mm.

  Before bead dispersion, kneading and dispersing with a strong shearing force using a two-roll, three-roll, ball mill, tron mill, disper, kneader, kneader, homogenizer, blender, single- or twin-screw extruder, etc. It is also possible to perform processing.

  For details on kneading and dispersing, see T.W. C. “Paint Flow and Pigment Dispersion” by Patton (published by John Wiley and Sons, 1964) and the like.

  The pigment dispersion of the present invention is suitably used for a photocurable composition used for producing a color filter.

<Photocurable composition>
The photocurable composition of the present invention comprises at least the pigment dispersion composition of the present invention described above, an alkali-soluble resin, a photopolymerizable compound, and a photopolymerization initiator. May be included. Since this photocurable composition includes the specific polymer described above and a dispersant having a polyester chain in the molecule, the pigment is maintained in a good dispersion state in the composition, and good color characteristics are obtained. For example, when a color filter is configured, high contrast can be obtained.
Hereinafter, each component contained in the photocurable composition of the present invention will be described in detail.

(Pigment dispersion composition)
The photocurable composition of the present invention is constituted by using at least one kind of the pigment dispersion composition of the present invention. Details of the pigment dispersion composition of the present invention constituting the photocurable composition are as described above.

  As content of the pigment dispersion composition in the photocurable composition of this invention, content of a pigment becomes the range of 5-70 mass% with respect to the total solid (mass) of a photocurable composition. The amount is preferable, and an amount in the range of 15 to 60% by mass is more preferable. When the content of the pigment dispersion composition is within the above range, the color density is sufficient and effective in securing excellent color characteristics.

[Alkali-soluble resin]
The photocurable composition of the present invention contains at least one alkali-soluble resin.
The alkali-soluble resin is a linear organic polymer, and promotes at least one alkali-solubility in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). It can be appropriately selected from alkali-soluble resins having a group (for example, carboxyl group, phosphoric acid group, sulfonic acid group, etc.). Of these, more preferred are those which are soluble in an organic solvent and can be developed with a weak alkaline aqueous solution.

  For example, a known radical polymerization method can be applied to the production of the alkali-soluble resin. Polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, etc. when producing an alkali-soluble resin by radical polymerization can be easily set by those skilled in the art, and the conditions are determined experimentally. It can also be done.

  As said linear organic high molecular polymer, the polymer which has carboxylic acid in a side chain is preferable. For example, JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54-25957, JP-A-59-53836, JP-A-59-71048 As described, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc., and side chain Examples thereof include acidic cellulose derivatives having a carboxylic acid, polymers obtained by adding an acid anhydride to a polymer having a hydroxyl group, and high molecular polymers having a (meth) acryloyl group in the side chain.

  Of these, benzyl (meth) acrylate / (meth) acrylic acid copolymers and multi-component copolymers composed of benzyl (meth) acrylate / (meth) acrylic acid / other monomers are particularly suitable. In addition, those obtained by copolymerizing 2-hydroxyethyl methacrylate are also useful. The polymer can be used by mixing in an arbitrary amount.

  In addition to the above, 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate described in JP-A-7-140654 Macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, etc. Is mentioned.

  As a specific structural unit of the alkali-soluble resin, a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is particularly suitable.

  Examples of the other monomer copolymerizable with (meth) acrylic acid include alkyl (meth) acrylate, aryl (meth) acrylate, and vinyl compounds. Here, the hydrogen atom of the alkyl group and the aryl group may be substituted with a substituent.

  Specific examples of the alkyl (meth) acrylate and aryl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl ( Examples include meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl acrylate, tolyl acrylate, naphthyl acrylate, and cyclohexyl acrylate.

Examples of the vinyl compound include styrene, α-methylstyrene, vinyl toluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinyl pyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macromonomer, polymethyl methacrylate macromonomer, and CH ₂ ═CR. ²¹ R ²² [wherein R ²¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ²² represents an aromatic hydrocarbon ring having 6 to 10 carbon atoms. ], CH ₂ = C (R ²¹ ) (COOR ²³ ) [wherein R ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ²³ represents an alkyl group having 1 to 8 carbon atoms or 6 carbon atoms. Represents -12 aralkyl groups. ], Etc. can be mentioned.

These other copolymerizable monomers can be used singly or in combination of two or more. Preferred other copolymerizable monomers are selected from CH ₂ ═CR ²¹ R ²² , CH ₂ ═C (R ¹ ) (COOR ²³ ), phenyl (meth) acrylate, benzyl (meth) acrylate and styrene. It is at least one, and particularly preferably, CH ₂ = CR ²¹ R ²² and / or CH ₂ = C (R ²¹ ) (COOR ²³ ). These R ²¹ , R ²² and R ²³ are as defined above.

  As content of alkali-soluble resin in a photocurable composition, 1-20 mass% is preferable with respect to the total solid of this composition, More preferably, it is 2-15 mass%, Most preferably, it is 3 ˜12% by mass.

[Photopolymerizable compound]
The photocurable composition of the present invention contains at least one photopolymerizable compound. The polymerizable compound that can be used in the present invention is an addition polymerizable compound having at least one ethylenically unsaturated double bond, and is a compound having at least one terminal ethylenically unsaturated bond, preferably two or more. To be elected. Such a compound group is widely known in the industrial field, and can be used without any particular limitation in the present invention. These have chemical forms such as monomers, prepolymers, i.e. dimers, trimers and oligomers, or mixtures thereof and copolymers thereof. Examples of monomers and copolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), and esters and amides thereof. In this case, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound is used. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, amino group or mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and monofunctional or polyfunctional A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an epoxy group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, a halogen group or In addition, a substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid.

  Specific examples of the monomer of an ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol. Diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate , Tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate , Pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer, isocyanuric acid There are EO-modified triacrylate and the like.

  Methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, Hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacryloxy- 2-hydroxypro ) Phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane.

  Itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate Sorbitol tetritaconate, etc. Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate. Examples of isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate. Examples of maleic acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

  Examples of other esters include aliphatic alcohol esters described in JP-B-51-47334 and JP-A-57-196231, JP-A-59-5240, JP-A-59-5241, and JP-A-2-226149. Those having the aromatic skeleton described above and those having an amino group described in JP-A-1-165613 are also preferably used. Furthermore, the ester monomers described above can also be used as a mixture.

  Specific examples of amide monomers of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis. -Methacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide and the like. Examples of other preferable amide monomers include those having a cyclohexylene structure described in JP-B-54-21726.

  In addition, urethane-based addition polymerizable compounds produced by using an addition reaction of isocyanate and hydroxyl group are also suitable, and specific examples thereof include, for example, one molecule described in JP-B-48-41708. A vinyl urethane containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group represented by the following general formula (6) to a polyisocyanate compound having two or more isocyanate groups. Compounds and the like.

CH ₂ = C (R ^A ) COOCH ₂ CH (R ^B ) OH (6)
(However, R ^A and R ^B represent H or CH _3. )

  Also, urethane acrylates such as those described in JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765, JP-B-58-49860, JP-B-56-17654, Urethane compounds having an ethylene oxide skeleton described in JP-B-62-39417 and JP-B-62-39418 are also suitable. Further, by using addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238, It is possible to obtain a photopolymerizable composition excellent in the photosensitive speed.

  Other examples include polyester acrylates, epoxy resins and (meth) acrylic acid as described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, and JP-A-52-30490. Mention may be made of polyfunctional acrylates and methacrylates such as reacted epoxy acrylates. Further, specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337 and JP-B-1-40336, vinylphosphonic acid compounds described in JP-A-2-25493, and the like can also be mentioned. . In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Furthermore, Journal of Japan Adhesion Association vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as photocurable monomers and oligomers, can also be used.

  About these addition polymerizable compounds, the details of usage methods such as the structure, single use or combination, addition amount and the like can be arbitrarily set in accordance with the performance design of the final photocurable composition. For example, it is selected from the following viewpoints.

  From the viewpoint of sensitivity, a structure having a large unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. Further, in order to increase the strength of the cured film, those having three or more functionalities are preferable, and further, different functional numbers and different polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrene compound, vinyl ether compound). A method of adjusting both sensitivity and intensity by using a combination of these materials is also effective.

  In addition, the selection of an addition polymerization compound is also required for compatibility with other components (for example, binder polymers such as alkali-soluble resins, photopolymerization initiators, and colorants (pigments)) and dispersibility. The usage method is an important factor, and for example, compatibility may be improved by using a low-purity compound or using two or more kinds in combination.

In addition, a specific structure may be selected for the purpose of improving adhesion with a substrate or the like.
The addition polymerizable compound is preferably used in the range of 5 to 70% by mass, more preferably 10 to 60% by mass with respect to the non-volatile component in the photocurable composition. These may be used alone or in combination of two or more. In addition, the use method of the addition polymerizable compound can arbitrarily select an appropriate structure, blending, and addition amount from the viewpoint of polymerization inhibition with respect to oxygen, resolution, fogging property, refractive index change, surface adhesiveness, and the like.

(Photopolymerization initiator)
The photocurable composition of the present invention contains at least one photopolymerization initiator.
Examples of the photopolymerization initiator include halomethyl oxadiazole 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 each specification such as US Pat. No. 4,318,791 and European Patent Publication No. EP88050A, benzophenones described in US Pat. No. 4,199,420 Aromatic thiol compounds, such as thioxanthones or acridine compounds described in Fr-2456541, compounds such as coumarins or lophine dimers described in JP-A-10-62986, JP-A-8- Sulfonium organoboron complexes described in Japanese Patent No. 015521 , Etc. I can be mentioned.

  Among them, as photopolymerization initiators, acetophenone series, ketal series, benzophenone series, benzoin series, benzoyl series, xanthone series, triazine series, halomethyloxadiazole series, acridine series, coumarin series, lophine dimers series, A biimidazole type is preferred.

Examples of the acetophenone photopolymerization initiator include 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, and 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, zenzoin 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.
Preferable 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.

As a photoinitiator which can be used for this invention, it is not limited to the above photoinitiator, Another well-known thing can also be used. For example, a vicinal polykettle aldonyl compound described in US Pat. No. 2,367,660 and an α-carbonyl compound described in US Pat. Nos. 2,367,661 and 2,367,670. An acyloin ether described in US Pat. No. 2,448,828, an α-hydrocarbon-substituted aromatic acyloin compound described in US Pat. No. 2,722,512, US Pat. , 046,127 and 2,951,758, a triallylimidazole dimer / p-aminophenylketone combination described in US Pat. No. 3,549,367, And benzothiazole compounds / trihalomethyl-s-triazine compounds described in JP-A-51-48516.
Moreover, these photoinitiators can also be used together.

  As content of the photoinitiator in a photocurable composition, 0.1-15.0 mass% is preferable with respect to the total solid of this composition, More preferably, it is 0.5-10.0. % By mass. When the content of the photopolymerization initiator is within the above range, the polymerization reaction can be favorably progressed to form a film with good strength.

  The photocurable composition of the present invention may contain a sensitizer for the purpose of improving the radical generation efficiency of the photopolymerization initiator (radical initiator) and increasing the photosensitive wavelength. The sensitizer that can be used in the present invention is preferably a sensitizer that sensitizes a radical initiator by an electron transfer mechanism or an energy transfer mechanism.

Examples of the sensitizer that can be used in the present invention include those belonging to the compounds listed below and having an absorption wavelength in a wavelength region of 300 nm to 450 nm.
Examples of preferred sensitizers include those belonging to the following compounds and having an absorption wavelength in the range of 330 nm to 450 nm.
For example, polynuclear aromatics (for example, phenanthrene, anthracene, pyrene, perylene, triphenylene, 9,10-dialkoxyanthracene), xanthenes (for example, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), thioxanthones (Isopropylthioxanthone, diethylthioxanthone, chlorothioxanthone), cyanines (eg thiacarbocyanine, oxacarbocyanine), merocyanines (eg merocyanine, carbomerocyanine), phthalocyanines, thiazines (eg thionine, methylene blue, toluidine blue) , Acridines (eg, acridine orange, chloroflavin, acriflavine), anthraquinones (eg, anthraquinone), squariums (eg Squalium), acridine orange, coumarins (eg 7-diethylamino-4-methylcoumarin), ketocoumarin, phenothiazines, phenazines, styrylbenzenes, azo compounds, diphenylmethane, triphenylmethane, distyrylbenzenes, carbazole , Porphyrins, spiro compounds, quinacridone, indigo, styryl, pyrylium compounds, pyromethene compounds, pyrazolotriazole compounds, benzothiazole compounds, barbituric acid derivatives, thiobarbituric acid derivatives, acetophenone, benzophenone, thioxanthone, Michler's ketone and other aromatics Examples include ketone compounds and heterocyclic compounds such as N-aryloxazolidinones.

  The content of the sensitizer is preferably in the range of 0.1 to 30% by mass and in the range of 1 to 20% by mass with respect to the mass of the total solid content of the photocurable composition from the viewpoint of sensitivity and storage stability. Is more preferable, and the range of 2 to 15% by mass is still more preferable.

  The photocurable composition of the present invention preferably contains a co-sensitizer. In the present invention, the co-sensitizer has functions such as further improving the sensitivity of the sensitizing dye and initiator to actinic radiation or suppressing the inhibition of polymerization of the polymerizable compound by oxygen.

  Examples of such co-sensitizers include amines such as MR Sander et al., “Journal of Polymer Society”, Vol. 10, page 3173 (1972), Japanese Examined Patent Publication No. 44-20189, Japanese Patent Laid-Open No. 51-82102. Publication, JP 52-134692, JP 59-138205, JP 60-84305, JP 62-18537, JP 64-33104, Research Disclosure 33825 Specifically, triethanolamine, p-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, p-methylthiodimethylaniline and the like can be mentioned.

  Other examples of co-sensitizers include thiols and sulfides, for example, thiol compounds described in JP-A-53-702, JP-B-55-500806, JP-A-5-142773, and JP-A-56. And the like. Specific examples include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, 2-mercapto-4 (3H) -quinazoline, β-mercaptonaphthalene. Etc.

  Other examples include amino acid compounds (eg, N-phenylglycine), organometallic compounds described in Japanese Patent Publication No. 48-42965 (eg, tributyltin acetate), and hydrogen described in Japanese Patent Publication No. 55-34414. Examples thereof include donors and sulfur compounds described in JP-A-6-308727 (eg, trithian etc.).

  The content of the co-sensitizer is preferably in the range of 0.1 to 30% by mass with respect to the mass of the total solid content of the photosensitive composition from the viewpoint of improving the curing rate due to the balance between polymerization growth rate and chain transfer. The range of 1-25 mass% is more preferable, and the range of 0.5-20 mass% is still more preferable.

  Next, components other than the above that may be contained in the photocurable composition will be described.

〔solvent〕
Generally the photocurable composition of this invention can be suitably prepared using a solvent with the said component.

  Solvents 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, lactic acid Ethyl, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and methyl 3-oxypropionate and ethyl 3-oxypropionate 3-oxypropionic acid alkyl esters (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate), and 2-oxypropionic acid 2-oxypropionic acid alkyl esters such as til, ethyl 2-oxypropionate, and propyl 2-oxypropionate (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, Methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, 2-ethoxy 2-methyl methyl propionate), and 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, 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;
Aromatic hydrocarbons such as toluene, xylene and the like can be mentioned.

Of 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 suitable.
A solvent may be used independently and may be used in combination of 2 or more type.

[Other ingredients]
In the photocurable composition of the present invention, if necessary, a fluorine-based organic compound, a thermal polymerization inhibitor, a colorant, a photopolymerization initiator, other fillers, the above general formula (1) or (2) Various additives such as a polymer compound other than the polymer compound and alkali-soluble resin represented, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber, and an aggregation inhibitor can be contained.

<Fluorine organic compounds>
By containing a fluorinated organic compound, the liquid properties (particularly fluidity) of the coating liquid can be improved, and the uniformity of the coating thickness and the liquid-saving property 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. This is also effective in that a film having a uniform thickness with small thickness unevenness can be formed.

  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 is within 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 fluorine-based 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.).

Fluorine-based organic compounds are particularly effective in preventing coating unevenness and thickness unevenness when, for example, a coating film to be formed is thinned. It is also effective in slit coating that easily causes liquid breakage.
The addition amount of the fluorinated organic compound is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on the total mass of the pigment dispersion composition or the photocurable composition. It is.

<Thermal polymerization initiator>
It is also effective to include a thermal polymerization initiator in the photocurable composition of the present invention. Examples of the thermal polymerization initiator include various azo compounds and peroxide compounds. Examples of the azo compounds include azobis compounds. Examples of the peroxide compounds include ketones. Examples thereof include peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxyesters, peroxydicarbonates, and the like.

<Surfactant>
The photocurable composition of the present invention is preferably composed of various surfactants from the viewpoint of improving coatability, and various nonionic, cationic, and anionic surfactants can be used. Among these, a nonionic surfactant and a fluorosurfactant having a perfluoroalkyl group are preferable.
Specific examples of the fluorosurfactant include Megafac (registered trademark) series manufactured by Dainippon Ink and Chemicals, Inc., and Fluorard (registered trademark) series manufactured by 3M.

  In addition to the above, in the photocurable composition, as specific examples of additives, fillers such as glass and alumina; itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid Copolymers, acidic cellulose derivatives, polymers having hydroxyl groups, acid anhydrides added, alcohol-soluble nylons, alkali-soluble resins such as phenoxy resins formed from bisphenol A and epichlorohydrin; nonionics, kachins , Anionic surfactants, specifically phthalocyanine derivatives (commercial product EFKA-745 (manufactured by Morishita Sangyo)); organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid (co) Polymer Polyflow No. 75, no. 90, no. Cationic surfactants such as 95 (manufactured by Kyoeisha Yushi Chemical Co., Ltd.) and W001 (manufactured by Yusho Co., Ltd.);

  Examples of other additives include 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 (nonionic surfactants such as Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1 manufactured by BASF; W004, W005, W017 Anionic surfactants such as EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, E Polymer dispersing agents such as KA 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, 5000 , 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000 and other various Solsperse dispersants (manufactured by Zeneca); Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (Asahi Denka) and Isonet S-20 (Sanyo Kasei); 2- (3-t-butyl-5-methyl-2- Hydroxyphenyl) -5-chlorobenzoto Examples thereof include ultraviolet absorbers such as riazole and alkoxybenzophenone; and aggregation inhibitors such as sodium polyacrylate.

  Further, when the alkali solubility of the uncured part is promoted and the developability of the photocurable composition is further improved, the photocurable composition is an organic carboxylic acid, preferably a low molecular weight organic compound having a molecular weight of 1000 or less. Carboxylic acid can be added. 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, and camphoric acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, and 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.

<Thermal polymerization inhibitor>
It is preferable to add a thermal polymerization inhibitor to the photocurable composition of the present invention, for example, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, Benzoquinone, 4,4′-thiobis (3-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2-mercaptobenzimidazole and the like are useful.

  The photocurable composition of the present invention contains an alkali-soluble resin, a photopolymerizable compound, and a photopolymerization initiator (preferably together with a solvent) in the pigment dispersion composition of the present invention described above, and is necessary for this. Accordingly, it can be prepared by mixing an additive such as a surfactant.

<Color filter and manufacturing method thereof>
The color filter of the present invention is produced by forming a colored film (colored pattern) on a substrate such as glass using the above-described photocurable composition of the present invention. The photo-curable composition of the invention is applied to the substrate directly or via another layer (preferably applied by a coating method such as spin coating, slit coating, cast coating, roll coating) to form a photosensitive film. Then, the formed photosensitive film is exposed through a predetermined mask pattern, and after exposure, the uncured portion is developed and removed with a developing solution to develop a colored pattern (for example, a colored pixel) (for example, a colored pixel). The color filter can be most preferably manufactured.
Thereby, the color filter used for a liquid crystal display element and a solid-state image sensor has few process difficulties, and can be manufactured with high quality and low cost.
In this case, the radiation used for exposure is particularly preferably ultraviolet rays such as g-line, h-line, i-line, and j-line.

  Drying (prebaking) of the film with the photocurable composition of the present invention applied (preferably applied) on the substrate is performed under conditions of 10 to 300 seconds in a temperature range of 50 to 140 ° C. using a hot plate, an oven or the like. Can be done.

In development, the uncured part after exposure is eluted in the developer, leaving only the cured part. The development temperature is usually 20 to 30 ° C., and the development time is 20 to 90 seconds.
Any developer can be used as long as it dissolves the film of the photocurable composition in the uncured part while not dissolving the cured part. Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used.

  As said organic solvent, what was enumerated as the above-mentioned solvent which can be used when preparing the pigment dispersion composition or photocurable composition of this invention is mentioned.

Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, Concentration of an alkaline compound such as tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene, in a concentration of 0.001 to 10% by mass, preferably 0.01 to An alkaline aqueous solution dissolved so as to be 1% by mass can be mentioned.
In addition, when alkaline aqueous solution is used as a developing solution, generally it wash | cleans (rinse) with water after image development.

After the development, excess developer is washed away, dried, and then generally heated (post-baked) at a temperature of 100 to 240 ° C.
Post-baking is heating after development for complete curing, and is usually performed at about 200 ° C. to 250 ° C. (hard baking). This post-bake treatment is performed continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulation dryer), a high-frequency heater, or the like so that the coating film after development is in the above-described condition. be able to.

  By repeating the above operation in accordance with the desired number of hues and sequentially repeating for each color, a color filter in which a cured film colored with a plurality of colors is formed can be produced.

  When the film is formed by applying the photocurable composition of the present invention on a substrate, the dry thickness of the film is generally 0.3 to 5.0 μm, preferably 0.5 to 3.5 μm, Most desirably, the thickness is 1.0 to 2.5 μm.

As the substrate, for example, non-alkali glass, soda glass, Pyrex (registered trademark) glass, quartz glass used for liquid crystal display elements or the like, and those obtained by attaching a transparent conductive film to these, solid-state imaging elements, etc. Examples of the photoelectric conversion element substrate include a silicon substrate and a plastic substrate. 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 its surface.

  Examples of other layers in the case where the photocurable composition is applied to the substrate via another layer include a gas barrier layer and a solvent resistant layer.

In the above, the application of the pigment dispersion composition and the photocurable composition of the present invention has been described mainly focusing on the use of a color filter. However, the formation of a black matrix that isolates each colored pixel constituting the color filter is also described. Can be applied.
The black matrix is subjected to pattern exposure and development using the photocurable composition (pigment dispersion composition) of the present invention using a black pigment such as carbon black or titanium black as a pigment, and then further post-posting as necessary. It can be formed by baking to promote curing of the film.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, it is not limited to a following example. Unless otherwise specified, “%” and “part” are based on mass.

[Synthesis Example 1]
(Synthesis of Polymer 1)
M-1 5.0 g, MM-1 (AA-6: manufactured by Toa Gosei Co., Ltd.) 37.5 g, MAA 7.5 g, and 1-methoxy-2-propanol 73.0 g were introduced into a nitrogen-substituted three-necked flask. The mixture was stirred with a stirrer (Shinto Kagaku Co., Ltd .: Three One Motor), heated while flowing nitrogen into the flask, and heated to 90 ° C. To this was added 0.1 g of 2,2-azobis (2,4-dimethylvaleronitrile) (“V-65” manufactured by Wako Pure Chemical Industries, Ltd.), and the mixture was heated and stirred at 90 ° C. for 2 hours. After 2 hours, 0.1 g of V-65 was further added, and after 3 hours of heating and stirring, a 30% solution of polymer 1 was obtained.
It was 23,000 as a result of measuring the weight average molecular weight of the obtained high molecular compound by the gel permeation chromatography method (GPC) which used polystyrene as the standard substance.
From the titration with sodium hydroxide, the acid value per solid content was 98 mgKOH / g.

[Synthesis Example 2]
(Synthesis of Polymer 3)
M-6 18.0 g, MM-1 (AA-6: manufactured by Toa Gosei Co., Ltd.) 140.4 g, MAA 21.6 g, and 1-methoxy-2-propanol 178.0 g were introduced into a nitrogen-substituted three-necked flask. The mixture was stirred with a stirrer (Shinto Kagaku Co., Ltd .: Three One Motor), heated while flowing nitrogen into the flask, and heated to 90 ° C. To this was added 0.9 g of 2,2-azobis (2,4-dimethylvaleronitrile) (“V-65” manufactured by Wako Pure Chemical Industries, Ltd.), and the mixture was heated and stirred at 90 ° C. for 2 hours. After 2 hours, 0.9 g of V-65 was further added, and after 3 hours of heating and stirring, 240.0 g of 1-methoxy-2-propyl acetate was added to the resulting reaction solution to obtain a 30% solution of polymer 2. It was.
As a result of measuring the weight average molecular weight of the obtained polymer compound by a gel permeation chromatography method (GPC) using polystyrene as a standard substance, it was 20,000.
From the titration with sodium hydroxide, the acid value per solid content was 79 mgKOH / g.

  In the same manner, polymers 2, 4 to 31, which are specific polymers, were synthesized. Table 1 below shows the composition (type and use ratio) of the monomers used for the synthesis of the polymers 1 to 31, the weight average molecular weight of the obtained polymer, and the acid value.

  In addition, M-1, M-3, M-6, M-9, M-11, M-15, M-25, and M-27 used for the synthesis of the specific polymer are represented by the general formula (1). It is an exemplary compound shown as a specific example of the monomer to be prepared. Details of other monomers are shown in the column of Table 1.

[Example 1]
<Preparation of red pigment dispersion composition (R-1)>
The components of the following composition (a-1) were mixed, and using a homogenizer, the rotational speed was 3000 r. p. m. And mixed for 3 hours to prepare a mixed solution containing the pigment.
[Composition (a-1)]
・ C. I. Pigment Red 254 ... 85 parts C.I. I. Pigment Red 177 15 parts 30% solution of Polymer 1 (pigment dispersant) 70 parts Solsperse 24000GR
(Nippon Lubrizol Co., Ltd .; polyester dispersant) ... 10 parts, 1-methoxy-2-propyl acetate ... 820 parts

Subsequently, the mixed solution obtained above was further subjected to a dispersion treatment for 6 hours using a bead disperser Dispermat (manufactured by GETZMANN) using 0.3 mmφ zirconia beads. Thereafter, the dispersion treatment was further performed at a flow rate of 500 g / min under a pressure of 2000 kg / cm ³ using a high-pressure disperser NANO-3000-10 with a decompression mechanism (manufactured by Nippon BEE Co., Ltd.). This dispersion treatment was repeated 10 times to obtain a red pigment dispersion composition (R-1).

<Evaluation of pigment dispersion composition>
The following (1-1) and (1-2) were evaluated about the obtained red pigment dispersion composition (R-1). The results are shown in Table 2 below.
(1-1) Measurement and Evaluation of Viscosity About the obtained red pigment dispersion composition (R-1), using an E-type viscometer, viscosity η ¹ of the pigment dispersion composition immediately after dispersion and after dispersion (to room temperature) The viscosity η ² of the pigment dispersion composition after 1 week was measured, and the degree of thickening was evaluated. The evaluation results are shown in Table 2 below. Here, the low viscosity indicates that the increase in viscosity due to the dispersant is suppressed, and the dispersibility and dispersion stability of the pigment are good.

(1-2) Measurement and Evaluation of Contrast The obtained pigment dispersion composition was applied on a glass substrate, and a sample was prepared so that the thickness of the coating film after drying was 1 μm. This sample was placed between two polarizing plates, the amount of transmitted light was measured when the polarization axis was parallel and when the polarization axis was parallel, and the ratio was taken as contrast. 512 color display 10.4 “size TFT-LCD color filter, planting, Koseki, Fukunaga, Yamanaka”). The results of measurement evaluation are shown in Table 2 below. Here, a high contrast indicates that the pigment is uniformly dispersed in a highly refined state, and thus the transmittance, that is, the coloring power is high.

[Examples 2-3, Comparative Examples 1-3]
In Example 1, 70 parts of a 30% solution of polymer 1 used for the preparation of the red pigment dispersion composition (R-1) was replaced with 30 of each polymer (specific polymer or comparative polymer) shown in Table 2. The red pigment dispersion compositions (R-2) and (R-3) of Examples 2 to 3 and the red color of Comparative Examples 1 to 3 were the same as Example 1 except that the amount was changed to 70 parts by weight. Pigment dispersion compositions (CR-1), (CR-2) and (CR-3) were obtained.
Furthermore, the obtained pigment dispersion compositions were measured and evaluated for viscosity and contrast in the same manner as in the above (1-1) and (1-2). The results are shown in Table 2 below.

[Example 4]
<Preparation of green pigment dispersion (G-1)>
The components of the following composition (a-2) were mixed, and the rotational speed was 3000 r. p. m. And mixed for 3 hours to prepare a mixed solution containing the pigment.
[Composition (a-2)]
・ C. I. Pigment Green 36 ... 65 parts C.I. I. Pigment Yellow 150 ... 35 parts · 30% solution of Polymer 1 (pigment dispersant) ... 70 parts · Solsperse 24000GR
(Nippon Lubrizol Co., Ltd .; polyester dispersant) ... 40 parts, 1-methoxy-2-propyl acetate ... 790 parts

Subsequently, the mixed solution obtained above was subjected to dispersion treatment in the same manner as in Example 1 to obtain a green pigment dispersion composition (G-1). Further, for each of the obtained pigment dispersion compositions, Viscosity and contrast were measured and evaluated in the same manner as (1-1) and (1-2). The results are shown in Table 2 below.

[Examples 5-6, Comparative Examples 4-6]
In Example 4, 30 parts of a 30% solution of polymer 1 used for the preparation of the green pigment dispersion composition (G-1) was replaced with 30 parts of each polymer (specific polymer or comparative polymer) shown in Table 2. The green pigment dispersion compositions (G-2) and (G-3) of Examples 5 to 6 and the green color of Comparative Examples 4 to 6 were the same as in Example 4 except that the amount was changed to 70 parts by weight. Pigment dispersion compositions (CG-1), (CG-2) and (CG-3) were obtained.
Furthermore, the obtained pigment dispersion compositions were measured and evaluated for viscosity and contrast in the same manner as in the above (1-1) and (1-2). The results are shown in Table 2.

[Example 7]
<Preparation of blue pigment dispersion (B-1)>
The components of the following composition (a-3) were mixed, and the rotational speed was 3000 r. p. m. And mixed for 3 hours to prepare a mixed solution containing the pigment.
[Composition (a-3)]
・ C. I. Pigment Blue 15; 6 ... 85 parts C.I. I. Pigment Violet 23 15 parts 30% solution of Polymer 1 (pigment dispersant) 70 parts Ajisper PB821
(Manufactured by Ajinomoto Fine Chemicals; polyester-based dispersant) ... 10 parts, 1-methoxy-2-propyl acetate ... 820 parts

Subsequently, the mixed solution obtained above was subjected to a dispersion treatment in the same manner as in Example 1 to obtain a blue pigment dispersion composition (B-1). Further, the obtained pigment dispersion composition (B-1) was obtained. ), Viscosity and contrast were measured and evaluated in the same manner as (1-1) and (1-2). The results are shown in Table 2 below.

[Examples 8 to 9, Comparative Examples 7 to 9]
In Example 7, 30 parts of a 30% solution of polymer 1 used for the preparation of the blue pigment dispersion composition (B-1) was replaced with 30 parts of each polymer (specific polymer or comparative polymer) shown in Table 2. The blue pigment dispersion compositions (B-2) and (B-3) of Examples 8 to 9 and the blue colors of Comparative Examples 7 to 9 were the same as Example 7 except that the amount was changed to 70 parts by weight. Pigment dispersion compositions (CB-1), (CB-2) and (CB-3) were obtained.
Furthermore, the obtained pigment dispersion compositions were measured and evaluated for viscosity and contrast in the same manner as in the above (1-1) and (1-2). The results are shown in Table 2 below.

[Example 10]
<Preparation of a red photocurable composition>
Each component described in the following composition (a-4) is further added to the pigment dispersion composition (R-1) obtained in Example 1, and the mixture is stirred and mixed, whereby the red photocurable composition of Example 10 is used. (Red color resist solution) was prepared.
[Composition (a-4)]
・ Dipentaerythritol pentahexaacrylate: 80 parts (photopolymerizable compound)
4- [o-bromo-pN, N-di (ethoxycarbonyl) aminophenyl] -2,6-di (trichloromethyl) -S-triazine 30 parts (photopolymerization initiator)
Benzyl methacrylate / methacrylic acid (= 70/30 [molar ratio]) copolymer (weight average molecular weight: 10,000) propylene glycol monomethyl ether acetate solution (solid content 40%) ... 200 parts (alkali-soluble resin)
1-methoxy-2-propyl acetate (solvent) 490 parts

<Preparation of color filter using photocurable composition>
The obtained red photocurable composition (red color resist solution) was applied on a 100 mm × 100 mm glass substrate (1737, manufactured by Corning) so that the x value serving as an index of color density was 0.650. And dried in an oven at 90 ° C. for 60 seconds (pre-baking). Thereafter, the entire surface of the coating film was exposed at 200 mJ / cm ² (illuminance 20 mW / cm ² ), and the exposed coating film was 1% aqueous solution of alkali developer CDK-1 (manufactured by Fuji Film Electronics Materials Co., Ltd.). And rested for 60 seconds. After standing still, pure water was sprayed in a shower to wash away the developer. Then, the coating film that has been exposed and developed as described above is heated in an oven at 220 ° C. for 1 hour (post-baking) to form a colored pattern (colored resin film) for the color filter on the glass substrate, A colored filter substrate (color filter) was produced.

<Evaluation of color filter>
About the produced colored filter substrate, the following (2-1) and (2-2) were evaluated. The results are shown in Table 3 below.

(2-1) Contrast A polarizing plate is placed on the colored resin film of the colored filter substrate, and the colored resin film is sandwiched between them. The luminance when the polarizing plate is parallel and the luminance when the polarizing plate is orthogonal are obtained using BM-5 manufactured by Topcon Corporation. The value obtained by dividing the parallel brightness by the orthogonal brightness (= the parallel brightness / the orthogonal brightness) was used as an index for evaluating the contrast. Larger values indicate higher contrast.

(2-2) Developability In the exposure process, the presence or absence of a residue in a region not irradiated with light (unexposed portion) was observed with an optical microscope to evaluate the developability.
A: No residue was observed at all in the unexposed area.
Δ: A slight residue was confirmed in the unexposed area, but there was no practical problem.
X: Residue was remarkably confirmed in the unexposed part.

[Examples 11-12, Comparative Examples 10-12]
The pigment dispersion composition (R-1) used in Example 10 is replaced with the pigment dispersion compositions (R-2), (R-3), and (CR) obtained in Examples 2-3 and Comparative Examples 1-3. -1) A red photocurable composition (red color resist solution) was prepared in the same manner as in Example 10 except that each of them was replaced with (CR-2) and (CR-3). 12 and the colored filter substrate (color filter) of Comparative Examples 10-12 were produced.
Furthermore, the obtained colored filter substrate was evaluated for contrast and developability in the same manner as in (2-1) and (2-2). The results are shown in Table 3 below.

[Example 13]
<Adjustment of green color resist solution>
The components described in the following composition (a-5) are further added to the pigment dispersion composition (G-1) obtained in Example 4 and mixed by stirring. The green light curable composition of Example 13 is then mixed. (Green color resist solution) was prepared.
[Composition (a-5)]
Dipentaerythritol pentahexaacrylate 50 parts (photopolymerizable compound)
4- [o-bromo-pN, N-di (ethoxycarbonyl) aminophenyl] -2,6-di (trichloromethyl) -S-triazine 20 parts (photopolymerization initiator)
Benzyl methacrylate / methacrylic acid (= 70/30 [molar ratio]) copolymer (weight average molecular weight: 10,000) propylene glycol monomethyl ether acetate solution (solid content 40%) ... 50 parts (alkali-soluble resin)
・ 1-methoxy-2-propyl acetate (solvent): 180 parts

<Preparation and evaluation of color filter using photocurable composition>
The obtained green light curable composition (green color resist solution) was applied on a 100 mm × 100 mm glass substrate (1737, manufactured by Corning) so that the y value as an index of color density was 0.600. And dried in an oven at 90 ° C. for 60 seconds (pre-baking). Thereafter, the entire surface of the coating film was exposed at 200 mJ / cm ² (illuminance 20 mW / cm ² ), and the exposed coating film was 1% aqueous solution of alkali developer CDK-1 (manufactured by Fuji Film Electronics Materials Co., Ltd.). And rested for 60 seconds. After standing still, pure water was sprayed in a shower to wash away the developer. Then, the coating film that has been exposed and developed as described above is heated in an oven at 220 ° C. for 1 hour (post-baking) to form a colored pattern (colored resin film) for the color filter on the glass substrate, A colored filter substrate (color filter) was produced.

  Furthermore, the obtained colored filter substrate was evaluated for contrast and developability in the same manner as in (2-1) and (2-2). The results are shown in Table 3 below.

[Examples 14-15, Comparative Examples 13-15]
The pigment dispersion composition (G-1) used in Example 13 was replaced with the pigment dispersion compositions (G-2), (G-3), and (CG) obtained in Examples 5-6 and Comparative Examples 4-6. -1) A green light curable composition (green color resist solution) was prepared in the same manner as in Example 13 except that it was replaced with (CG-2) and (CG-3). 15 and Comparative Example 13 to 15 colored filter substrates (color filters) were produced.
Furthermore, the obtained colored filter substrate was evaluated for contrast and developability in the same manner as in (2-1) and (2-2). The results are shown in Table 3 below.

[Example 16]
<Preparation of blue light curable composition>
The components described in the following composition (a-6) are further added to the pigment dispersion composition (B-1) obtained in Example 7, and the mixture is stirred and mixed, whereby the blue light curable composition of Example 16 is used. (Blue color resist solution) was prepared.
[Composition (a-6)]
Dipentaerythritol pentahexaacrylate 150 parts (photopolymerizable compound)
4- [o-bromo-pN, N-di (ethoxycarbonyl) aminophenyl] -2,6-di (trichloromethyl) -S-triazine ... 60 parts (photopolymerization initiator)
Benzyl methacrylate / methacrylic acid (= 70/30 [molar ratio]) copolymer (weight average molecular weight: 10,000) propylene glycol monomethyl ether acetate solution (solid content 40%) ... 400 parts (alkali-soluble resin)
1-methoxy-2-propyl acetate (solvent) 1440 parts

<Preparation and evaluation of color filter using photocurable composition>
The obtained blue light curable composition (blue color resist solution) was applied on a 100 mm × 100 mm glass substrate (1737, manufactured by Corning) so that the y value serving as an index of color density was 0.090. And dried in an oven at 90 ° C. for 60 seconds (pre-baking). Thereafter, the entire surface of the coating film was exposed at 200 mJ / cm ² (illuminance 20 mW / cm ² ), and the exposed coating film was 1% aqueous solution of alkali developer CDK-1 (manufactured by Fuji Film Electronics Materials Co., Ltd.). And rested for 60 seconds. After standing still, pure water was sprayed in a shower to wash away the developer. Then, the coating film that has been exposed and developed as described above is heated in an oven at 220 ° C. for 1 hour (post-baking) to form a colored pattern (colored resin film) for the color filter on the glass substrate, A colored filter substrate (color filter) was produced.
Furthermore, the obtained colored filter substrate was evaluated for contrast and developability in the same manner as in (2-1) and (2-2). The results are shown in Table 3 below.

[Examples 17 to 18, Comparative Examples 16 to 18]
The pigment dispersion composition (B-1) used in Example 16 was replaced with the pigment dispersion compositions (B-2), (B-3), and (CB) obtained in Examples 8 to 9 and Comparative Examples 7 to 8. -1) A blue light curable composition (blue color resist solution) was prepared in the same manner as in Example 13 except that it was replaced with (CB-2) and (CB-3). 15 and Comparative Example 13 to 15 colored filter substrates (color filters) were produced.
Furthermore, the obtained colored filter substrate was evaluated for contrast and developability in the same manner as in (2-1) and (2-2). The results are shown in Table 3 below.

[Example 19]
<Preparation of red pigment dispersion composition (R-4)>
The components of the following composition (b-1) were mixed, and the rotational speed was 3,000 r.m. using a homogenizer. p. m. And mixed for 3 hours to prepare a mixed solution containing the pigment.
[Composition (b-1)]
・ C. I. Pigment Red 254 ... 60 parts C.I. I. Pigment Red 177 ... 40 parts-30% solution of the polymer 1 (pigment dispersant) ... 70 parts-Solsperse 24000GR
(Nippon Lubrizol Co., Ltd .; polyester dispersant) ... 10 parts, 1-methoxy-2-propyl acetate ... 820 parts

Subsequently, the mixed solution obtained above was further subjected to dispersion treatment for 6 hours with a bead disperser disperse mat (manufactured by GETZMANN) using 0.3 mmφ zirconia beads. The dispersion treatment was performed at a flow rate of 500 g / min under a pressure of 2000 kg / cm ³ using −3000-10 (manufactured by Nippon BEE Co., Ltd.) This dispersion treatment was repeated 10 times to obtain a red pigment dispersion composition (R-4).

<Evaluation of pigment dispersion composition>
The obtained red pigment dispersion composition (R-4) was evaluated in the above (1-1) and (1-2). The evaluation results are shown in Table 4 below.

[Examples 20 to 21, Comparative Examples 19 to 21]
In Example 19, 70 parts of a 30% solution of Polymer 1 used for the preparation of the red pigment dispersion composition (R-4) was replaced with 30 of each polymer (specific polymer or comparative polymer) shown in Table 2. The red pigment dispersion compositions (R-5) and (R-6) of Examples 20 to 21 and the red color of Comparative Examples 19 to 21 were the same as in Example 19, except that the percentage solution was changed to 70 parts. Pigment dispersion compositions (CR-4), (CR-5) and (CR-6) were obtained.
Furthermore, about each obtained pigment dispersion composition, the said (1-1) and (1-2) were evaluated.

[Example 22]
<Preparation of green pigment dispersion (G-4)>
Components of the following composition (b-2) were mixed, and the rotational speed was 3,000 r.m. using a homogenizer. p. m. And mixed for 3 hours to prepare a mixed solution containing the pigment.
[Composition (b-2)]
・ C. I. Pigment Green 36 ... 60 copies I. Pigment Yellow 150 ... 40 parts · 30% solution of Polymer 3 (pigment dispersant) ... 70 parts · Solsperse 24000GR
(Nippon Lubrizol Co., Ltd .; polyester dispersant) ... 40 parts, 1-methoxy-2-propyl acetate ... 790 parts

Subsequently, the mixed solution obtained above was subjected to a dispersion treatment in the same manner as in Example 19 to obtain a green pigment dispersion composition (G-4). Further, each of the obtained pigment dispersion compositions (G- For 4), the viscosity and contrast were measured and evaluated in the same manner as (1-1) and (1-2). The results are shown in Table 2 below.

[Examples 23 to 24, Comparative Examples 22 to 24]
In Example 22, 30 parts of a 30% solution of polymer 3 used for the preparation of the green pigment dispersion composition (G-4) was replaced with 30 of each polymer (specific polymer or comparative polymer) shown in Table 4. The green pigment dispersion compositions (G-5) and (G-6) of Examples 23 to 24 and the green color of Comparative Examples 22 to 24 were the same as Example 22 except that the amount was changed to 70 parts by weight. Pigment dispersion compositions (CG-4), (CG-5) and (CG-6) were obtained.
Furthermore, the obtained pigment dispersion compositions were measured and evaluated for viscosity and contrast in the same manner as in the above (1-1) and (1-2). The results are shown in Table 4 below.

[Example 25]
<Preparation of blue pigment dispersion (B-4)>
Components of the following composition (b-3) were mixed, and the rotational speed was 3,000 r.m. using a homogenizer. p. m. And mixed for 3 hours to prepare a mixed solution containing the pigment.
[Composition (b-3)]
・ C. I. Pigment Blue 15; 6 ... 80 parts C.I. I. Pigment violet 23 ... 20 parts · 30% solution of polymer 4 (pigment dispersant) ... 70 parts · Azisper PB821
(Ajinomoto Fine Chemical Co., Ltd .; polyester dispersant) 10 parts 1-methoxy-2-propyl acetate 820 parts

Subsequently, the mixed solution obtained above was subjected to a dispersion treatment in the same manner as in Example 19 to obtain a blue pigment dispersion composition (B-4). Further, each of the obtained pigment dispersion compositions (B- For 4), the viscosity and contrast were measured and evaluated in the same manner as (1-1) and (1-2). The results are shown in Table 4 below.

[Examples 26 to 27, Comparative Examples 26 to 27]
In Example 25, 30 parts of a 30% solution of the polymer 4 used for the preparation of the blue pigment dispersion composition (B-4) was replaced with 30 parts of each polymer (specific polymer or comparative polymer) shown in Table 4. The blue pigment dispersion compositions (B-5) and (B-6) of Examples 26 to 27 and the blue color of Comparative Examples 26 to 27 were the same as in Example 25 except that the amount was changed to 70 parts by weight. Pigment dispersion compositions (CB-4), (CB-5) and (CB-6) were obtained.
Furthermore, the obtained pigment dispersion compositions were measured and evaluated for viscosity and contrast in the same manner as in the above (1-1) and (1-2). The results are shown in Table 4 below.

[Example 28]
<Preparation of a red photocurable composition>
The components described in the following composition (b-4) were further added to the pigment dispersion composition (R-4) obtained in Example 19 and mixed by stirring. The red photocurable composition of Example 28 was then mixed. (Red color resist solution) was prepared.
[Composition (b-4)]
・ Dipentaerythritol pentahexaacrylate: 80 parts (photopolymerizable compound)
4- [o-bromo-pN, N-di (ethoxycarbonyl) aminophenyl] -2,6-di (trichloromethyl) -S-triazine 30 parts (photopolymerization initiator)
Benzyl methacrylate / methacrylic acid (= 70/30 [molar ratio]) copolymer (weight average molecular weight: 10,000) propylene glycol monomethyl ether acetate solution (solid content 40%) ... 200 parts (alkali-soluble resin)
1-methoxy-2-propyl acetate (solvent) 490 parts

<Preparation of color filter using photocurable composition>
The obtained red photocurable composition (red color resist solution) was applied on a 100 mm × 100 mm glass substrate (1737, manufactured by Corning) so that the x value serving as an index of color density was 0.650. And dried in an oven at 90 ° C. for 60 seconds (pre-baking). Thereafter, the entire surface of the coating film was exposed at 200 mJ / cm ² (illuminance 20 mW / cm ² ), and the exposed coating film was 1% aqueous solution of alkali developer CDK-1 (manufactured by Fuji Film Electronics Materials Co., Ltd.). And rested for 60 seconds. After standing still, pure water was sprayed in a shower to wash away the developer. Then, the coating film that has been exposed and developed as described above is heated in an oven at 220 ° C. for 1 hour (post-baking) to form a colored pattern (colored resin film) for the color filter on the glass substrate, A colored filter substrate (color filter) was produced.

<Evaluation of color filter>
The produced colored filter substrate was evaluated for contrast and developability in the same manner as in (2-1) and (2-2). The results are shown in Table 5 below.

[Examples 29-30, Comparative Examples 28-30]
The pigment dispersion composition (R-4) used in Example 28 was replaced with the pigment dispersion compositions (R-5), (R-6), and (CR) obtained in Examples 20 to 21 and Comparative Examples 19 to 21. -4) A red light curable composition (red color resist solution) was prepared in the same manner as in Example 28 except that each of them was replaced with (CR-5) and (CR-6). 30 and the color filter substrate (color filter) of Comparative Examples 28-30 were produced.
Furthermore, the obtained colored filter substrate was evaluated for contrast and developability in the same manner as in (2-1) and (2-2). The results are shown in Table 5 below.

[Example 31]
<Adjustment of green color resist solution>
The components described in the following composition (b-5) are further added to the pigment dispersion composition (G-4) obtained in Example 22, and the mixture is stirred and mixed. Thus, the green light curable composition of Example 31 is used. (Green color resist solution) was prepared.
[Composition (b-5)]
Dipentaerythritol pentahexaacrylate 50 parts (photopolymerizable compound)
4- [o-bromo-pN, N-di (ethoxycarbonyl) aminophenyl] -2,6-di (trichloromethyl) -S-triazine 20 parts (photopolymerization initiator)
Benzyl methacrylate / methacrylic acid (= 70/30 [molar ratio]) copolymer (weight average molecular weight: 10,000) propylene glycol monomethyl ether acetate solution (solid content 40%) ... 50 parts (alkali-soluble resin)
・ 1-methoxy-2-propyl acetate (solvent): 180 parts

<Preparation and evaluation of color filter using photocurable composition>
The prepared photocurable composition (color resist solution) was applied on a 100 mm × 100 mm glass substrate (1737, manufactured by Corning) so that the y value serving as an index of color density was 0.600. It was dried in an oven at 60 ° C. for 60 seconds (pre-baking). Thereafter, the entire surface of the coating film was exposed at 200 mJ / cm ² (illuminance 20 mW / cm ² ), and the exposed coating film was 1% aqueous solution of alkali developer CDK-1 (manufactured by Fuji Film Electronics Materials Co., Ltd.). And rested for 60 seconds. After standing still, pure water was sprayed in a shower to wash away the developer. Then, the coating film that has been exposed and developed as described above is heated in an oven at 220 ° C. for 1 hour (post-baking) to form a colored pattern (colored resin film) for the color filter on the glass substrate, A colored filter substrate (color filter) was produced.

  Furthermore, the obtained colored filter substrate was evaluated for contrast and developability in the same manner as in (2-1) and (2-2). The results are shown in Table 5 below.

[Examples 32-33, Comparative Examples 31-33]
The pigment dispersion composition (G-4) used in Example 31 was replaced with the pigment dispersion compositions (G-5), (G-6), and (CG) obtained in Examples 23 to 24 and Comparative Examples 22 to 24. -4) A green light curable composition (green color resist solution) was prepared in the same manner as in Example 31 except that each of them was replaced with (CG-5) and (CG-6). 33 and colored filter substrates (color filters) of Comparative Examples 31 to 33 were produced.
Furthermore, the obtained colored filter substrate was evaluated for contrast and developability in the same manner as in (2-1) and (2-2). The results are shown in Table 5 below.

[Example 34]
<Preparation of blue light curable composition>
Each component described in the following composition (b-6) is further added to the pigment dispersion composition (B-4) obtained in Example 25, followed by stirring and mixing, and the blue light curable composition of Example 34 is obtained. (Blue color resist solution) was prepared.

[Composition (b-6)]
Dipentaerythritol pentahexaacrylate 150 parts (photopolymerizable compound)
4- [o-bromo-pN, N-di (ethoxycarbonyl) aminophenyl] -2,6-di (trichloromethyl) -S-triazine ... 60 parts (photopolymerization initiator)
Benzyl methacrylate / methacrylic acid (= 70/30 [molar ratio]) copolymer (weight average molecular weight: 10,000) propylene glycol monomethyl ether acetate solution (solid content 40%) ... 400 parts (alkali-soluble resin)
1-methoxy-2-propyl acetate (solvent) 1440 parts

<Preparation and evaluation of color filter using photocurable composition>
The obtained blue light curable composition (blue color resist solution) was applied on a 100 mm × 100 mm glass substrate (1737, manufactured by Corning) so that the y value serving as an index of color density was 0.090. And dried in an oven at 90 ° C. for 60 seconds (pre-baking). Thereafter, the entire surface of the coating film was exposed at 200 mJ / cm ² (illuminance 20 mW / cm ² ), and the exposed coating film was 1% aqueous solution of alkali developer CDK-1 (manufactured by Fuji Film Electronics Materials Co., Ltd.). And rested for 60 seconds. After standing still, pure water was sprayed in a shower to wash away the developer. Then, the coating film that has been exposed and developed as described above is heated in an oven at 220 ° C. for 1 hour (post-baking) to form a colored pattern (colored resin film) for the color filter on the glass substrate, A colored filter substrate (color filter) was produced.

  Furthermore, the obtained colored filter substrate was evaluated for contrast and developability in the same manner as in (2-1) and (2-2). The results are shown in Table 5 below.

[Examples 35 to 36, Comparative Examples 34 to 36]
The pigment dispersion composition (B-4) used in Example 34 was replaced with the pigment dispersion compositions (B-5), (B-6), and (CB) obtained in Examples 26 to 27 and Comparative Examples 25 to 27. -4), a blue light curable composition (blue color resist solution) was prepared in the same manner as in Example 34 except that it was replaced with (CB-5) and (CB-6). 36 and colored filter substrates (color filters) of Comparative Examples 34 to 36 were produced.
Furthermore, the obtained colored filter substrate was evaluated for contrast and developability in the same manner as in (2-1) and (2-2). The results are shown in Table 5 below.

[Example 37]
<Preparation of red pigment dispersion composition (R-7)>
Components of the following composition (c-1) were mixed, and the rotational speed was 3,000 r.m. using a homogenizer. p. m. And mixed for 3 hours to prepare a mixed solution containing the pigment.
[Composition (c-1)]
・ C. I. Pigment Red 254 ... 80 parts I. Pigment Red 177 ... 20 parts · 30% solution of the polymer 3 (pigment dispersant) ... 70 parts · Solsperse 24000GR
(Nippon Lubrizol Co., Ltd .; polyester dispersant) ... 10 parts, 1-methoxy-2-propyl acetate ... 820 parts

Subsequently, the mixed solution obtained above was further subjected to dispersion treatment for 6 hours with a bead disperser disperse mat (manufactured by GETZMANN) using 0.3 mmφ zirconia beads. The dispersion treatment was performed at a flow rate of 500 g / min under a pressure of 2000 kg / cm ³ using −3000-10 (manufactured by Nippon BEE Co., Ltd.) This dispersion treatment was repeated 10 times to obtain a red pigment dispersion composition (R-7).

<Evaluation of pigment dispersion composition>
The obtained red pigment dispersion composition (R-7) was evaluated in the above (1-1) and (1-2). The evaluation results are shown in Table 6 below.

[Examples 38 to 44, Comparative Examples 37 to 39]
In Example 37, 30 parts of a 30% solution of Polymer 3 used for the preparation of the red pigment dispersion composition (R-7) was replaced with 30 parts of each polymer (specific polymer or comparative polymer) shown in Table 6. The red pigment dispersion compositions (R-8) to (R-14) of Examples 38 to 44 and the red color of Comparative Examples 37 to 39 were the same as Example 37 except that the content was changed to 70 parts by weight. Pigment dispersion compositions (CR-7) to (CR-9) were obtained.
Furthermore, about each obtained pigment dispersion composition, the said (1-1) and (1-2) were evaluated.

[Example 45]
<Preparation of green pigment dispersion (G-7)>
The components of the following composition (c-2) were mixed, and the rotational speed was 3,000 r.m. using a homogenizer. p. m. And mixed for 3 hours to prepare a mixed solution containing the pigment.
[Composition (c-2)]
・ C. I. Pigment Green 36 ... 90 parts I. Pigment Yellow 150 ... 10 parts · 30% solution of Polymer 13 (pigment dispersant) ... 70 parts · Solsperse 24000GR
(Nippon Lubrizol Co., Ltd .; polyester dispersant) ... 40 parts, 1-methoxy-2-propyl acetate ... 790 parts

Subsequently, the mixed solution obtained above was subjected to a dispersion treatment in the same manner as in Example 37 to obtain a green pigment dispersion composition (G-7). Further, each pigment dispersion composition (G- For 7), the viscosity and contrast were measured and evaluated in the same manner as (1-1) and (1-2). The results are shown in Table 6 below.

[Examples 46 to 51, Comparative Examples 40 to 42]
In Example 45, 30 parts of a 30% solution of the polymer 13 used for the preparation of the green pigment dispersion composition (G-7) was replaced with 30 parts of each polymer (specific polymer or comparative polymer) shown in Table 6. The green pigment dispersion compositions (G-8) to (G-13) of Examples 46 to 51 and the green color of Comparative Examples 40 to 42 were the same as in Example 45 except that the percentage solution was changed to 70 parts. Pigment dispersion compositions (CG-7) to (CG-9) were obtained.
Furthermore, the obtained pigment dispersion compositions were measured and evaluated for viscosity and contrast in the same manner as in the above (1-1) and (1-2). The results are shown in Table 6 below.

[Example 52]
<Preparation of blue pigment dispersion (B-7)>
The components of the following composition (c-3) were mixed, and the rotational speed was 3,000 r.m. using a homogenizer. p. m. And mixed for 3 hours to prepare a mixed solution containing the pigment.
[Composition (c-3)]
・ C. I. Pigment Blue 15; 6 70 parts C.I. I. Pigment Violet 23 ... 30 parts · 30% solution of Polymer 4 (pigment dispersant) ... 70 parts · Azisper PB821
(Manufactured by Ajinomoto Fine Chemicals; polyester-based dispersant) ... 10 parts, 1-methoxy-2-propyl acetate ... 820 parts

Subsequently, the mixed solution obtained above was subjected to a dispersion treatment in the same manner as in Example 37 to obtain a blue pigment dispersion composition (B-7). Further, the obtained pigment dispersion compositions (B- For 7), the viscosity and contrast were measured and evaluated in the same manner as (1-1) and (1-2). The results are shown in Table 6 below.

[Examples 53 to 56, Comparative Examples 43 to 45]
In Example 52, 70 parts of a 30% solution of polymer 4 used for the preparation of the blue pigment dispersion composition (B-7) was replaced with 30 of each polymer (specific polymer or comparative polymer) shown in Table 6. The blue pigment dispersion compositions (B-8) to (B-11) of Examples 53 to 56 and the blue color of Comparative Examples 43 to 45 were the same as in Example 525 except that the amount was changed to 70 parts by weight. Pigment dispersion compositions (CB-7) to (CB-9) were obtained.
Furthermore, the obtained pigment dispersion compositions were measured and evaluated for viscosity and contrast in the same manner as in the above (1-1) and (1-2). The results are shown in Table 6 below.

[Example 57]
<Preparation of a red photocurable composition>
The components described in the following composition (c-4) were further added to the pigment dispersion composition (R-7) obtained in Example 37, and mixed by stirring. The red light curable composition of Example 57 was then mixed. (Red color resist solution) was prepared.
[Composition (c-4)]
・ Dipentaerythritol pentahexaacrylate: 80 parts (photopolymerizable compound)
4- [o-bromo-pN, N-di (ethoxycarbonyl) aminophenyl] -2,6-di (trichloromethyl) -S-triazine 30 parts (photopolymerization initiator)
Benzyl methacrylate / methacrylic acid (= 70/30 [molar ratio]) copolymer (weight average molecular weight: 10,000) propylene glycol monomethyl ether acetate solution (solid content 40%) ... 200 parts (alkali-soluble resin)
1-methoxy-2-propyl acetate (solvent) 490 parts

<Preparation of color filter using photocurable composition>
The obtained red photocurable composition (red color resist solution) was applied on a 100 mm × 100 mm glass substrate (1737, manufactured by Corning) so that the x value serving as an index of color density was 0.650. And dried in an oven at 90 ° C. for 60 seconds (pre-baking). Thereafter, the entire surface of the coating film was exposed at 200 mJ / cm ² (illuminance 20 mW / cm ² ), and the exposed coating film was 1% aqueous solution of alkali developer CDK-1 (manufactured by Fuji Film Electronics Materials Co., Ltd.). And rested for 60 seconds. After standing still, pure water was sprayed in a shower to wash away the developer. Then, the coating film that has been exposed and developed as described above is heated in an oven at 220 ° C. for 1 hour (post-baking) to form a colored pattern (colored resin film) for the color filter on the glass substrate, A colored filter substrate (color filter) was produced.

<Evaluation of color filter>
The produced colored filter substrate was evaluated for contrast and developability in the same manner as in (2-1) and (2-2). The results are shown in Table 6 below.

[Examples 58 to 64, Comparative Examples 46 to 48]
The pigment dispersion compositions (R-7) used in Example 57 were obtained in the pigment dispersion compositions (R-8) to (R-14) obtained in Examples 38 to 44 and Comparative Examples 37 to 39. A red light curable composition (red color resist solution) was prepared in the same manner as in Example 57 except that the pigment dispersion compositions (CR-4) to (CR-9) were replaced. Colored filter substrates (color filters) of -64 and Comparative Examples 46-48 were produced.
Furthermore, the obtained colored filter substrate was evaluated for contrast and developability in the same manner as in (2-1) and (2-2). The results are shown in Table 7 below.

[Example 65]
<Preparation of green color resist solution>
The components described in the following composition (c-5) were further added to the pigment dispersion composition (G-7) obtained in Example 45, and mixed by stirring. The green light curable composition of Example 65 was then mixed. (Green color resist solution) was prepared.
[Composition (c-5)]
Dipentaerythritol pentahexaacrylate 50 parts (photopolymerizable compound)
4- [o-bromo-pN, N-di (ethoxycarbonyl) aminophenyl] -2,6-di (trichloromethyl) -S-triazine 20 parts (photopolymerization initiator)
Benzyl methacrylate / methacrylic acid (= 70/30 [molar ratio]) copolymer (weight average molecular weight: 10,000) propylene glycol monomethyl ether acetate solution (solid content 40%) ... 50 parts (alkali-soluble resin)
・ 1-methoxy-2-propyl acetate (solvent): 180 parts

<Preparation and evaluation of color filter using photocurable composition>
The prepared photocurable composition (color resist solution) was applied on a 100 mm × 100 mm glass substrate (1737, manufactured by Corning) so that the y value serving as an index of color density was 0.600. It was dried in an oven at 60 ° C. for 60 seconds (pre-baking). Thereafter, the entire surface of the coating film was exposed at 200 mJ / cm ² (illuminance 20 mW / cm ² ), and the exposed coating film was 1% aqueous solution of alkali developer CDK-1 (manufactured by Fuji Film Electronics Materials Co., Ltd.). And rested for 60 seconds. After standing still, pure water was sprayed in a shower to wash away the developer. Then, the coating film that has been exposed and developed as described above is heated in an oven at 220 ° C. for 1 hour (post-baking) to form a colored pattern (colored resin film) for the color filter on the glass substrate, A colored filter substrate (color filter) was produced.

  Furthermore, the obtained colored filter substrate was evaluated for contrast and developability in the same manner as in (2-1) and (2-2). The results are shown in Table 7 below.

[Examples 66 to 71, Comparative Examples 49 to 51]
The pigment dispersion composition (G-7) used in Example 65 was obtained in the pigment dispersion compositions (G-8) to (G-13) obtained in Examples 46 to 51 and Comparative Examples 40 to 42. A green light curable composition (green color resist solution) was prepared in the same manner as in Example 65 except that the pigment dispersion compositions (CG-7) to (CG-9) were replaced. To 71 and Comparative Examples 49 to 51 were prepared as colored filter substrates (color filters).
Furthermore, the obtained colored filter substrate was evaluated for contrast and developability in the same manner as in (2-1) and (2-2). The results are shown in Table 7 below.

[Example 72]
<Preparation of blue pigment dispersion (B-7)>
The components described in the following composition (c-6) are further added to the pigment dispersion composition (B-7) obtained in Example 52, and the mixture is stirred and mixed. The blue light curable composition of Example 72 is then mixed. (Blue color resist solution) was prepared.
[Composition (c-6)]
Dipentaerythritol pentahexaacrylate 150 parts (photopolymerizable compound)
4- [o-bromo-pN, N-di (ethoxycarbonyl) aminophenyl] -2,6-di (trichloromethyl) -S-triazine ... 60 parts (photopolymerization initiator)
Benzyl methacrylate / methacrylic acid (= 70/30 [molar ratio]) copolymer (weight average molecular weight: 10,000) propylene glycol monomethyl ether acetate solution (solid content 40%) ... 400 parts (alkali-soluble resin)
1-methoxy-2-propyl acetate (solvent) 1440 parts

<Preparation and evaluation of color filter using photocurable composition>
The obtained blue light curable composition (blue color resist solution) was applied on a 100 mm × 100 mm glass substrate (1737, manufactured by Corning) so that the y value serving as an index of color density was 0.090. And dried in an oven at 90 ° C. for 60 seconds (pre-baking). Thereafter, the entire surface of the coating film was exposed at 200 mJ / cm ² (illuminance 20 mW / cm ² ), and the exposed coating film was 1% aqueous solution of alkali developer CDK-1 (manufactured by Fuji Film Electronics Materials Co., Ltd.). And rested for 60 seconds. After standing still, pure water was sprayed in a shower to wash away the developer. Then, the coating film that has been exposed and developed as described above is heated in an oven at 220 ° C. for 1 hour (post-baking) to form a colored pattern (colored resin film) for the color filter on the glass substrate, A colored filter substrate (color filter) was produced.

  Furthermore, the obtained colored filter substrate was evaluated for contrast and developability in the same manner as in (2-1) and (2-2). The results are shown in Table 7 below.

[Examples 73 to 76, Comparative Examples 52 to 54]
The pigment dispersion compositions (B-7) used in Example 72 were obtained in the pigment dispersion compositions (B-8) to (B-11) obtained in Examples 53 to 56 and Comparative Examples 43 to 45. A green light curable composition (green color resist solution) was prepared in the same manner as in Example 72 except that the pigment dispersion compositions (CB-7) to (CB-9) were replaced. Colored filter substrates (color filters) of -76 and Comparative Examples 52-54 were produced.
Furthermore, the obtained colored filter substrate was evaluated for contrast and developability in the same manner as in (2-1) and (2-2). The results are shown in Table 7 below.

[Examples 77 to 78, Comparative Examples 55 to 58]
<Preparation of Red Pigment Dispersion Compositions (R-15) to (R-16), (CR-11) to (CR-13)>
Components of the following composition (d-1) were mixed, and the rotational speed was 3,000 r.m. using a homogenizer. p. m. And mixed for 3 hours to prepare each mixed solution containing the pigment.
[Composition (d-1)]
・ C. I. Pigment Red 254 ... 70 parts C.I. I. Pigment Red 177 ... 30 parts / 30% solution of a specific polymer (pigment dispersant) ... Types / amounts shown in Table 8 / Polyester dispersants ... Types / amounts shown in Table 8 / 1-methoxy-2-propyl acetate ... 820 copies

Subsequently, each mixed solution obtained above was further subjected to a dispersion treatment for 6 hours with a bead disperser disperse mat (made by GETZMANN) using 0.2 mmφ zirconia beads, and then further a high pressure disperser with a decompression mechanism. Dispersion treatment was performed using NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) at a flow rate of 500 g / min under a pressure of 2000 kg / cm ³ . This dispersion treatment was repeated 10 times to obtain red pigment dispersion compositions (R-15) to (R-16) and (CR-11) to (CR-13).

<Evaluation of pigment dispersion composition>
The obtained red pigment dispersion compositions (R-15) to (R-16) and (CR-11) to (CR-13) were evaluated for the above (1-1) and (1-2). . The evaluation results are shown in Table 8 below.

[Examples 79 to 80, Comparative Examples 59 to 62]
<Preparation of Green Pigment Dispersion Compositions (G-14) to (G-15), (CG-10) to (CG-13)>
Components of the following composition (d-2) were mixed, and the rotational speed was 3,000 r.m. using a homogenizer. p. m. And mixed for 3 hours to prepare each mixed solution containing the pigment.
[Composition (d-2)]
・ C. I. Pigment Green 36 ... 80 parts I. Pigment Yellow 150 ... 20 parts-30% solution of specific polymer (pigment dispersant) ... Types and amounts shown in Table 8-Polyester dispersants ... Types and amounts shown in Table 8-1-methoxy-2-propyl acetate ... 790 parts

Subsequently, the mixed solution obtained above was subjected to a dispersion treatment in the same manner as in Example 19 to obtain green pigment dispersion compositions (G-14) to (G-15), (CG-10) to (CG-). 13) obtained. Further, for each of the obtained pigment dispersion compositions (G-14) to (G-15) and (CG-10) to (CG-13), the above (1-1) and (1- In the same manner as in 2), the viscosity and contrast were measured and evaluated. The results are shown in Table 8 below.

Each of the pigment dispersion compositions of the above-described Examples has a low viscosity of the composition, excellent dispersibility and dispersion stability of the pigment, and a coating obtained by this pigment dispersion composition can obtain a high contrast. I understand. The reason why the coating film of the pigment dispersion composition of the example achieves high contrast is presumed to be because the pigment particles are uniformly dispersed in a finely divided state.
On the other hand, all of the pigment dispersion compositions of the comparative examples had a high viscosity in comparison with the examples, and the film obtained using the pigment dispersion composition did not provide sufficient contrast.

  Furthermore, all the colored filter substrates (color filters of the examples) prepared using the photocurable compositions of the examples obtained high contrast and exhibited good developability. On the other hand, the contrast of the colored filter substrate of each comparative example was inferior, and sufficient developability was not obtained.

Claims (9)

A pigment dispersion comprising at least a pigment, a solvent, a dispersant having a polyester chain in the molecule, and a polymer containing a copolymer unit derived from a monomer represented by the following general formula (1) Composition.

[In General Formula (1), R ¹ represents a hydrogen atom or a substituted or unsubstituted alkyl group. R ² represents a single bond or a divalent linking group. Y represents -CO-, -C (= O) O-, -CONH-, -OC (= O)-, or a phenylene group. Z represents a group having a nitrogen-containing heterocyclic structure. ]   The pigment dispersion composition according to claim 1, wherein the polymer is a graft copolymer further comprising a copolymer unit derived from a polymerizable oligomer having an ethylenically unsaturated bond at a terminal.   The pigment dispersion composition according to claim 1 or 2, wherein the polymer is a polymer further comprising a copolymer unit derived from a monomer having an acid group.   The pigment dispersion composition according to any one of claims 1 to 3, wherein Z in the general formula (1) is a group having a nitrogen-containing heterocyclic structure having 6 or more carbon atoms. object.   A photocurable composition comprising the pigment dispersion composition according to any one of claims 1 to 4, a photopolymerizable compound, and a photopolymerization initiator.   Furthermore, alkali-soluble resin is contained, The photocurable composition of Claim 5 characterized by the above-mentioned.   The photocurable composition according to claim 5 or 6, which is used for a color filter.   A color filter comprising a colored pattern formed using the photocurable composition for a color filter according to claim 7 on a substrate.   A photosensitive film forming step of forming a photosensitive film by applying the photocurable composition for a color filter according to claim 7 directly or via another layer to the substrate, and a pattern on the formed photosensitive film And a color pattern forming step of forming a color pattern by sequentially performing exposure and development.