JP2008081732A - Pigment dispersion composition, photocurable composition, color filter, and manufacturing method of color filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a pigment dispersion composition and a photocurable composition which are excellent in the pigment-dispersibility and dispersion stability and to provide a color filter to give high contrast, and a manufacturing method thereof. <P>SOLUTION: The pigment dispersion composition or the like contains in an organic solvent a pigment and a polymer containing a copolymerization unit derived from a monomer expressed by general formula (1), wherein R<SP>1</SP>is a hydrogen atom or a substituted or unsubstituted alkyl group; R<SP>2</SP>is an alkylene group; W is -C(=O)O-, -CONH-, a phenylene group or the like; X is -S-, -CONH-, -C(=O)S-, -NHCONH-, -NHC(=O)S- or the like; Y is -NR<SP>3</SP>-, -O-, -S-, or -N= and forms a cyclic structure by connecting an N atom through an atomic group adjacent to this; R<SP>3</SP>is a hydrogen atom, an alkyl group or an aryl group; and m and n are each independently 0 or 1. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a pigment dispersion composition, a photocurable composition containing the same, a color filter 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 photocurable composition. It is manufactured by forming a colored pattern using a photolithography method or the like.

  In recent years, the use of color filters in liquid crystal display (LCD) applications has tended to expand not only to monitors but also to televisions (TVs). With this trend of expanding applications, advanced color characteristics such as chromaticity and contrast. Has come to be required. In addition, in the image sensor (solid-state imaging device) application, a device having high color characteristics is also demanded.

In response to the above requirements, it is required to disperse the pigment in a finer state (good dispersibility) and to disperse in a stable state (good dispersion stability). If the dispersibility is insufficient, fringes (jagged edges) and surface irregularities occur in the formed colored resist film, the chromaticity and dimensional accuracy of the produced color filter are reduced, and the contrast is remarkably high. There is a problem of deterioration. Further, when the dispersion stability is insufficient, in the color filter manufacturing process, in particular, the uniformity of the film thickness in the coating process of the photocurable composition is reduced, or the photosensitivity in the exposure process is low. The problem that it falls, or the alkali solubility in a image development process falls easily arises. Furthermore, when the dispersion stability of the pigment is poor, there is also a problem that with the passage of time, the constituent components of the photocurable composition cause aggregation, the viscosity increases, and the pot life becomes extremely short.
However, when the pigment particle size is made finer, the surface area of the pigment particles increases, so the cohesion between the pigment particles increases, and it is difficult to achieve both dispersibility and dispersion stability at a high level. 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 that a pigment dispersion having a small pigment particle size and excellent dispersion stability can be obtained by carrying out a dispersion treatment using a coalescence (for example, see Patent Documents 1 and 2).
However, since the copolymer containing the macromonomer described in Patent Documents 1 and 2 does not have a functional group that promotes adsorption to the pigment, it does not function alone as a dispersant and needs to be used in combination with other dispersants. There is a problem that. In addition, when such a copolymer containing a macromonomer is used as a pigment dispersant, the thickening effect seen in the polymer dispersant can be suppressed, but the pigment is not sufficiently refined. There is a problem that dispersibility is not sufficient.

In order to improve the dispersion stability of the pigment, a graft having a partial structure of an organic dye (for example, see Patent Document 3), a nitrogen-containing heterocycle (for example, see Patent Document 4), and a cyclic imide group (for example, see Patent Document 5) A polymer is disclosed.
However, the present condition is that the pigment dispersion composition excellent in the dispersibility and dispersion stability of a pigment, and the photocurable composition containing the same are not yet provided.
JP-A-8-259876 JP-A-10-339949 JP 2003-26950 A JP 2003-26949 A JP 2003-277673 A

The present invention has been made in view of the problems in the prior art, and an object thereof is to achieve the following objects.
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 as a pigment dispersant, and have completed the present invention.
That is, the means for solving the problems are as follows.

  <1> A pigment dispersion composition comprising, in an organic solvent, a pigment and a polymer containing a copolymer unit derived from a monomer represented by the following general formula (1).

In the general formula (1), R ¹ represents a hydrogen atom or a substituted or unsubstituted alkyl group. R ² represents an alkylene group. W represents -CO-, -C (= O) O-, -CONH-, -OC (= O)-, or a phenylene group. X is —O—, —S—, —C (═O) O—, —CONH—, —C (═O) S—, —NHCONH—, —NHC (═O) O—, —NHC (= O) S-, -OC (= O)-, -OCONH-, or -NHCO-. Y represents —NR ³ —, —O—, —S—, or —N═, and is linked to an N atom through an atomic group adjacent thereto to form a cyclic structure. R ³ represents a hydrogen atom, an alkyl group, or an aryl group. m and n each independently represents 0 or 1.

<2> The pigment dispersion as described in <1> above, wherein in the general formula (1), the cyclic structure formed by Y linking to an N atom via an adjacent atomic group is a condensed ring structure Composition.
<3> The above <1> or <2>, 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 as described.
<4> The polymer according to any one of <1> to <3>, wherein the polymer is a polymer including a copolymer unit derived from a monomer having an acid group. Pigment dispersion composition.
<5> The pigment dispersion composition according to any one of <1> to <4>, wherein the polymer has an acid value of 10 to 150 mgKOH / g.

  <6> The pigment is C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment green 36, C.I. I. Pigment red 177, C.I. I. Pigment red 254, C.I. I. Pigment blue 15: 6, and C.I. I. The pigment dispersion composition according to any one of <1> to <5>, wherein the pigment dispersion composition is at least one pigment selected from the group consisting of CI Pigment Violet 23. OK

<7> A photocurable composition comprising the pigment dispersion composition according to any one of <1> to <6>, a photopolymerizable compound, and a photopolymerization initiator. .
<8> The photocurable composition according to <7>, further comprising an alkali-soluble resin.
<9> The above photopolymerization initiator, wherein the photopolymerization initiator is at least one photopolymerization initiator selected from the group consisting of a triazine compound, a lophine dimer compound, and an oxime compound. > Or <8>. OK
<10> The photocurable composition according to any one of <7> to <9>, wherein the photocurable composition is for a color filter.

<11> A color filter having a colored pattern using the photocurable composition according to <10> on a substrate.
<12> A photosensitive film forming step of forming a photosensitive film by applying the photocurable composition according to <10> directly or through another layer to a substrate, and the formed photosensitive film And a color pattern forming step of forming a color pattern by sequentially performing pattern exposure and development.

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

<Pigment dispersion composition>
The pigment dispersion composition of the present invention contains a pigment and a polymer containing a copolymer unit derived from a monomer represented by the following general formula (1) in an organic solvent. .

[Polymer containing copolymerized units derived from monomer represented by general formula (1)]
The pigment dispersion composition of the present invention is required to contain a polymer containing a copolymer unit derived from a monomer represented by the following general formula (1).
In the pigment dispersion composition of the present invention, the specific polymer can function as a pigment dispersant. In the following description, the “polymer containing a copolymer unit derived from the monomer represented by the general formula (1)” may be referred to as a “specific pigment dispersant” as appropriate.

In the general formula (1), R ¹ represents a hydrogen atom or a substituted or unsubstituted alkyl group. R ² represents an alkylene group. W represents -CO-, -C (= O) O-, -CONH-, -OC (= O)-, or a phenylene group. X is —O—, —S—, —C (═O) O—, —CONH—, —C (═O) S—, —NHCONH—, —NHC (═O) O—, —NHC (= O) S-, -OC (= O)-, -OCONH-, or -NHCO-. Y represents —NR ³ —, —O—, —S—, or —N═, and is linked to an N atom through an atomic group adjacent thereto to form a cyclic structure. R ³ represents a hydrogen atom, an alkyl group, or an aryl group. m and n each independently represents 0 or 1.

  Hereinafter, the monomer represented by the general formula (1), which is an essential copolymer unit in the specific polymer that is an important component of the present invention, will be described in detail.

In the general formula (1), R ¹ represents a hydrogen atom or a substituted or unsubstituted alkyl group.
The alkyl group represented by R ¹ is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and particularly preferably an alkyl group having 1 to 4 carbon atoms.
When the alkyl group represented by R ¹ is a substituted alkyl group, examples of the substituent that can be introduced include a hydroxy group, an alkoxy group, an aryloxy group, an acyloxy group, and a halogen group.
Specific examples of preferred alkyl groups represented by R ¹ include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, and n-hexyl group. Cyclohexyl group, 2-hydroxyethyl group, 3-hydroxypropyl group, 2-hydroxypropyl group, 2-methoxyethyl group, and the like.
R ¹ is particularly preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

R ² represents an alkylene group.
The alkylene group represented by R ² is preferably an alkylene group having 1 to 12 carbon atoms, more preferably an alkylene group having 1 to 8 carbon atoms, and particularly preferably an alkylene group having 1 to 4 carbon atoms.
The alkylene group represented by R ² may have a substituent when it can be introduced, and examples of the substituent include a hydroxy group, an alkoxy group, an aryloxy group, an acyloxy group, and the like. It is done.
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.

  W represents —CO—, —C (═O) O—, —CONH—, —OC (═O) —, or a phenylene group, and —C (═O) O—, —CONH—, or a phenylene group. It is preferable that

Y represents —NR ³ —, —O—, —S—, or —N═, and is linked to an N atom through an atomic group adjacent thereto to form a cyclic structure.
R ³ represents a hydrogen atom, an alkyl group, or an aryl group. The alkyl group represented by R ^3, an alkyl group having 1 to 12 carbon atoms preferably. Examples of the aryl group represented by R ^3, a phenyl group, a naphthyl group are preferably exemplified.
R ³ is more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and particularly preferably a hydrogen atom or a methyl group. Y is —S—, —NH—, or —N. = Is particularly preferred.

  Examples of the cyclic structure formed by linking Y with an N atom through an atomic group adjacent thereto include imidazole ring, pyrimidine ring, triazole ring, tetrazole ring, thiazole ring, oxazole ring, and the like, and , A condensed ring structure such as a benzimidazole ring, a benzthiazole ring, a benzoxazole ring, a purine ring, a quinazoline ring, and a perimidine ring, and a condensed ring structure is preferable from the viewpoint of affinity with a pigment. Of the condensed ring structures, a benzimidazole ring, a benzthiazole ring, and a benzoxazole ring are particularly preferred.

  X is —O—, —S—, —C (═O) O—, —CONH—, —C (═O) S—, —NHCONH—, —NHC (═O) O—, —NHC (= O) S-, -OC (= O)-, -OCONH-, or -NHCO-. X is particularly preferably —O—, —S—, —CONH—, —NHCONH—, and —NHC (═O) S—.

  m and n each independently represents 0 or 1, and it is particularly preferred that both m and n are 1.

  Preferred specific examples (monomer M-1 to monomer M-18) of the monomer represented by the general formula (1) are listed below, but the present invention is not limited thereto.

  The specific pigment dispersant in the present invention has an ethylenically unsaturated bond at the terminal together with a copolymer unit derived from the monomer represented by the general formula (1) from the viewpoint of imparting dispersion stability of the pigment. A graft copolymer containing a copolymer unit derived from the polymerizable oligomer is particularly preferred.

  Such a polymerizable oligomer having an ethylenically unsaturated 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.

Moreover, it is preferable that this macromonomer has the number average molecular weight (Mn) of polystyrene conversion in the range of 1000-10000, and the range of 2000-9000 is especially preferable.
The polymer chain part 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 and polycaprolactone are generally used.

  The polymerizable oligomer is preferably an oligomer represented by the following general formula (2).

In General Formula (2), 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. R ¹² is preferably a group in which an alkylene group having 1 to 4 carbon atoms or an alkylene group having 1 to 4 carbon atoms is linked by breaking an ester bond. The alkylene group represented by R ¹² may further have a substituent (for example, a hydroxyl group).
Y 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 is preferably a phenyl group or —COOR ¹⁴ where R ¹⁴ represents an alkyl group having 1 to 12 carbon atoms.
q represents an integer of 20 to 200.

  Preferred examples of the polymerizable oligomer (macromonomer) that can be used for the synthesis of the specific pigment dispersant in the present invention 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 pigment dispersant according to the present invention preferably further contains a copolymer unit derived from a monomer having an acid group. When the specific pigment dispersant further contains a copolymer unit derived from a monomer having an acid group, for example, when the pigment dispersion composition of the present invention is applied to pattern formation by a photolithographic method, the pattern formability is further improved. Can be improved.

  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 pigment dispersant according to the present invention may further contain a copolymerizable vinyl monomer as a copolymer component 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.

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.
In addition, in this specification, when showing either or both of "acryl and methacryl", it may describe as "(meth) acryl".

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 styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chlorostyrene, dichlorostyrene, bromostyrene, chloromethyl. Examples thereof include styrene, hydroxystyrene protected with a group deprotectable by an acidic substance (for example, t-Boc and the like), methyl vinylbenzoate, and α-methylstyrene.
Examples of vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and methoxyethyl vinyl ether.

The specific pigment dispersant in the present invention preferably has an acid value of 10 to 150 mgKOH / g, more preferably 20 to 140 mgKOH / g, and particularly preferably 30 to 120 mgKOH / g.
When the acid value of the specific pigment dispersant is in the range of 10 to 150 mgKOH / g, when the pigment dispersion composition of the present invention is applied as a resist solution, the alkali solubility is appropriately maintained, and good developability is obtained. As well as achieving excellent dispersion stability of the pigment.
As a means for maintaining the acid value of the specific pigment dispersant within the above-mentioned appropriate range, for example, a means for containing 1% or more of a copolymer component having an acid group in the polymer constituting the specific pigment dispersant, or a specific pigment Examples include means for adding an acid anhydride to the polymer constituting the dispersant by a polymer reaction.

  Here, the acid value of the specific pigment dispersant is the number of mg of potassium hydroxide necessary to neutralize 1 g of the pigment dispersant. The unit of the acid value is mgKOH / g. The acid value is obtained by titrating the resin solution with an alkaline solution (for example, an aqueous sodium hydroxide solution or an aqueous potassium hydroxide solution) to obtain a neutralization point, and is calculated from the amount of the alkaline solution required to reach this neutralization point. be able to. In titration, for example, the neutralization point can be determined by a titration method using a titration indicator such as phenolphthalein or a method using an automatic potentiometric titrator.

  As a preferable aspect of the specific pigment dispersant according to the present invention, it contains 2 to 50% by mass of a copolymer unit derived from the monomer represented by the general formula (1), and is further ethylenically unsaturated at the terminal. 10 to 90% by mass of a copolymer unit derived from a polymerizable oligomer having a bond, 1 to 30% by mass of a copolymer unit derived from a monomer having an acid group, and 0 to a copolymer unit derived from a vinyl monomer A copolymer containing ˜20% by mass can be preferably mentioned.

  The preferable molecular weight of the specific pigment dispersant according to the present invention is preferably 15,000 to 200,000 in terms of weight average molecular weight (Mw) and 8,000 to 100,000 in terms of number average molecular weight (Mn). The molecular weight can be measured by GPC.

  Specific examples of the specific pigment dispersant [Exemplary Compound 1 to Exemplified Compound 16] that can be suitably used in the pigment dispersion composition of the present invention are listed below together with their weight average molecular weights, but the present invention is not limited to these. Absent.

Exemplary Compound (1): Monomer M-2 / terminal methacryloylated polymethyl methacrylate copolymer (10/90 mass%, weight average molecular weight 50000, acid value: 0 mgKOH / g)
Illustrative compound (2): Monomer M-2 / methacrylic acid / terminated methacryloylated polymethyl methacrylate copolymer (10/15/75 mass%, weight average molecular weight 30000, acid value: 98 mgKOH / g)
Exemplary Compound (3): Monomer M-3 / 2-hydroxyethyl methacrylate / terminal methacryloylated polymethyl methacrylate copolymer (5/10/85% by mass, weight average molecular weight 40000, acid value: 0 mgKOH / g )
Exemplary compound (4): Monomer M-3 / methacrylic acid / benzyl methacrylate copolymer / terminal methacryloylated polymethyl methacrylate copolymer (15/5/10/65 mass%, weight average molecular weight 60000, acid (Value: 33 mg KOH / g)
Exemplary compound (5): Monomer M-4 / terminal methacryloylated polymethyl methacrylate copolymer (10/90 mass%, weight average molecular weight 80000, acid value: 0 mgKOH / g)

Exemplary Compound (6): Monomer M-4 / Methacrylic acid / Terminal methacryloylated polymethyl methacrylate copolymer (10/15/75% by mass, weight average molecular weight 30000, acid value: 98 mgKOH / g)
Exemplary compound (7): Monomer M-5 / acrylic acid / terminal methacryloylated polymethyl methacrylate copolymer (25/15/60 mass%, weight average molecular weight 60000,
Acid value: 117 mgKOH / g)
Exemplary Compound (8): Monomer M-5 / Terminal Methacryloylated Polybutyl Acrylate Copolymer (15/85% by Mass, Weight Average Molecular Weight 40000, Acid Value: 0 mgKOH / g)
Exemplary compound (9): Monomer M-6 / 2-hydroxyethyl methacrylate / terminal methacryloylated polymethyl methacrylate copolymer (15/10/75% by mass, weight average molecular weight 80000, acid value: 0 mgKOH / g) )
Exemplary Compound (10): Monomer M-6 / Terminal Methacryloylated Polymethyl Methacrylate Copolymer (12/88% by Mass, Weight Average Molecular Weight 50000, Acid Value: 0 mgKOH / g)

Exemplary compound (11): Monomer M-7 / methacrylic acid / terminated methacryloylated polymethyl methacrylate copolymer (10/15/75% by mass, weight average molecular weight 25000, acid value: 98 mgKOH / g)
Illustrative compound (12): Monomer M-7 / methacrylic acid / benzyl methacrylate / methoxypolyethylene glycol methacrylate copolymer (10/10/50/30 mass%, weight average molecular weight 40000, acid value: 65 mgKOH / g )
Exemplary Compound (13): Monomer M-10 / 2-hydroxyethyl methacrylate / terminal methacryloylated polystyrene copolymer (5/10/85% by mass, weight average molecular weight 20000, acid value: 0 mgKOH / g)
Illustrative compound (14): monomer M-10 / methacrylic acid / terminated methacryloylated polymethyl methacrylate copolymer (10/15/75% by mass, weight average molecular weight 35000, acid value: 98 mgKOH / g)
Illustrative compound (15): Monomer M-10 / methoxypolyethylene glycol methacrylate copolymer (15: 85% by mass, weight average molecular weight 15000, acid value: 0 mgKOH / g)
Illustrative compound (16): Monomer M-13 / methacrylic acid / terminated methacryloylated polymethyl methacrylate copolymer (10/15/75 mass%, weight average molecular weight 20000, acid value: 98 mgKOH / g)

Illustrative compound (17): Monomer M-4 / methacrylic acid / terminated methacryloylated polymethyl methacrylate copolymer (10/15/75% by mass, weight average molecular weight 25000, acid value: 98 mgKOH / g)
Exemplary compound (18): Monomer M-4 / acrylic acid / terminal methacryloylated polystyrene copolymer (10/10/80 mass%, weight average molecular weight 20000,
Acid value: 78mgKOH / g)
Exemplary Compound (19): Monomer M-4 / Succinic anhydride adduct of 2-hydroxyethyl methacrylate / terminal methacryloylated polymethyl methacrylate copolymer (8/15/77% by mass, weight average molecular weight 25000, Acid value: 37mgKOH / g)
Exemplary Compound (20): Monomer M-4 / acrylic acid / benzyl methacrylate / terminal methacryloylated polymethyl methacrylate copolymer (10/10/10/70% by mass, weight average molecular weight 25000, acid value: 78 mgKOH / g)

Illustrative compound (21): Monomer M-10 / acrylic acid / terminal methacryloylated polymethyl methacrylate copolymer (15/10/75% by mass, weight average molecular weight 25000, acid value: 78 mgKOH / g)
Illustrative compound (22): monomer M-11 / methacrylic acid / terminated methacryloylated polymethyl methacrylate copolymer (15/10/75% by mass, weight average molecular weight 25000, acid value: 65 mgKOH / g)
Exemplary compound (23): Monomer M-11 / terminal methacryloylated polymethyl methacrylate copolymer (15/85 mass%, weight average molecular weight 30000, acid value: 0 mgKOH / g)

The copolymer as described above, which is a specific pigment dispersant in the present invention, contains a monomer represented by the general formula (1), a polymerizable oligomer used in combination as required, and other monomers in a solvent. It can be obtained by radical polymerization. As the radical polymerization initiator, a known compound is used, and an azo initiator (for example, dimethyl-2,2′-azobis (2-methylpropionate), azobisisobutyronitrile, 2,2′- Azobis (2-amidinopropane) dihydrochloride, etc.) and peroxides (benzoyl peroxide, potassium persulfate, etc.) are preferably used. In addition to the initiator, a chain transfer agent (for example, 2-mercaptoethanol, 3-mercaptopropionic acid, 2-mercaptoacetic acid, dodecyl mercaptan) may be added and synthesized.
A specific synthesis example will be described later.

  As content in the pigment dispersion composition of a specific pigment dispersant, 0.5-100 mass% is preferable with respect to the mass of the pigment mentioned later, and 3-70 mass% is more preferable. When the amount of the pigment dispersant is within this range, a sufficient pigment dispersion effect can be obtained. Even if the pigment dispersant is added in an amount of more than 100% by mass, a further improvement effect of the pigment dispersion effect may not be expected.

The pigment dispersion composition of the present invention comprises a pigment and a specific pigment dispersant in an organic solvent, and can be constituted using other components such as a resin component as necessary.
Since this pigment dispersion composition contains a specific pigment dispersant, the dispersion state of the pigment in the organic solvent is improved, and good color characteristics are obtained. For example, when a color filter is constructed, a high contrast is obtained. Can do. In particular, the organic pigment exhibits an excellent dispersion effect.

[Pigment]
The pigment dispersion composition of the present invention contains a pigment, and various conventionally known inorganic pigments or organic pigments can be appropriately selected and used as the pigment.
In consideration of the fact that it is preferable that the pigment has a high transmittance, whether it is an inorganic pigment or an organic pigment, it is preferable to use a pigment having a particle size as small as possible. 0.01 μm to 0.1 μm is preferable, and 0.01 μm to 0.05 μm is more preferable.

  Examples of the inorganic pigment include metal compounds represented by metal oxides, metal complex salts, and the like. Specific examples include metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony, and composite oxides of the above metals.

Examples of the organic pigment include the following.
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;

Although it does not specifically limit as a pigment in this invention, The following 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 Green 36
C. I. Pigment Black 7

Among these, the following pigments are particularly preferable.
C. I. Pigment Yellow 139,150
C. I. Pigment Red 177,254
C. I. Pigment Violet 23
C. I. Pigment Blue 15: 6
C. I. Pigment Green 36

These organic pigments can be used alone or in various combinations in order to increase color purity. Specific examples of combinations are shown below.
For example, as a red pigment, an anthraquinone pigment, a perylene pigment, a diketopyrrolopyrrole pigment alone or at least one of them, a bisazo yellow pigment, an isoindoline yellow pigment, a quinophthalone yellow pigment or a perylene red pigment A mixture of these 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, if the ratio exceeds 100: 50, the dominant wavelength may be shorter than the NTSC target hue in some cases. 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, 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, a phthalocyanine pigment can be used alone, or a mixture thereof 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 the 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 of the pigment in a pigment dispersion composition, 40-90 mass% is preferable with respect to the total solid (mass) of this composition, and 50-80 mass% is more preferable. When the pigment content is within the above range, the color density is sufficient and it is effective to ensure excellent color characteristics.

[Organic solvent]
Examples of the organic solvent used for preparing the pigment dispersion composition of the present invention include 2-acetoxy-1-methoxypropane, 1-methoxy-2-propanol, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, ethyl acetate, butyl acetate, and lactic acid. Examples thereof include ethyl, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, n-propanol, 2-propanol, n-butanol, cyclohexanol, ethylene glycol, diethylene glycol, toluene and xylene.
The amount of the organic solvent added is appropriately selected according to the use of the pigment dispersion composition, etc., but when used for the preparation of the photocurable composition described later, from the viewpoint of handleability, the pigment and the pigment dispersion are added. It can add so that the solid content density | concentration containing an agent may be 5-50 mass%.

The preparation of the pigment dispersion composition of the present invention is not particularly limited, but, for example, with a pigment, a pigment dispersant and a solvent, using a vertical or horizontal sand grinder, pin mill, slit mill, ultrasonic disperser, etc. 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.
In addition, before carrying out bead dispersion, while applying 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 a kneading and dispersing process.
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 composition of the present invention can be applied to inkjet inks and the like in addition to forming color filters.
In addition, if the pigment dispersion composition of this invention is a case where it is applied to a color filter formation use, it is preferable that it is soluble in alkaline aqueous solution.

<Photocurable composition>
The photocurable composition of the present invention comprises the above-described pigment dispersion composition of the present invention, a photopolymerizable compound, and a photopolymerization initiator, and preferably further contains an alkali-soluble resin. Depending on, other components may be included.
Since this photocurable composition contains the specific pigment dispersant according to the present invention described above, the pigment is maintained in a good dispersion state in the composition, and good color characteristics can be obtained. When 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 using at least one of the above-described pigment dispersion compositions 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. An 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 this range, the color density is sufficient and effective in securing excellent color characteristics.

[Alkali-soluble resin]
The photocurable composition of the present invention preferably contains at least one alkali-soluble resin. By containing the alkali-soluble resin in the photocurable composition, the pattern formability can be further improved when the photocurable composition is applied to pattern formation by a photolithography method.
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, CH _2. = CR ¹ R ² [wherein R ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ² represents an aromatic hydrocarbon ring having 6 to 10 carbon atoms. ], CH ₂ = C (R ¹ ) (COOR ³ ) [wherein R ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ³ 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. Other preferred copolymerizable monomers are selected from CH ₂ ═CR ¹ R ² , CH ₂ ═C (R ¹ ) (COOR ³ ), phenyl (meth) acrylate, benzyl (meth) acrylate and styrene. It is at least one, and particularly preferably CH ₂ ═CR ¹ R ² and / or CH ₂ ═C (R ¹ ) (COOR ³ ). These R ¹ , R ² and R ³ 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 photopolymerizable compound that can be used in the present invention is an addition polymerizable compound having at least one ethylenically unsaturated double bond, and a compound having at least one terminal ethylenically unsaturated bond, preferably two or more. Chosen from. 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 And sorbitol tetritaconate. 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 (A) to a polyisocyanate compound having two or more isocyanate groups. Compounds and the like.

^{_{CH 2 = C (R 34)}} COOCH 2 CH (R 35) OH (A)
(However, R ³⁴ and R ³⁵ 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, other components (for example, binder polymers such as alkali-soluble resins, photopolymerization initiators, compatibility with colorants (pigments), and dispersibility are also included in the photocurable composition. The selection / use method is an important factor. For example, the 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 the 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 US Pat. No. 4,318791, European Patent Publication EP-88050A, etc., described in US Pat. Aromatic ketone compounds such as benzophenones, (thio) xanthones or acridine compounds described in Fr-2456541, compounds such as coumarins or lophine dimers described in JP-A-10-62986, JP-A Sulfonium organoboron such as in Japanese Patent No. 8-015521 Body, etc., etc. can be mentioned.

  Among them, the photocurable composition of the present invention includes an acetophenone compound, a ketal compound, a benzophenone compound, a benzoin compound, a benzoyl compound, a xanthone compound, a triazine compound, a halomethyl oxadi as a photopolymerization initiator. More preferably, it contains a photopolymerization initiator selected from an azole compound, an acridine compound, a coumarin compound, a lophine dimer compound, a biimidazole compound, an oxime compound, a triazine compound, It is particularly preferable that it contains a photopolymerization initiator selected from lophine dimers and oxime compounds.

  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 compound 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.

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

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

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

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

  Examples of the oxime-based photopolymerization initiator include 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, o-benzoyl-4 ′-(benzmercapto) benzoyl-hexyl-ketoxime. Furthermore, J. Org. C. S. Perkin II (1979) p1653-1660), J. et al. C. S. Perkin II (1979) p156-162, Journal of Photopolymer Science and Technology (1995) p202-232, JP 2000-66385 A, JP 2000-80068 A, JP 2004-534797 A, etc. The compound of this is mentioned.

  Examples of photopolymerization initiators other than the above include 2,4,6-trimethylphenylcarbonyl-diphenylphosphonyl oxide, hexafluorophospho-trialkylphenylphosphonium salt, and the like.

The photopolymerization initiator that can be used in the present invention is not limited to the above photopolymerization initiator, and other known photopolymerization initiators 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 this range, the polymerization reaction can proceed well 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 photocurable composition of the present invention preferably contains a co-sensitizer. In the photocurable composition of the present invention, the co-sensitizer has functions such as further improving the sensitivity of the sensitizing dye and the initiator to active radiation, or suppressing the polymerization inhibition 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, p. Publication, JP 52-134692, JP 59-138205, JP 60-84305, JP 62-18537, JP 64-33104, Research Disclosure 33825 Specific examples thereof include triethanolamine, p-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, p-methylthiodimethylaniline and the like.

  Other examples of co-sensitizers include thiols and sulfides such as thiol compounds described in JP-A-53-702, JP-B-55-500806, JP-A-5-142772, No. 56-75643, such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-4 (3H) -quinazoline, β-mercapto. And naphthalene.

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, trithiane).
The content of these co-sensitizers is in the range of 0.1 to 30% by mass with respect to the mass of the total solid content of the photocurable composition from the viewpoint of improving the curing rate due to the balance between polymerization growth rate and chain transfer. Is preferable, 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 will be described.
〔solvent〕
Generally the photocurable composition of this invention can be suitably prepared using a solvent with the said component.
Examples of the solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, Ethyl lactate, 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 such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate), and 2-oxypropio 2-oxypropionic acid alkyl esters such as methyl acid, 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- Ethyl ethoxy-2-methylpropionate), 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 monomethyl ether acetate (herein) Among them, also called 2-acetoxy-1-methoxypropane), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate and the like;
Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone;
Aromatic hydrocarbons such as toluene, xylene and the like can be mentioned.

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

[Other ingredients]
In the photocurable composition of the present invention, if necessary, a fluorine-based organic compound, a thermal polymerization inhibitor, a filler, a specific pigment dispersant and a polymer compound other than the alkali-soluble resin, a surfactant, and adhesion promotion. Various additives such as an agent, 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 this 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 esters (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, etc., various Solsperse dispersants (manufactured by Zeneca); 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-chlorobenzo Riazor, ultraviolet absorbers such as alkoxy benzophenone; and it can be exemplified aggregation inhibitor 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.
Specifically, the photocurable composition of the present 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). A photosensitive film is formed, and the formed photosensitive film is exposed through a predetermined mask pattern. After the exposure, the uncured portion is developed and removed with a developer, so that each color (for example, three colors or four colors) is obtained. By forming a colored pattern (for example, colored pixels), a color filter can be most suitably produced.
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 for 10 seconds to 300 seconds in a temperature range of 50 ° C. to 140 ° C. using a hot plate, oven, or the like. Can be performed under the following conditions.

In development, the uncured part after exposure is eluted in the developer, leaving only the cured part. The development temperature is usually 20 ° C. to 30 ° C., and the development time is 20 seconds 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 organic solvent or 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, the excess developer is washed away, dried, and then generally heated (post-baked) at a temperature of 100 ° C. to 240 ° C. The post-baking is a post-development heating for complete curing, and is usually performed at a temperature of about 200 ° C. to 250 ° C. (hard baking). This post-bake treatment is performed continuously or batchwise by 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 a 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 μm to 5.0 μm, preferably 0.5 μm to 3.5 μm, Most desirably, the thickness is 1.0 μm 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-baked as necessary. And it can form by accelerating hardening of a film.

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

[Synthesis Example 1]
(Synthesis of monomer 1)
9.51 parts of 2-aminopyrimidine are dissolved in 30 parts of pyridine and heated to 45 ° C. To this, 17.1 parts of 2-methacryloyloxyethyl isocyanate is added dropwise, and the mixture is further heated and stirred at 50 ° C. for 5 hours. The reaction solution was poured into 200 parts of distilled water while stirring, and the resulting precipitate was filtered and washed to obtain 23.8 parts of monomer 1 (explained Compound M-2).

(Synthesis of polymer 1)
5.0 parts of the monomer 1, 37.5 parts of polymethyl methacrylate having a methacryloyl group at the terminal (AA-6: manufactured by Toa Gosei Co., Ltd.), 7.5 parts of methacrylic acid, and 1-methoxy-2-propanol 116. 7 parts are introduced into a nitrogen-substituted three-necked flask, stirred with a stirrer (Shinto Kagaku Co., Ltd .: Three-One Motor), heated to 78 ° C. while flowing nitrogen into the flask. 0.1 part of dimethyl-2,2′-azobis (2-methylpropionate) (“V-601” manufactured by Wako Pure Chemical Industries, Ltd.) was added to this, and the mixture was heated and stirred at 78 ° C. for 2 hours. . Two hours later, 0.1 part of V-601 was further added, and the mixture was heated and stirred for 3 hours to obtain a 30% solution of Polymer 1 (Exemplary Compound (2) described above).

[Synthesis Example 2]
(Synthesis of monomer 2)
13.3 parts of 2-aminobenzimidazole are dissolved in 30 parts of pyridine and heated to 45 ° C. To this, 17.1 parts of 2-methacryloyloxyethyl isocyanate is added dropwise, and the mixture is further heated and stirred at 50 ° C. for 5 hours. This reaction solution was poured into 200 parts of distilled water while stirring, and the resulting precipitate was filtered and washed to obtain 27.3 parts of monomer 2 (explained Compound M-4).

(Synthesis of polymer 2)
5.0 parts of the monomer 2, 37.5 parts of polymethyl methacrylate having a methacryloyl group at the terminal (AA-6: manufactured by Toa Gosei Co., Ltd.), 7.5 parts of methacrylic acid, and 1-methoxy-2-propanol 116. 7 parts are introduced into a nitrogen-substituted three-necked flask, stirred with a stirrer (Shinto Kagaku Co., Ltd .: Three-One Motor), heated to 78 ° C. while flowing nitrogen into the flask. 0.1 part of dimethyl-2,2′-azobis (2-methylpropionate) (“V-601” manufactured by Wako Pure Chemical Industries, Ltd.) was added to this, and the mixture was heated and stirred at 78 ° C. for 2 hours. . Two hours later, 0.1 part of V-601 was further added, and the mixture was heated and stirred for 3 hours to obtain a 30% solution of Polymer 2 (Exemplary Compound (6) described above).

[Synthesis Example 3]
(Synthesis of Polymer 3)
5.0 parts of the monomer 2, 37.5 parts of polymethyl methacrylate having a methacryloyl group at the end (AA-6: manufactured by Toa Gosei Co., Ltd.), 7.5 parts of methacrylic acid, 0.90 part of n-dodecyl mercaptan, and 116.7 parts of 1-methoxy-2-propanol was introduced into a nitrogen-substituted three-necked flask, stirred with a stirrer (Shinto Kagaku Co., Ltd .: Three-One Motor), and heated while flowing nitrogen into the flask. The temperature is raised to ° C. 0.26 parts of dimethyl-2,2′-azobis (2-methylpropionate) (“V-601” manufactured by Wako Pure Chemical Industries, Ltd.) was added thereto, and the mixture was heated and stirred at 75 ° C. for 3 hours. . Further, 0.26 part of V-601 was added, and after 3 hours of heating and stirring, 0.26 part of V-601 was added again and stirring was performed for 3 hours, whereby polymer 3 (exemplified compound (17) described above) was obtained. A 30% solution of was obtained.

[Synthesis Example 4]
(Synthesis of polymer 4)
5.0 parts of the monomer 2, 40.0 parts of polystyrene having a methacryloyl group at the end (AS-6: manufactured by Toa Gosei Co., Ltd.), 5.0 parts of acrylic acid, 0.76 parts of n-dodecyl mercaptan, and 1- 116.7 parts of methoxy-2-propanol was introduced into a nitrogen-substituted three-necked flask, stirred with a stirrer (Shinto Kagaku Co., Ltd .: Three-One Motor), and heated to 75 ° C. while flowing nitrogen into the flask. Raise the temperature. 0.22 parts of dimethyl-2,2′-azobis (2-methylpropionate) (“V-601” manufactured by Wako Pure Chemical Industries, Ltd.) was added thereto, and the mixture was heated and stirred at 75 ° C. for 3 hours. . Further, 0.22 part of V-601 was added, and after 3 hours of heating and stirring, 0.22 part of V-601 was added again and stirring was performed for 3 hours, whereby polymer 4 (exemplified compound (18) described above) was obtained. A 30% solution of was obtained.

[Synthesis Example 5]
(Synthesis of polymer 5)
4.0 parts of the monomer 2, 38.5 parts of polymethyl methacrylate having a methacryloyl group at the end (AA-6: manufactured by Toa Gosei Co., Ltd.), and a succinic anhydride adduct of 2-hydroxyethyl methacrylate (Shin Nakamura Chemical ( Co., Ltd., NK ester SA: the following structure) 7.5 parts, 0.43 parts of n-dodecyl mercaptan and 116.7 parts of 1-methoxy-2-propanol were introduced into a nitrogen-substituted three-necked flask, and a stirrer ( The mixture is stirred with Shinto Kagaku Co., Ltd. (Three-One Motor) and heated to 75 ° C. while flowing nitrogen into the flask. 0.12 part of dimethyl-2,2′-azobis (2-methylpropionate) (“V-601” manufactured by Wako Pure Chemical Industries, Ltd.) was added thereto, and the mixture was stirred with heating at 75 ° C. for 3 hours. . Further, 0.12 part of V-601 was added, and after 3 hours of heating and stirring, 0.12 part of V-601 was added again and stirring was performed for 3 hours, whereby polymer 5 (exemplified compound (19) described above) was obtained. A 30% solution of was obtained.

[Synthesis Example 6]
(Synthesis of polymer 6)
5.0 parts of the monomer 2, 35.0 parts of polymethyl methacrylate having a methacryloyl group at the terminal (AA-6: manufactured by Toa Gosei Co., Ltd.), 5.0 parts of acrylic acid, 5.0 parts of benzyl methacrylate, n- 0.98 parts of dodecyl mercaptan and 116.7 parts of 1-methoxy-2-propanol were introduced into a nitrogen-substituted three-necked flask, stirred with a stirrer (Shinto Kagaku Co., Ltd .: Three-One Motor), and nitrogen was added to the flask. Heat up to 75 ° C. while flowing in. 0.28 parts of dimethyl-2,2′-azobis (2-methylpropionate) (“V-601” manufactured by Wako Pure Chemical Industries, Ltd.) was added thereto, and the mixture was heated and stirred at 75 ° C. for 3 hours. . Further, 0.28 part of V-601 was added, and after 3 hours of heating and stirring, 0.28 part of V-601 was added again and stirring was performed for 3 hours, whereby polymer 6 (exemplified compound (20) described above) was obtained. A 30% solution of was obtained.

[Synthesis Example 7]
(Synthesis of monomer 3)
15.0 parts of 2-mercaptobenzimidazole and 13.8 parts of potassium carbonate are dissolved in 30 parts of dimethyl sulfoxide and heated to 45 ° C. To this, 22.9 parts of chloromethylstyrene is added dropwise and stirred at 50 ° C. for another 5 hours. This reaction solution was poured into 200 parts of distilled water while stirring, and the resulting precipitate was filtered and washed to obtain 25.6 parts of monomer 3 (explained Exemplified Compound M-10).

(Synthesis of polymer 7)
5.0 parts of the monomer 3, 37.5 parts of polymethyl methacrylate having a methacryloyl group at the terminal (AA-6: manufactured by Toa Gosei Co., Ltd.), 7.5 parts of methacrylic acid, and 1-methoxy-2-propanol 116. 7 parts are introduced into a nitrogen-substituted three-necked flask, stirred with a stirrer (Shinto Kagaku Co., Ltd .: Three-One Motor), heated to 78 ° C. while flowing nitrogen into the flask. 0.1 part of dimethyl-2,2′-azobis (2-methylpropionate) (“V-601” manufactured by Wako Pure Chemical Industries, Ltd.) was added to this, and the mixture was heated and stirred at 78 ° C. for 2 hours. . Two hours later, 0.1 part of V-601 was further added, and the mixture was heated and stirred for 3 hours to obtain a 30% solution of polymer 7 (the above-described exemplary compound (14)).

[Synthesis Example 8]
(Synthesis of polymer 8)
7.5 parts of the monomer 3, 37.5 parts of polymethyl methacrylate having a methacryloyl group at the terminal (AA-6: manufactured by Toa Gosei Co., Ltd.), 5.0 parts of acrylic acid, 0.84 parts of n-dodecyl mercaptan, and 116.7 parts of 1-methoxy-2-propanol was introduced into a nitrogen-substituted three-necked flask, stirred with a stirrer (Shinto Kagaku Co., Ltd .: Three-One Motor), and heated while flowing nitrogen into the flask. The temperature is raised to ° C. 0.24 parts of dimethyl-2,2′-azobis (2-methylpropionate) (“V-601” manufactured by Wako Pure Chemical Industries, Ltd.) was added thereto, and the mixture was heated and stirred at 75 ° C. for 3 hours. . Further, 0.24 part of V-601 was added, and after 3 hours of heating and stirring, 0.24 part of V-601 was added again and stirring was performed for 3 hours, whereby polymer 8 (exemplified compound (21) described above) was obtained. A 30% solution of was obtained.

[Synthesis Example 9]
(Synthesis of monomer 4)
16.7 parts of 2-mercaptobenzthiazole and 13.8 parts of potassium carbonate are dissolved in 30 parts of dimethyl sulfoxide and heated to 45 ° C. To this, 22.9 parts of chloromethylstyrene is added dropwise and stirred at 50 ° C. for another 5 hours. The reaction solution was poured into 200 parts of distilled water with stirring, and the resulting precipitate was filtered and washed to obtain 26.9 parts of monomer 4 (Exemplary Compound M-11 described above).

(Synthesis of polymer 9)
7.5 parts of the monomer 4, 37.5 parts of polymethyl methacrylate having a methacryloyl group at the end (AA-6: manufactured by Toa Gosei Co., Ltd.), 5.0 parts of methacrylic acid, 0.74 parts of n-dodecyl mercaptan, and 116.7 parts of 1-methoxy-2-propanol was introduced into a nitrogen-substituted three-necked flask, stirred with a stirrer (Shinto Kagaku Co., Ltd .: Three-One Motor), and heated while flowing nitrogen into the flask. The temperature is raised to ° C. 0.21 part of dimethyl-2,2′-azobis (2-methylpropionate) (“V-601” manufactured by Wako Pure Chemical Industries, Ltd.) was added thereto, and the mixture was heated and stirred at 75 ° C. for 3 hours. . Further, 0.21 part of V-601 was added and, after 3 hours of heating and stirring, 0.21 part of V-601 was added again and stirring was performed for 3 hours, whereby polymer 9 (Exemplary Compound (22) described above) was obtained. A 30% solution of was obtained.

[Synthesis Example 10]
(Synthesis of polymer 10)
7.5 parts of the monomer 4, 37.5 parts of polymethyl methacrylate having a methacryloyl group at the terminal (AA-6: manufactured by Toagosei Co., Ltd.), 5.0 parts of benzyl methacrylate, 0.50 parts of n-dodecyl mercaptan, And 16.7 parts of 1-methoxy-2-propanol were introduced into a nitrogen-substituted three-necked flask, stirred with a stirrer (Shinto Kagaku Co., Ltd .: Three-One Motor), and heated while flowing nitrogen into the flask. The temperature is raised to 75 ° C. 0.14 part of dimethyl-2,2′-azobis (2-methylpropionate) (“V-601” manufactured by Wako Pure Chemical Industries, Ltd.) was added thereto, and the mixture was stirred at 75 ° C. for 3 hours. . Further, 0.14 part of V-601 was added, and after 3 hours of heating and stirring, 0.14 part of V-601 was added again and stirring was performed for 3 hours, whereby polymer 10 (exemplified compound (23) described above) was obtained. A 30% solution of was obtained.

[Example 1]
<Preparation of pigment dispersion composition (R1)>
The components of the following composition (1) are mixed, and using a homogenizer, the rotational speed is 3,000 r. p. m. And mixed for 3 hours to prepare a mixed solution containing the pigment.
[Composition (1)]
・ C. I. Pigment Red 254 ... 90 parts C.I. I. Pigment Red 177 ... 10 parts-30% solution of Polymer 1 (specific pigment dispersant) ... 150 parts-2-acetoxy-1-methoxypropane ... 750 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 (R1).

<Evaluation of pigment dispersion composition>
The following evaluation was performed about the obtained pigment dispersion composition (R1).
(1) Measurement and Evaluation of Viscosity For the obtained pigment dispersion composition (R1), using an E-type viscometer, the viscosity η ¹ of the pigment dispersion composition (R1) immediately after dispersion and after dispersion (at room temperature) The viscosity η ² of the pigment dispersion composition after one week passed was measured, and the degree of thickening was evaluated. The evaluation results are shown in Table 1 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.

(2) Measurement and Evaluation of Contrast The obtained pigment dispersion composition (R1) 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 when the polarization axis was parallel and perpendicular was measured, and the ratio was taken as the contrast. (This evaluation method 512 color display 10.4 "color TFT-LCD color filter, planting, Koseki, Fukunaga, Yamanaka"). The results of measurement evaluation are shown in Table 1 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 to 10]
In Example 1, except that the specific pigment dispersant (Polymer 1) was replaced with Polymer 2 to Polymer 10 which were specific pigment dispersants obtained in Synthesis Examples 2 to 10, respectively. In the same manner as in Example 1, red pigment dispersion compositions (R2) to (R10) were prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1 below.

[Example 11]
In Example 1, except that the red pigment dispersion composition was replaced with a pigment dispersion composition obtained using a mixed solution containing a green pigment of the following composition (2), the same procedure as in Example 1 was carried out. A green pigment dispersion composition (G1) was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 2 below.
[Composition (2)]
・ C. I. Pigment Green 36 ... 60 copies I. Pigment Yellow 150 ... 40 parts-30% solution of Polymer 1 (specific pigment dispersant) ... 150 parts-2-acetoxy-1-methoxypropane ... 750 parts

[Examples 12 to 20]
A green pigment dispersion was obtained in the same manner as in Example 11 except that the specific pigment dispersant (polymer 1) used in Example 11 was replaced with the polymer 2 to polymer 10 (specific pigment dispersant). Compositions (G2) to (G10) were prepared and evaluated in the same manner as in Example 11. The results are shown in Table 2 below.

[Example 21]
Example 1 was carried out in the same manner as in Example 1 except that the red pigment dispersion composition was replaced with a blue pigment dispersion composition obtained using a mixed solution containing a blue pigment having the following composition (3). A blue pigment dispersion composition (B1) was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 3 below.

[Composition (3)]
・ C. I. Pigment Blue 15; 6 ... 85 parts C.I. I. Pigment Violet 23 ... 15 parts-30% solution of Polymer 1 (specific pigment dispersant) ... 150 parts-2-acetoxy-1-methoxypropane ... 750 parts

[Examples 22 to 30]
In Example 21, a blue pigment dispersion composition was obtained in the same manner as in Example 21, except that the polymer 1 (specific pigment dispersant) was replaced with the polymer 2 to polymer 10 (specific pigment dispersant), respectively. Products (B1) to (B10) were prepared and evaluated in the same manner as in Example 21. The results are shown in Table 3 below.

[Comparative Example 1]
In Example 1, a red pigment dispersion composition was obtained in the same manner as in Example 1 except that the polymer 1 (specific pigment dispersant) was replaced with EFKA4047 (manufactured by EFKA) (hereinafter referred to as D-1). A product (R11) was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1 below.

[Comparative Example 2]
In Example 1, the polymer 1 (specific pigment dispersant) was mixed with N-vinylimidazole and terminal methacryloylated polymethyl methacrylate copolymer D-2 (= 15/85 [mass ratio], weight average molecular weight: weight average molecular weight. A red pigment dispersion composition (R12) was prepared in the same manner as in Example 1 except that it was changed to 30000), and the same evaluation as in Example 1 was performed. The results are shown in Table 1 below.

[Comparative Example 3]
In Example 1, the polymer 1 (specific pigment dispersant) was converted into methacrylic acid and terminal methacryloylated polymethyl methacrylate copolymer D-3 (= 15/85 [mass ratio], weight average molecular weight: weight average molecular weight 30000). A red pigment dispersion composition (R13) was prepared in the same manner as in Example 1 except that it was replaced with and evaluated in the same manner as in Example 1. The results are shown in Table 1 below.

[Comparative Example 4]
In Example 1, the polymer 1 (specific pigment dispersant) was mixed with 2-dimethylaminoethyl methacrylate and a terminal methacryloylated polymethyl methacrylate copolymer D-4 (= 15/85 [mass ratio], weight average molecular weight: A red pigment dispersion composition (R14) was prepared in the same manner as in Example 1 except that the weight average molecular weight was changed to 20000), and the same evaluation as in Example 1 was performed. The results are shown in Table 1 below.

[Comparative Example 5]
In Example 1, the polymer 1 (specific pigment dispersant) was mixed with a monomer having the following structure and a terminal methacryloylated polymethyl methacrylate copolymer D-5 (= 18/82 [mass ratio], weight average molecular weight: weight average molecular weight. A red pigment dispersion composition (R15) was prepared in the same manner as in Example 1 except that it was changed to 20000), and the same evaluation as in Example 1 was performed. The results are shown in Table 1 below.

[Comparative Example 6]
In Example 1, the polymer 1 (specific pigment dispersant) was mixed with a monomer having the following structure and a terminal methacryloylated polymethyl methacrylate copolymer D-5 (= 18/82 [mass ratio], weight average molecular weight: weight average molecular weight. A red pigment dispersion composition (R16) was prepared in the same manner as in Example 1 except that it was changed to 20000), and the same evaluation as in Example 1 was performed. The results are shown in Table 1 below.

[Comparative Examples 7-12]
In Example 11, a green pigment was obtained in the same manner as in Example 11 except that the polymer 1 (specific pigment dispersant) was replaced with any of the above-described copolymers D-1 to D-6. Dispersion compositions (G11) to (G16) were prepared and evaluated in the same manner as in Example 11. The results are shown in Table 2 below.

[Comparative Examples 13 to 18]
In Example 21, a blue pigment was obtained in the same manner as in Example 21, except that the polymer 1 (pigment dispersant) was replaced with any of the above-described copolymers D-1 to D-6. Dispersion compositions (B11) to (B16) were prepared and evaluated in the same manner as in Example 21. The results are shown in Table 3 below.

As shown in Tables 1 to 3, all of the pigment dispersion compositions of Examples using the polymers 1 to 10 which are specific pigment dispersants according to the present invention have a low viscosity of the composition, and the pigment dispersion It can be seen that the coating obtained by this pigment dispersion composition can provide high contrast. The reason why the coating obtained by the pigment dispersion composition of the present invention achieves high contrast is presumed to be because the pigment particles are uniformly dispersed in a finely divided state.
On the other hand, the pigment dispersion composition of the comparative example using a known pigment dispersant outside the scope of the present invention has a relatively high viscosity, the dispersibility of the pigment is lower than that of the present invention, and the dispersion stability. The film obtained using the pigment dispersion composition did not have sufficient contrast.

[Example 31]
<Preparation of photocurable composition>
The components described in the following composition (4) are further added to the pigment dispersion composition (R1) containing the red pigment obtained in Example 1, and the mixture is stirred and mixed. The photocurable composition of the present invention containing the red pigment. A product (color resist solution) was prepared.
[Composition (4)]
・ Dipentaerythritol hexaacrylate: 80 parts
(Photopolymerizable compound)
4- [o-bromo-pN, N-di (ethoxycarbonyl) aminophenyl] -2,6-di (trichloromethyl) -S-triazine 30 parts (photopolymerization initiator)
-2-acetoxy-1-methoxypropane solution of benzyl methacrylate / methacrylic acid (= 70/30 [mass ratio]) copolymer (weight average molecular weight: 10,000) (solid content 30%) ... 300 parts (alkali Soluble resin)
・ 2-acetoxy-1-methoxypropane (solvent) 390 parts

<Preparation of color filter using photocurable composition>
The obtained photocurable composition (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. It was 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 (color filter) was evaluated as follows. The results are shown in Table 4 below.

(3) Contrast A polarizing plate is placed on the colored resin film of the colored filter substrate, the colored resin film is sandwiched, and the luminance when the polarizing plate is parallel and the luminance when orthogonal are measured using BM-5 manufactured by Topcon Corporation. Then, 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.

(4) 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 32 to 40]
Photocuring was performed in the same manner as in Example 31 except that the pigment dispersion composition (R1) was replaced with the pigment dispersion compositions (R2) to (R10) obtained in Examples 2 to 10 in Example 31. Composition (color resist solution) was prepared. Using this color resist solution, a colored filter substrate (color filter) was produced and evaluated in the same manner as in Example 31. The results are shown in Table 4 below.

[Example 41]
The components described in the following composition (5) are further added to the pigment dispersion composition (G1) obtained in Example 11 and mixed by stirring. The photocurable composition (color resist) of the present invention containing a green pigment is then added. Liquid).
[Composition (5)]
・ Dipentaerythritol hexaacrylate: 50 parts (photopolymerizable compound)
4- [o-bromo-pN, N-di (ethoxycarbonyl) aminophenyl] -2,6-di (trichloromethyl) -S-triazine 20 parts (photopolymerization initiator)
-2-acetoxy-1-methoxypropane solution of benzyl methacrylate / methacrylic acid (= 70/30 [mass ratio]) copolymer (weight average molecular weight: 10,000) (solid content 30%) ... 70 parts (alkali Soluble resin)
・ 2-acetoxy-1-methoxypropane (solvent): 160 parts

<Production and evaluation of color filter using photocurable composition>
The obtained photocurable composition (color resist solution) was applied onto 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 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 heat-treated in a 220 ° C. oven 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.
The measurement of the contrast of the produced colored filter substrate and the evaluation of developability were performed in the same manner as in the evaluation of Example 31. The results are shown in Table 5 below.

[Examples 42 to 50]
Photocuring was performed in the same manner as in Example 41 except that the pigment dispersion composition (G1) was replaced with the pigment dispersion compositions (G2) to (G10) obtained in Examples 12 to 20 in Example 41. Composition (color resist solution) was prepared. Using this color resist solution, a colored filter substrate (color filter) was produced and evaluated in the same manner as in Example 31. The results are shown in Table 5 below.

[Example 51]
The components described in the following composition (6) are further added to the pigment dispersion composition (B1) obtained in Example 21, and the mixture is stirred and mixed. The photocurable composition (color resist) of the present invention containing a blue pigment. Liquid).
[Composition (6)]
・ Dipentaerythritol hexaacrylate: 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 [mass ratio]) copolymer (weight average molecular weight: 10,000) 2-acetoxy-1-methoxypropane solution (solid content 30%) ... 600 parts (alkali Soluble resin)
2-acetoxy-1-methoxypropane (solvent) 1240 parts

<Production and evaluation of color filter using photocurable composition>
The prepared photocurable composition (color resist solution) was applied onto 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. 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 heat-treated in a 220 ° C. oven 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.
Measurement of the contrast of the produced colored filter substrate and evaluation of developability were performed in the same manner as in Example 31. The results are shown in Table 6 below.

[Examples 52 to 60]
Photocuring was carried out in the same manner as in Example 51 except that the pigment dispersion composition (B1) was replaced with the pigment dispersion compositions (B2) to (B10) obtained in Examples 22 to 30 in Example 51. Composition (color resist solution) was prepared. Using this color resist solution, a colored filter substrate (color filter) was produced and evaluated in the same manner as in Example 31. The results are shown in Table 6 below.

[Comparative Examples 19-24]
Example 31 Example 31 except that the pigment dispersion composition (R1) obtained in Example 1 was replaced with the pigment dispersion compositions (R11) to (R16) obtained in Comparative Examples 1 to 6. In the same manner as in 31, a photocurable composition (color resist solution) was prepared. Using this color resist solution, a colored filter substrate (color filter) was produced and evaluated in the same manner as in Example 31. The results are shown in Table 4 below.

[Comparative Examples 25-30]
In Example 41, Example 41 was performed except that the pigment dispersion (G1) obtained in Example 11 was replaced with the pigment dispersion compositions (G11) to (G16) obtained in Comparative Examples 7 to 12. In the same manner as above, a photocurable composition (color resist solution) was prepared. Using this color resist solution, a colored filter substrate (color filter) was produced and evaluated in the same manner as in Example 41. The results are shown in Table 5 below.

[Comparative Examples 31-36]
Example 51 is the same as Example 51 except that the pigment dispersion (B1) obtained in Example 21 was replaced with the pigment dispersions (B11) to (B16) obtained in Comparative Examples 13 to 18. Similarly, a photocurable composition (color resist solution) was prepared. Using this color resist solution, a colored filter substrate (color filter) was produced and evaluated in the same manner as in Example 51. The results are shown in Table 6 below.

  As shown in Tables 4 to 6, all of the colored filter substrates (color filters of the examples) prepared using the photocurable compositions of the examples comprising the pigment dispersion composition of the present invention are high. Contrast was obtained and good developability was exhibited. On the other hand, the contrast of the colored filter substrate of the comparative example was inferior, and sufficient developability was not obtained.

Claims (12)

A pigment dispersion composition comprising a pigment and a polymer containing a copolymer unit derived from a monomer represented by the following general formula (1) in an organic solvent.

[In General Formula (1), R ¹ represents a hydrogen atom or a substituted or unsubstituted alkyl group. R ² represents an alkylene group. W represents -CO-, -C (= O) O-, -CONH-, -OC (= O)-, or a phenylene group. X is —O—, —S—, —C (═O) O—, —CONH—, —C (═O) S—, —NHCONH—, —NHC (═O) O—, —NHC (= O) S-, -OC (= O)-, -OCONH-, or -NHCO-. Y represents —NR ³ —, —O—, —S—, or —N═, and is linked to an N atom through an atomic group adjacent thereto to form a cyclic structure. R ³ represents a hydrogen atom, an alkyl group, or an aryl group. m and n each independently represents 0 or 1. ]   2. The pigment dispersion composition according to claim 1, wherein in the general formula (1), the cyclic structure formed by Y linking to an N atom via an adjacent atomic group is a condensed ring structure.   The pigment dispersion according to claim 1 or 2, 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. Composition.   The pigment dispersion composition according to any one of claims 1 to 3, 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 4, wherein the acid value of the polymer is 10 to 150 mgKOH / g.   The pigment is C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment green 36, C.I. I. Pigment red 177, C.I. I. Pigment red 254, C.I. I. Pigment blue 15: 6, and C.I. I. The pigment dispersion composition according to any one of claims 1 to 5, wherein the pigment dispersion composition is at least one pigment selected from the group consisting of CI Pigment Violet 23.   A photocurable composition comprising the pigment dispersion composition according to any one of claims 1 to 6, a photopolymerizable compound, and a photopolymerization initiator.   Furthermore, alkali-soluble resin is contained, The photocurable composition of Claim 7 characterized by the above-mentioned.   The photopolymerization initiator is at least one photopolymerization initiator selected from the group consisting of a triazine compound, a lophine dimer compound, and an oxime compound. The photocurable composition according to 8.   The photocurable composition according to any one of claims 7 to 9, wherein the photocurable composition is for a color filter.   A color filter comprising a colored pattern formed using the photocurable composition according to claim 10 on a substrate.   A photosensitive film forming step of forming the photosensitive film by applying the photocurable composition according to claim 10 directly or through another layer to the substrate, and pattern exposure and development on the formed photosensitive film And a colored pattern forming step of forming a colored pattern by sequentially performing the steps.