JP2008189792A - Pigment dispersion composition, curable composition, color filter and method for producing the same - Google Patents

Abstract

[PROBLEMS] To improve the fine dispersibility of pigment in a pigment dispersion composition, improve storage stability and coloring power, and to improve the photosensitivity, storage stability, coloring power, support adhesion, and developability of a colored curable composition. , And a reduction in development residue and color density (color loss) can be suppressed, and a pattern having a good cross-sectional shape can be formed.
A pigment dispersion composition containing at least (A) a compound having an unsaturated double bond and a molecular weight of less than 4000, (B) a pigment, and (C) a solvent, and a colored curable composition using the same. It is.
[Selection figure] None

Description

  The present invention relates to a pigment dispersion composition, a liquid crystal display element (LCD), a solid-state image sensor ( The present invention relates to a curable composition suitable for forming a colored region such as a color filter used for CCD, CMOS, etc., a color filter using the curable composition, and a method for producing the same.

  Conventionally, pigments exhibit a clear color tone and high coloring power, and are widely used in many fields. Among these pigments, those that are practically important are generally those of fine particles, and by virtue of preventing the pigment from agglomerating and miniaturizing, a clear color tone and high coloring power are obtained. However, when the pigment is made finer, its surface area increases and aggregation is promoted, and the dispersion of the pigment often shows high viscosity. For this reason, when this pigment dispersion is prepared on an industrial scale, it is difficult to take out the pigment dispersion from the disperser, it cannot be transported by pipeline, and it cannot be used due to gelation during storage. There are problems such as.

Therefore, conventionally, it is known to use various dispersants in order to obtain a pigment dispersion or a colored photosensitive composition having excellent fluidity and dispersibility. This dispersant is roughly classified into a polymer dispersant and a low molecular compound dispersant.
Examples of the polymer dispersant include polyacrylate, sodium maleate olefin copolymer, terminal carboxyl group-containing polyester (see, for example, Patent Document 1), acidic groups starting from tetrakis (2-hydroxyalkyl) ethylenediamine, and Polyester having a basic group (see, for example, Patent Document 2), macromonomer (an oligomer having an ethylenically unsaturated group at the terminal), a monomer having a hydroxyl group, a carboxy group-containing monomer, and other monomers. Such a copolymer (see, for example, Patent Document 3) is known.
Moreover, as low molecular weight compound dispersants, sorbitan fatty acid esters, polyoxyethylene alkylamines, alkyldiamines, alkanolamine derivatives, and the like are known (for example, see Patent Document 4), and dispersions in which pigment mother nuclei are introduced. There are examples of agents (for example, see Patent Documents 5 to 6).

  By the way, a colored photosensitive composition containing a pigment is useful as a material for a color filter used for a solid-state imaging device, a liquid crystal display, and the like. When a color filter is produced using the colored photosensitive composition, the quality, A pigment dispersion method that is excellent in terms of production stability and the like is widely adopted.

  In particular, when a color filter using a pigment is used as a color filter for a liquid crystal display, a finer particle size is required for the colorant (organic pigment, etc.) used to improve contrast (for example, patents). Reference 7). This is due to a factor that the polarization axis rotates due to light scattering, birefringence, and the like by the pigment. If the pigment is not sufficiently refined, light is scattered and absorbed by the pigment, resulting in a decrease in light transmittance, resulting in a low contrast and, furthermore, a curing sensitivity when patterning by exposure. It falls (for example, refer nonpatent literature 1). For this reason, in a colored photosensitive composition containing a pigment dispersed therein, it is necessary to disperse the pigment in a highly refined state.

  When the pigment is refined as described above, the surface area of the pigment is increased. Therefore, the use of the refined pigment tends to increase the amount of the dispersant added for dispersing the pigment in the curable composition. Moreover, in the curable composition for color filter use, in order to improve color purity, a higher content of the colorant (organic pigment) in the solid content is required. However, if a dispersant or a colorant is contained at a high concentration in the curable composition, the content of the photopolymerization initiator and the photopolymerizable monomer in the curable composition will be relatively reduced. The curable composition is desired to have low energy curability for improving the yield by shortening the exposure time, but there is a problem that it is difficult to obtain the curability of the exposed portion.

In addition, curing with low energy is also desired for curable compositions for color filters for solid-state imaging devices. As for color filters for solid-state imaging devices, the color patterns are becoming thinner to improve the image quality due to high light condensing property and light color separation property, and accordingly, the pigment concentration in the composition tends to be improved.
Furthermore, in pigment-based color filters, color unevenness is liable to occur due to the relatively coarse particles of the pigment, and as a result, the pigment in the curable composition is reduced with the miniaturization of the pigment to reduce the color unevenness. There is a tendency for the content of the dispersant to increase. Therefore, there is a problem that it is difficult to obtain curability.

  In order to cope with problems such as color unevenness in the formed coloring pattern, a technique using an organic solvent-soluble dye instead of a pigment as a colorant has been proposed (for example, see Patent Document 8). In such a dye-based color filter, with the increase in the dye concentration, problems such as a polymerization-inhibiting effect derived from the dye and a decrease in stability over time such as dye precipitation have become prominent.

  As described above, the curable composition for color filter use is a component necessary for curing the curable composition in any application for liquid crystal displays and solid-state imaging devices, and a photopolymerization initiator and The content of the photopolymerizable monomer is limited, and since the colorant concentration is high, there are problems such as low sensitivity and insufficient curing and insufficient adhesion to the substrate. It was.

In order to solve these problems, conventionally, a technique for improving the sensitivity by imparting polymerizability to a resin introduced mainly for imparting film formability and developability has been studied (for example, Patent Document 7). -8, refer nonpatent literature 2-3).
Japanese Patent Publication No.54-34009 JP-A-2-245231 JP-A-8-259876 US Pat. No. 3,536,510 Japanese Patent Publication No. 5-72943 JP-A-8-48890 JP 2000-321863 A JP 2003-029018 A 512 color display 10.4 "size color filter for TFT-LCD, Ueki, Koseki, Fukunaga, Yamanaka, 7th Color Optic Conference (1990) Latest Color Filter Technology Trends (85-87, Information Technology Publishing) State-of-the-art color filter process technology and chemicals (129-150, CM Publishing)

  However, satisfactory photosensitivity has not been obtained even with the above resins. In addition, problems such as generation of a development residue in an unexposed area, shape formation in an exposed area, and a decrease in color density (color loss) due to diffusion of a fine pigment in a cured area into the developer are still not solved. This is the actual situation.

  Furthermore, since the exposure sensitivity is insufficient, curing is insufficient in the deep part of the film using the curable composition, such as near the substrate interface, and therefore the adhesion to the substrate is poor, and the pattern shape is a reverse taper type. There are also issues such as. Further, in applications such as a color filter having a plurality of color patterns, when the coating liquid for forming the second color pattern is applied after the first color pattern is formed, the first color pigment is contained in the second color coating liquid. The problem that the color density is lowered (color loss) is not solved.

An object of the present invention is to solve the above-described conventional problems and achieve the following objects. That is,
An object of the present invention is to provide a pigment dispersion composition that suppresses pigment aggregation and is excellent in pigment fine dispersion, storage stability, and high coloring power. Also,
The present invention has high photosensitivity, excellent storage stability, coloring power, and support adhesion, suppresses a decrease in color density (color loss) in a cured part, has good developability, and has little development residue. An object of the present invention is to provide a colored curable composition capable of forming a colored pattern having a tapered or rectangular cross section. further,
An object of the present invention is to provide a color filter having excellent support adhesion and a colored pattern having a tapered or rectangular cross section and a method for producing a color filter excellent in productivity of the color filter.

  The present invention has been achieved based on the following effects presumed by using a specific compound as a pigment dispersant. However, the following effects of the present invention are not necessarily clear, and are estimated as follows.

That is, by adding a specific compound having a low molecular weight having an unsaturated double bond at the time of dispersing a dispersed pigment, a “pigment promoted by bridging a plurality of pigment particles by a dispersed resin, which has been a problem until now, has been considered as a problem. In order to sterically inhibit the “aggregation”, the pigment is efficiently dispersed, and this is cured by including the pigment by a crosslinking reaction, so that the pigment is prevented from diffusing into the developer or the coating solution. In addition, the specific compound having a low molecular weight (A) having an unsaturated double bond used in the present invention has a high unsaturated bond density, so that the double bond amount in the film at the time of film formation is increased, and exposure is performed. Sensitivity is greatly improved. As a result, even in the deep part of the film formed on the substrate by the curable composition of the present invention, such as the vicinity of the substrate interface, the curing becomes good, the support adherence is excellent, and the pattern shape can be prevented from becoming a reverse taper type. . Furthermore, since the specific compound suppresses the aggregation of the pigment, the penetration of the developing solution into the unexposed portion proceeds rapidly, and the molecular weight is small, so that it easily diffuses into the developing solution. Excellent removability can be exhibited. On the other hand, since sufficient sclerosis | hardenability is acquired in an exposure part, it can suppress the influence of a developing solution etc.
As described above, in pattern formation using the curable composition of the present invention, both excellent curability in the exposed area and excellent removability in the unexposed area are achieved, and a desired cross-sectional shape (particularly, the layered pattern is changed to It is considered that a good pattern can be formed which gives a shape in which the pattern profile of the cut surface when cut along a plane perpendicular to the layer surface is a taper type or a rectangle.

Specific means for solving the above problems are as follows.
<1> A pigment dispersion composition containing at least (A) a compound having an unsaturated double bond and a molecular weight of less than 4000, (B) a pigment, and (C) a solvent.
<2> A curable composition containing the pigment dispersion composition according to <1> and (D) a photopolymerization initiator.
<3> (E) The curable composition according to <2>, further including a photopolymerizable compound.
<4> A color filter having a colored pattern formed on the support by the curable composition according to <2> or <3>.
<5> (A) A step of preparing a curable composition using a pigment dispersion composition containing at least a compound having an unsaturated double bond and a molecular weight of less than 4000, (B) a pigment, and (C) a solvent; A colored layer forming step of forming a colored layer comprising the curable composition by applying the curable composition on a support, and an exposure step of exposing the colored layer in a pattern manner through a mask, And a development step of developing a colored layer after exposure to form a colored pattern.

According to the present invention, it is possible to provide a pigment dispersion composition that suppresses the aggregation of the pigment, is excellent in the fine dispersibility of the pigment, is excellent in storage stability, and has high coloring power.
Further, according to the present invention, the photosensitivity is high, the storage stability, the coloring power, and the support adhesion are excellent, the decrease in color density (color loss) of the cured portion is suppressed, and the developability is good. It is possible to provide a colored curable composition with little development residue and capable of forming a colored pattern having a tapered or rectangular cross section.
Furthermore, according to the present invention, it is possible to provide a color filter having excellent support adhesion and having a tapered or rectangular colored pattern in cross section, and a color filter manufacturing method excellent in productivity of the color filter. it can.

  Hereinafter, the pigment dispersion composition, the curable composition, the color filter using the curable composition, and the method for producing the same will be described in detail.

<Pigment dispersion composition>
The pigment dispersion composition of the present invention contains (A) at least a compound having an unsaturated double bond and a molecular weight of less than 4000, (B) a pigment, and (C) a solvent, and, if necessary, other components. Can be used.
Hereinafter, each component which comprises the pigment dispersion composition of this invention is explained in full detail.

(A) Compound having an unsaturated double bond and a molecular weight of less than 4000 The pigment dispersion composition of the present invention comprises a compound having an unsaturated double bond and a molecular weight of less than 4000 (hereinafter referred to as “specific compound in the present invention”). At least one of them. Thereby, aggregation of the pigment is suppressed, and the fine dispersibility of the pigment and the storage stability after dispersion are improved, and the coloring power is improved.

  The specific compound in the present invention has a molecular weight of less than 4000. Here, the molecular weight means the molecular weight when the specific compound in the present invention has a single structure, and means the mass average molecular weight when it has a molecular weight distribution such as an oligomer. In this invention, the inhibitory effect of pigment aggregation improves because the molecular weight of the compound which has an unsaturated double bond to contain is less than 4000. Also, in the curable composition, the adhesion to the support is improved by improving the photosensitivity and photopolymerizability, and the pattern formability is improved by reducing the development residue in the unexposed area (for example, the cross-sectional shape of the pattern is tapered) In addition, the coloring power is improved by suppressing the diffusion of the pigment into the developer.

  The molecular weight of the specific compound in the present invention is preferably from 50 to 3000, more preferably from 100 to 2500, and even more preferably from 150 to 3000, from the viewpoint of dispersion stability of the pigment and developability in the curable composition. 2000, and most preferably 200-1500.

  The specific compound in the present invention is an addition-polymerizable compound having at least one ethylenically unsaturated double bond, has at least one, preferably two or more terminal ethylenically unsaturated bonds, and has a molecular weight of 4000. Less than. Such compounds include, for example, monofunctional monomers, or compounds obtained by polymerizing these alone or copolymerized using a plurality of types, with pendant ethylenically unsaturated double bonds, and chemical forms such as polyfunctional monomers. Or a mixture thereof. Furthermore, the specific compound in the present invention may be a compound further having properties such as polymerization initiating ability, coloring ability, sensitizing ability, co-sensitizing ability, polymerization inhibiting ability, surface activity ability, and substrate adsorption ability.

Examples of the monofunctional monomer are shown in the following (1) to (13).
(1) A monomer having a carboxy group such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, 4-carboxystyrene, and an acidic cellulose derivative having a carboxy group in the side chain can also be used.
(2) 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate Monomers having a hydroxyl group such as acrylic acid esters and methacrylic acid esters having an aliphatic hydroxyl group such as ethyleneoxy-modified products thereof, and hydroxystyrene.

(3) Methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, benzyl acrylate, acrylic acid-2- Alkyl acrylates such as chloroethyl, glycidyl acrylate, 3,4-epoxycyclohexylmethyl acrylate, vinyl acrylate, 2-phenylvinyl acrylate, 1-propenyl acrylate, allyl acrylate, 2-allyloxyethyl acrylate, propargyl acrylate;
(4) Methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, amyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, methacrylic acid-2- Alkyl methacrylates such as chloroethyl, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, vinyl methacrylate, 2-phenylvinyl methacrylate, 1-propenyl methacrylate, allyl methacrylate, 2-allyloxyethyl methacrylate, and propargyl methacrylate.
(5) Acrylamide, methacrylamide, N-methylolacrylamide, N-ethylacrylamide, N-hexylmethacrylamide, N-cyclohexylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N-nitrophenylacrylamide, N-ethyl- Acrylamide or methacrylamide such as N-phenylacrylamide, vinylacrylamide, vinylmethacrylamide, N, N-diallylacrylamide, N, N-diallylmethacrylamide, allylacrylamide, allylmethacrylamide.

(6) Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, and phenyl vinyl ether.
(7) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate and vinyl benzoate.
(8) Styrenes such as styrene, α-methylstyrene, methylstyrene, chloromethylstyrene, and p-acetoxystyrene.
(9) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.
(10) Olefins such as ethylene, propylene, isobutylene, butadiene and isoprene.

(11) N-vinylpyrrolidone, acrylonitrile, methacrylonitrile and the like.
(12) Unsaturated imides such as maleimide, N-acryloylacrylamide, N-acetylmethacrylamide, N-propionylmethacrylamide, N- (p-chlorobenzoyl) methacrylamide.
(13) A methacrylic acid monomer having a hetero atom bonded to the α-position. For example, compounds described in JP 2002-309057 A, JP 2002-311569 A, and the like.

  Next, preferable examples of the compound obtained by polymerizing a monofunctional monomer alone or copolymerizing using a plurality of types thereof are shown below.

The specific compound in the present invention can be used without particular limitation as long as it is a resin having an unsaturated double bond. However, from the viewpoint of improving photosensitivity, the unsaturated equivalent is preferably less than 3000, and more preferably 1500. Less than is preferable, and less than 600 is most preferable.
Here, the unsaturated equivalent means the molecular weight of the resin per unsaturated bond.
By making the unsaturated equivalent of the specific compound in the present invention less than 3000, that is, by increasing the number of unsaturated double bonds in the specific compound molecule in the present invention, the photopolymerization and sensitivity are improved, and the polymerizability is increased. The improvement also improves the adhesion of the support, which is preferable because a tapered or rectangular pattern tends to be obtained.
The lower limit of the unsaturated equivalent is preferably 150. By suppressing the unsaturated equivalent to 150 or more, it is preferable in that the increase in viscosity at the time of dispersion of the pigment is suppressed and a composition having better dispersion stability during storage tends to be obtained.

  Specific compounds in the present invention include, for example, glycidyl group-containing unsaturated compounds such as glycidyl (meth) acrylate and allyl glycidyl ether, and unsaturated alcohols such as allyl alcohol, 2-hydroxy acrylate, and 2-hydroxy methacrylate. A resin containing a hydroxyl group, a carboxyl group-containing resin having a hydroxyl group, a free isocyanate group-containing unsaturated compound, a resin obtained by reacting an unsaturated acid anhydride, and an addition reaction product of an epoxy resin and an unsaturated carboxylic acid. Resin obtained by reacting a product, resin obtained by reacting a hydroxyl group-containing polymerizable monomer with an addition reaction product of a conjugated diene copolymer and an unsaturated dicarboxylic anhydride, and a base treatment to cause an elimination reaction to give an unsaturated group By synthesizing a resin with a specific functional group and subjecting the resin to base treatment, Resins were generated KazuHajime can be cited as typical resins.

  Among them, a resin obtained by reacting a carboxyl group-containing resin with a glycidyl group-containing unsaturated compound such as glycidyl (meth) acrylate or allyl glycidyl ether, or a resin obtained by polymerizing a hydroxyl group-containing (meth) acrylic ester compound (meth) acrylic. Resins obtained by reacting (meth) acrylic acid esters having a free isocyanate group such as acid-2-isocyanatoethyl, resins having structural units represented by the following general formulas (1) to (3), and desorbing by base treatment A resin or the like in which an unsaturated group is generated by synthesizing a resin having a specific functional group that causes a release reaction and gives an unsaturated group, and performing a base treatment on the resin is more preferable.

  The specific compound in the present invention is preferably a polymer compound having at least one selected from structural units represented by any one of the following general formulas (1) to (3) as an unsaturated double bond moiety.

In the general formulas (1) to (3), A ¹ , A ² , and A ³ each independently represent an oxygen atom, a sulfur atom, or —N (R ²¹ ) —, and R ²¹ represents a substituent. It represents an alkyl group that may have. G ¹ , G ² , and G ³ each independently represent a divalent organic group. X and Z each independently represent an oxygen atom, a sulfur atom, or —N (R ²² ) —, and R ²² represents an alkyl group which may have a substituent. Y represents an oxygen atom, a sulfur atom, a phenylene group which may have a substituent, or —N (R ²³ ) —, and R ²³ represents an alkyl group which may have a substituent. R ^{1 to} R ²⁰ each independently represents a monovalent substituent.

In the general formula (1), R ^{1 to} R ³ each independently represents a monovalent substituent, and examples thereof include a hydrogen atom and an alkyl group which may further have a substituent. Among them, R ¹ , R ² is preferably a hydrogen atom, and R ³ is preferably a hydrogen atom or a methyl group.
R ^{4 to} R ⁶ each independently represents a monovalent substituent. Examples of R ⁴ include a hydrogen atom or an alkyl group which may further have a substituent. Among them, a hydrogen atom or a methyl group An ethyl group is preferred. R ⁵ and R ⁶ are each independently a hydrogen atom, a halogen atom, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, or an alkyl group that may further have a substituent, or a substituent. An aryl group which may further have a substituent, an aryloxy group which may further have a substituent, an alkylsulfonyl group which may further have a substituent, and further having a substituent An arylsulfonyl group which may be substituted may be mentioned. Among them, a hydrogen atom, an alkoxycarbonyl group, an alkyl group which may further have a substituent, and an aryl group which may further have a substituent are preferable.
Here, examples of the substituent that can be introduced include a methoxycarbonyl group, an ethoxycarbonyl group, an isopropyloxycarbonyl group, a methyl group, an ethyl group, and a phenyl group.

A ¹ represents an oxygen atom, a sulfur atom, or —N (R ²¹ ) —, and X represents an oxygen atom, a sulfur atom, or —N (R ²² ) —. Here, examples of R ²¹ and R ²² include an alkyl group which may have a substituent.
G ¹ represents a divalent organic group, but an alkylene group which may have a substituent is preferable. More preferably, it has an alkylene group which may have a substituent having 1 to 20 carbon atoms, a cycloalkylene group which may have a substituent having 3 to 20 carbon atoms, or a substituent having 6 to 20 carbon atoms. An aromatic group that may be present may be mentioned. Among them, a linear or branched alkylene group having 1 to 10 carbon atoms that may have a substituent, or cyclo that may have a substituent having 3 to 10 carbon atoms. An alkylene group and an aromatic group which may have a substituent having 6 to 12 carbon atoms are preferable in terms of performance such as strength and developability.
Here, a hydroxyl group is preferable as the substituent in G ¹ .

In the general formula (2), R ^{7 to} R ⁹ each independently represents a monovalent substituent, and examples thereof include a hydrogen atom and an alkyl group which may further have a substituent. Among them, R ⁷ , R ⁸ is preferably a hydrogen atom, and R ⁹ is preferably a hydrogen atom or a methyl group.
R ^{10 to} R ¹² each independently represents a monovalent substituent. Specific examples of the substituent include a hydrogen atom, a halogen atom, a dialkylamino group, an alkoxycarbonyl group, a sulfo group, and a nitro group. , A cyano group, an alkyl group which may further have a substituent, an aryl group which may further have a substituent, an alkoxy group which may further have a substituent, and an aryl which may further have a substituent Examples thereof include an oxy group, an alkylsulfonyl group that may further have a substituent, and an arylsulfonyl group that may further have a substituent. Among them, a hydrogen atom, an alkoxycarbonyl group, and a substituent may be further included. A good alkyl group and an aryl group which may further have a substituent are preferred.
Here, examples of the substituent that can be introduced include those exemplified in the general formula (1).

A ² each independently represents an oxygen atom, a sulfur atom, or —N (R ²¹ ) —, where R ²¹ is a hydrogen atom, an alkyl group that may have a substituent, or the like. Can be mentioned.
G ² represents a divalent organic group, but an alkylene group which may have a substituent is preferable. Preferably, it has an alkylene group which may have a substituent having 1 to 20 carbon atoms, a cycloalkylene group which may have a substituent having 3 to 20 carbon atoms, and a substituent which has 6 to 20 carbon atoms. Aromatic group, etc. may be mentioned. Among them, a linear or branched alkylene group having 1 to 10 carbon atoms which may have a substituent, or a cycloalkylene which may have a substituent having 3 to 10 carbon atoms. Group, and an aromatic group which may have a substituent having 6 to 12 carbon atoms is preferable in terms of performance such as strength and developability.
Here, the substituent in G ² is preferably a hydroxyl group.

Y represents an oxygen atom, a sulfur atom, -N ^{(R 23)} - represents a or phenylene group which may have a substituent. Here, examples of R ²³ include a hydrogen atom and an alkyl group which may have a substituent.

In the general formula (3), R ^{13 to} R ¹⁵ each independently represents a monovalent substituent, and examples thereof include a hydrogen atom and an alkyl group which may have a substituent. Among them, R ¹³ , R ¹⁴ is preferably a hydrogen atom, and R ¹⁵ is preferably a hydrogen atom or a methyl group.
R ^{16 to} R ²⁰ each independently represents a monovalent substituent, and R ^{16 to} R ²⁰ are, for example, a hydrogen atom, a halogen atom, a dialkylamino group, an alkoxycarbonyl group, a sulfo group, a nitro group, or a cyano group. , An alkyl group that may further have a substituent, an aryl group that may further have a substituent, an alkoxy group that may further have a substituent, an aryloxy group that may further have a substituent, Examples include an alkylsulfonyl group that may further have a substituent, an arylsulfonyl group that may further have a substituent, and the like. Among them, a hydrogen atom, an alkoxycarbonyl group, and an alkyl group that may further have a substituent An aryl group which may further have a substituent is preferable. Examples of the substituent that can be introduced include those listed in the general formula (1).
A ³ represents an oxygen atom, a sulfur atom, or —N (R ²¹ ) —, and Z represents an oxygen atom, a sulfur atom, or —N (R ²² ) —. Examples of R ²¹ and R ²² include the same as those in general formula (1).

G ³ represents a divalent organic group, and an alkylene group which may have a substituent is preferable. Preferably, it has an alkylene group which may have a substituent having 1 to 20 carbon atoms, a cycloalkylene group which may have a substituent having 3 to 20 carbon atoms, and a substituent which has 6 to 20 carbon atoms. Aromatic group, etc. may be mentioned. Among them, a linear or branched alkylene group having 1 to 10 carbon atoms which may have a substituent, or a cycloalkylene which may have a substituent having 3 to 10 carbon atoms. Group, and an aromatic group which may have a substituent having 6 to 12 carbon atoms is preferable in terms of performance such as strength and developability.
Here, the substituent in G ³ is preferably a hydroxyl group.

  As a specific compound in the present invention, the structural unit represented by the general formulas (1) to (3) is 20 mol% or more and less than 95 mol% in one molecule from the viewpoint of improving curability and reducing development residue. A compound included in a range is preferable. More preferably, it is 25-90 mol%. More preferably, it is the range of 30 mol% or more and less than 85 mol%.

  The synthesis of the polymer compound having the structural unit represented by the general formulas (1) to (3) is based on the synthesis method described in paragraph numbers [0027] to [0057] of JP-A-2003-262958. Can be done. Among them, the synthesis method 1) in the same publication is preferable, and this is shown in the following (1).

  Specific examples of the polymer compound having the structural units represented by the general formulas (1) to (3) include the following polymer compounds 1 to 17.

Moreover, the resin obtained by the synthesis method of the following (1) or (2) can be mentioned suitably.
(1) A structure in which a compound represented by the following general formula (4) is used as a copolymerization component, a proton is extracted using a base, L is eliminated, and the structure represented by the general formula (1) A method for obtaining a desired polymer compound having
In general formula (4), L represents an anionic leaving group, and preferred examples include a halogen atom and a sulfonic acid ester. R 3 ^{to R} 6, A ^{1, G 1,} and for X has the same meaning as in the general formula (1), as the base used in order to rise to elimination reaction, inorganic compounds, either organic compounds May be used. Details and preferred embodiments of this method are described in paragraphs [0028] to [0033] of JP-A No. 2003-262958.

  Preferred inorganic compound bases include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate and the like, and organic compound bases include sodium methoxide, sodium ethoxide, potassium t- Examples thereof include metal alkoxides such as butoxide, organic amine compounds such as triethylamine, pyridine and diisopropylethylamine.

(2) with respect to the following general formula (5) using the compound represented by as a copolymer component in the polymer, by base treatment to rise to elimination reaction to a specific functional group to remove X ^10, radical reactive groups How to get.
In General Formula (5), A ⁵ represents an oxygen atom, a sulfur atom, or —N (R ⁵⁴ ) —, A ⁶ represents an oxygen atom, a sulfur atom, or —NR ⁵⁸ —, and R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴ , R ⁵⁵ , R ⁵⁶ , R ⁵⁷ , and R ⁵⁸ each independently represent hydrogen or a monovalent organic group, X ¹⁰ represents a group to be removed by elimination reaction, and G ⁵ represents an organic linking group. n represents an integer of 1 to 10. Details and preferred embodiments of this method are described in detail in JP-A No. 2003-335814.

  Examples of the resin obtained by the synthesis method (2) include a polymer compound described in JP-A-2003-335814, specifically, for example, (i) a polyvinyl polymer compound, and (ii) a polyurethane polymer. Compound, (iii) polyurea polymer compound, (iv) poly (urethane-urea) polymer compound, (v) polyester polymer compound, (vi) polyamide polymer compound, (vii) acetal-modified polyvinyl alcohol Preferred examples include high-molecular compounds of the system and specific compounds obtained from the respective descriptions.

  Examples of the compound represented by the general formula (4) include the following compounds (M-1) to (M-12), but are not limited thereto.

  Next, examples (i-1 to i-52) of the compound represented by the general formula (5) are listed below.

The specific compound in the present invention needs to have a photopolymerizable unsaturated bond from the viewpoint of improving photosensitivity, and COOH, SO ₃ H, PO ₃ H ₂ from the viewpoint of enabling alkali development. , OSO ₃ H, OPO ₂ H ₂ are preferable. The specific compound in the present invention preferably has an acid value in the range of 20 to 300, preferably 40 to 200, more preferably 60 to 150 from the viewpoint of dispersion stability, balance between developability and sensitivity. .
Examples of monomers that can be used as the copolymerization monomer when synthesizing the specific compound in the present invention are the same as the above (1) to (13).

  Examples of polyfunctional monomers include esters of unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and aliphatic polyhydric alcohol compounds, unsaturated carboxylic acids and fatty acids Amides with aromatic polyamine compounds are used. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxy group, an amino group or a mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and a monofunctional or polyfunctional compound. 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 atom or the like 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 tris (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, tris (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer, isocyanur Examples include acid EO-modified triacrylate.

  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 tetracrotonate. 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- Those having an aromatic skeleton described in JP-A No. 5241 and JP-A-2-226149 and those containing 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 No. 54-21726.

  Further, urethane-based addition polymerizable compounds produced by using an addition reaction of isocyanate and hydroxyl group are also suitable. Specific examples thereof include, for example, one molecule described in JP-B-48-41708. A vinyl compound 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. A urethane compound etc. are mentioned.

^{_{CH 2 = C (R 10)}} COOCH 2 CH (R 11) OH formula (A)
(However, R ¹⁰ and R ¹¹ each independently represent H or CH _3. )

  Moreover, the urethane type addition polymeric compound which added the alcohol compound represented by the following general formula (A-1) instead of the compound represented by the said general formula (A) is also suitable.

In the general formula (A-1), R ³¹ and R ³² each independently represent a hydrogen atom or an alkyl group, and the alkyl group is preferably an alkyl group having 1 to 5 carbon atoms. R ³¹ and R ³² are more preferably a hydrogen atom or a methyl group, respectively.

R ³³ represents a hydrogen atom, an alkyl group, an alkoxy group, an allyl group, an aryl group, a functional group represented by the following general formula (A-2), or a functional group represented by the following general formula (A-3). Show. Especially, it is preferable that they are a hydrogen atom, a C1-C5 alkyl group, a C1-C5 alkoxy group, or a functional group represented by general formula (A-3), More preferably, methyl Group or a functional group represented by formula (A-3).

In the said general formula (A-2), n shows the integer of 1-10, Preferably, it is 1-5. In the general formulas (A-2) and (A-3), R ³⁴ represents a hydrogen atom or an alkyl group, and the alkyl group is preferably an alkyl group having 1 to 5 carbon atoms. In the general formula (A-3), a plurality of R ³⁴ present in the molecule may be the same or different from each other. R ³⁴ is more preferably a hydrogen atom or a methyl group.

  Examples of the alcohol compound represented by the general formula (A-1) include compounds (MA-1) to (MA-4) exemplified below, but are not limited thereto.

  Furthermore, in the present invention, urethane-based addition polymerizable compounds to which alcohol compounds such as the following compounds (MA-5) to (MA-12) are added are also suitable. In the following specific examples, m represents an integer of 1 to 20, R represents a hydrogen atom or a methyl group, and o, p, r, s, and t represent rational numbers of 0 to 20.

  Furthermore, the compound represented by the following general formula (B) can also be suitably used as the specific compound in the present invention.

In the formula, R ⁴¹ represents an n-valent organic group. ^R42 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ⁴³ and R ⁴⁵ each independently represents a hydrogen atom or a methyl group. X represents —O—, —NH—, —NR ⁴⁴ —, or —S—, and R ⁴⁴ represents a hydrogen atom or a monovalent organic group. n represents an integer of 1 to 12.

R ⁴¹ in the general formula (B) is an aliphatic residue, aromatic residue, or heterocyclic ring of a compound having at least one hydroxy group, primary amino group, secondary amino group, or thiol group in the molecule. It represents a residue or an aliphatic residue having a hetero atom, aromatic ring, or hetero ring in the molecule.

  The “aliphatic residue” is an aliphatic compound having at least one hydroxy group, primary amino group, secondary amino group, or thiol group in the molecule as a raw material for the synthesis of the specific compound in the present invention. When used, it represents an aliphatic group excluding the “hydroxy group, primary amino group, secondary amino group, or thiol group that reacts with an isocyanate compound during urethane bond formation reaction” from the structure of this raw material compound, and is unsubstituted Or may have a substituent. (In the case of having two or more substituents, these substituents may be the same or different.)

  The “substituent” may be any group that can be substituted, such as an aliphatic group, aromatic group, heterocyclic group, halogen atom, hydroxy group, thiol group, cyano group, nitro group, (meth) acrylate group. , Carboxy group, amino group, aliphatic amino group, aromatic amino group, heterocyclic amino group, aliphatic oxy group, aromatic oxy group, heterocyclic oxy group, aliphatic thio group, aromatic thio group, heterocyclic thio Group, aliphatic sulfonamide group, aromatic sulfonamide group, heterocyclic sulfonamide group, acyl group, acyloxy group, acylamino group, aliphatic oxycarbonyl group, aromatic oxycarbonyl group, heterocyclic oxycarbonyl group, aliphatic oxy Carbonylamino group, aromatic oxycarbonylamino group, heterocyclic oxycarbonylamino group, aliphatic thiocarbonylamino group, aromatic Ocarbonylamino group, heterocyclic thiocarbonylamino group, aliphatic aminocarbonylamino group, aromatic aminocarbonylamino group, heterocyclic aminocarbonylamino group, carbamoyl group, carbamoyloxy group, carbamoylamino group, aliphatic sulfonyl group, aromatic Aromatic sulfonyl group, heterocyclic sulfonyl group, aliphatic oxyamino group, aromatic oxyamino group, heterocyclic oxyamino group, silyl group, aliphatic oxysilyl group, silyloxy group, aliphatic oxycarbonyloxy group, aromatic oxycarbonyloxy group Group, heterocyclic oxycarbonyloxy group, sulfamoyloxy group, aliphatic sulfonyloxy group, aromatic sulfonyloxy group, anilino group, aliphatic azo group, aromatic azo group, heterocyclic azo group, aliphatic sulfinyl group, An aromatic sulfinyl group, It represents a heterocyclic sulfinyl group, an aliphatic sulfonyloxy group, an aromatic sulfonyloxy group, a heterocyclic sulfonyloxy group, a sulfamoyl group, a sulfo group, a phosphonyl group, a phosphonic acid group or phosphinoylamino group.

  Among them, preferred substituents are aliphatic groups, aromatic groups, heterocyclic groups, halogen atoms, hydroxyl groups, thiol groups, cyano groups, nitro groups, (meth) acryloyl groups, carboxy groups, amino groups, aliphatic amino groups. , Aromatic amino group, heterocyclic amino group, aliphatic oxy group, aromatic oxy group, heterocyclic oxy group, aliphatic thio group, aromatic thio group, aliphatic sulfonamido group, aromatic sulfonamido group, acyl group , Aliphatic oxycarbonyl group, aliphatic oxycarbonylamino group, aromatic oxycarbonylamino group, aliphatic thiocarbonylamino group, aromatic thiocarbonylamino group, aliphatic aminocarbonylamino group, aromatic aminocarbonylamino group, carbamoyl Group, aliphatic sulfonyl group, aromatic sulfonyl group, silyl group, aliphatic oxysilyl group, silyl Alkoxy group, an aliphatic carbonyloxy group, an aromatic carbonyl group, a heterocyclic carbonyloxy group, an aliphatic oxycarbonyl group, an aliphatic sulfonyloxy group, a sulfamoyl group, a sulfo group and a phosphonyl group or a phosphonic group.

  More preferred substituents include aliphatic groups, aromatic groups, heterocyclic groups, halogen atoms, hydroxyl groups, thiol groups, (meth) acryloyl groups, carboxy groups, amino groups, aliphatic groups, particularly from the viewpoint of sensitivity and solubility. Aromatic amino group, aromatic amino group, aliphatic oxy group, aromatic oxy group, heterocyclic oxy group, aliphatic thio group, aliphatic sulfonamido group, aliphatic oxycarbonyl group, aliphatic oxycarbonylamino group, silyl group An aliphatic oxysilyl group, an aliphatic carbonyloxy group, an aliphatic oxycarbonyloxy group, an aliphatic sulfonyloxy group, a sulfo group, or a phosphone group.

The “aliphatic group” means an alkyl group, an alkenyl group, or an alkynyl group. The aliphatic group may have a branch and may form a ring. Moreover, it may be unsubstituted or may have a substituent. When the aliphatic group has a substituent, it may have the substituents mentioned in the explanation of the above “substituent”, and when it has two or more substituents, those substituents may be the same or different. It may be. When the aliphatic group is an alkyl group, it may be linear, branched, or may form a ring, and preferably has 1 to 21 carbon atoms. It is more preferable that it is number 1-16, and it is especially preferable that it is C1-C12.
Examples of the alkyl group having 1 to 21 carbon atoms include methyl group, ethyl group, n-propyl group, n-butyl group, n-amyl group, n-hexyl group, n-heptyl group, n-octyl group, n- Nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n- Nonadecyl group, n-eicosanyl group, i-propyl group, sec-butyl group, i-butyl group, t-butyl group, 1-methylbutyl group, 1-ethylpropyl group, 2-methylbutyl group, i-amyl group, neopentyl Group, 1,2-dimethylpropyl group, 1,1-dimethylpropyl group, t-amyl group, 1,3-dimethylbutyl group, 3,3-dimethylbutyl group,

2-ethylbutyl group, 2-ethyl-2-methylpropyl group, linear or branched heptyl group, 1-methylheptyl group, 2-ethylhexyl group, 1,5-dimethylhexyl group, t-octyl group, branched nonyl Group, branched decyl group, branched undecyl group, branched dodecyl group, branched tridecyl group, branched tetradecyl group, branched pentadecyl group, branched hexadecyl group, branched heptadecyl group, branched octadecyl group, linear or Branched nonadecyl group, linear or branched eicosanyl group, cyclopropyl group, cyclopropylmethyl group, cyclobutyl group, cyclobutylmethyl group, cyclopentyl group, cyclohexyl group, cyclohexylmethyl group, cycloheptyl group, cyclooctyl group, cyclohexylpropyl Group, cyclododecyl group, Rubornyl group, bornyl group, cis-miltanyl group, isopinocanphenyl group, noradamantyl group, adamantyl group, adamantylmethyl group, 1- (1-adamantyl) ethyl group, 3,5-dimethyladamantyl group, quinuclidinyl group, cyclopentyl Preferred examples include an ethyl group and a bicyclooctyl group.

  Among the above, methyl group, ethyl group, n-propyl group, n-butyl group, n-amyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, i-propyl group, sec-butyl group, i-butyl group, t-butyl group, 1-methylbutyl group, 1-ethylpropyl group 2-methylbutyl group, i-amyl group, neopentyl group, 1,2-dimethylpropyl group, 1,1-dimethylpropyl group, t-amyl group, 1,3-dimethylbutyl group, 3,3-dimethylbutyl group 2-ethylbutyl group, 2-ethyl-2-methylpropyl group, linear or branched heptyl group, 1-methylheptyl group, 2-ethylhexyl group, 1,5-dimethylhexyl group, t-octyl Branched nonyl group, branched decyl group, branched undecyl group, branched dodecyl group, branched tridecyl group, branched tetradecyl group, cyclopropyl group, cyclopropylmethyl group, cyclobutyl group, cyclobutylmethyl group, cyclopentyl group Cyclohexyl group, cyclohexylmethyl group, cycloheptyl group, cyclooctyl group, cyclohexylpropyl group, cyclododecyl group, norbornyl group, bornyl group, cis-miltanyl group, isopinocamphenyl group, noradamantyl group, adamantyl group, adamantylmethyl More preferably a group, 1- (1-adamantyl) ethyl group, 3,5-dimethyladamantyl group, quinuclidinyl group, cyclopentylethyl group, or bicyclooctyl group,

  Further, methyl group, ethyl group, n-propyl group, n-butyl group, n-amyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, i -Propyl group, sec-butyl group, i-butyl group, t-butyl group, 1-methylbutyl group, 1-ethylpropyl group, 2-methylbutyl group, i-amyl group, neopentyl group, 1,2-dimethylpropyl group 1,1-dimethylpropyl group, t-amyl group, 1,3-dimethylbutyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, 2-ethyl-2-methylpropyl group, linear or branched Heptyl group, 1-methylheptyl group, 2-ethylhexyl group, 1,5-dimethylhexyl group, t-octyl group, branched nonyl group, branched decyl group, cyclopropyl group, cyclopropylmethyl , Cyclobutyl group, cyclobutylmethyl group, cyclopentyl group, cyclohexyl group, cyclohexylmethyl group, cycloheptyl group, cyclooctyl group, cyclohexylpropyl group, cyclododecyl group, norbornyl group, bornyl group, noradamantyl group, adamantylmethyl, adamantylmethyl A group, 1- (1-adamantyl) ethyl group, 3,5-dimethyladamantyl group, cyclopentylethyl group or bicyclooctyl group is particularly preferred.

  Of the alkyl groups exemplified above, an alkyl group substituted with fluorine is also particularly suitable. Examples of the fluorine-substituted alkyl group include a trifluoromethyl group, a trifluoroethyl group, a pentafluoroethyl group, a heptafluoropropyl group, Nonafluorobutyl group, tridecafluorohexyl group, pentadecafluoroheptyl group, heptadecafluorooctyl group, tridecafluorooctyl group, nonadecafluorononyl group, heptadecafluorodecyl group, or perfluorodecyl group are preferable. Among these, a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a nonafluorobutyl group, a tridecafluorohexyl group, and a pentadecafluoroheptyl group are more preferable, and further a trifluoromethyl group and a pentafluoroethyl group Heptafluoropropyl group, a nonafluorobutyl group or a tridecafluorohexyl group, is particularly preferred.

  When the aliphatic group is an alkenyl group, it may be unsubstituted or may have a substituent, and an alkenyl group having 2 to 21 carbon atoms is preferable. An alkenyl group having 2 to 16 carbon atoms is more preferable, and an alkenyl group having 2 to 10 carbon atoms is more preferable. Examples of the alkenyl group having 2 to 21 carbon atoms include a vinyl group, isopropenyl group, 2-propenyl group, 2-methyl-propenyl group, 1-methyl-1-propenyl group, 1-butenyl group and 3-butenyl group. 1-methyl-1-butenyl group, 1,1-dimethyl-3-butenyl group, 1-pentenyl group, 2-pentenyl group, 1-ethyl-1-pentenyl group, 1-hexenyl group, 1-heptenyl group, 2,6-dimethyl-5-heptenyl group, 9-decenyl group, 1-cyclopentenyl group, 2-cyclopentenylmethyl group, cyclohexenyl group, 1-methyl-2-cyclohexenyl group, 1,4-dihydro-2 -Methylphenyl group, octenyl group, citronellyl group, oleyl group, geranyl group, farnesyl group, 2- (1-cyclohexenyl) ethyl group and the like are preferable. It is.

  Among the above, vinyl group, isopropenyl group, 2-propenyl group, 2-methyl-propenyl group, 1-methyl-1-propenyl group, 1-butenyl group, 3-butenyl group, 1-methyl-1-butenyl group 1,1-dimethyl-3-butenyl group, 1-pentenyl group, 2-pentenyl group, 1-ethyl-1-pentenyl group, 1-hexenyl group, 1-heptenyl group, 1-cyclopentenyl group, 2-cyclo A pentenylmethyl group, a cyclohexenyl group, a 1-methyl-2-cyclohexenyl group, and a 1,4-dihydro-2-methylphenyl group are more preferable, and further a vinyl group, an isopropenyl group, a 2-propenyl group, and 2-methyl. -Propenyl group, 1-methyl-1-propenyl group, 1-butenyl group, 3-butenyl group, 1-methyl-1-butenyl group, 1,1-dimethyl-3- Tenenyl group, 1-pentenyl group, 2-pentenyl group, 1-ethyl-1-pentenyl group, 1-hexenyl group, 1-cyclopentenyl group, 2-cyclopentenylmethyl group, cyclohexenyl group, 1-methyl-2- A cyclohexenyl group and a 1,4-dihydro-2-methylphenyl group are particularly preferable.

The “aromatic group” means an aryl group. The aryl group may be unsubstituted or may have a substituent, and preferably has 6 to 21 carbon atoms. Especially, a C6-C15 aryl group is preferable and a C6-C10 aryl group is more preferable.
Preferred examples of the aryl group having 6 to 21 carbon atoms include a phenyl group, a naphthyl group, a biphenylenyl group, an acenaphthenyl group, a fluorenyl group, an anthracenyl group, an anthraquinonyl group, and a pyrenyl group. Group, naphthyl group, biphenylenyl group, acenaphthenyl group, fluorenyl group or anthracenyl group is more preferable, and further, phenyl group, naphthyl group, biphenylenyl group or fluorenyl group is particularly preferable.
The aryl group is preferably a phenyl group or a naphthyl group, and particularly preferably a phenyl group.

  The “heterocycle” has a heteroatom (eg, nitrogen atom, sulfur atom, oxygen atom) in the ring, and may be a saturated ring or an unsaturated ring, Or a condensed ring, which may be unsubstituted or may have a substituent. It is preferable that carbon number of a heterocyclic ring is 1-32, and 2-16 are more preferable. For example, isocyanuric ring, epoxy ring, oxetane ring, furan ring, tetrahydrofuran ring, pyran ring, tetrahydropyran ring, dioxane ring, trioxane ring, tetrahydrothiophene ring, thiophene ring, dithiane ring, trithiane ring, pyrrolidine ring, piperidine ring, piperazine Ring, triazine ring, triazacyclononane ring, morpholine ring, thiomorpholine ring, pyrrole ring, pyrazole ring, imidazole ring, triazole ring, tetrazole ring, oxazole ring, isoxazole ring, thiazole ring, thiadiazole ring, indole ring, carbazole Ring, benzofuran ring, pyridine ring, quinoline ring, pyrimidine ring, pyridazine ring, pyrazine ring, phenanthroline ring, quinazoline ring, acridine ring, uracil ring, lactone ring, etc.

  Among them, isocyanuric ring, epoxy ring, furan ring, tetrahydrofuran ring, pyran ring, tetrahydropyran ring, tetrahydrothiophene ring, thiophene ring, pyrrolidine ring, piperidine ring, piperazine ring, morpholine ring, thiomorpholine ring, pyrrole ring, pyrazole ring, imidazole Ring, triazole ring, oxazole ring, thiazole ring, thiadiazole ring, indole ring, carbazole ring, benzofuran ring, pyridine ring, quinoline ring, pyrimidine ring, pyridazine ring, pyrazine ring, uracil ring, lactone ring, especially isocyanuric ring, epoxy Ring, tetrahydrofuran ring, tetrahydropyran ring, tetrahydrothiophene ring, pyrrolidine ring, piperidine ring, morpholine ring, pyrrole ring, pyrazole ring, imidazole ring, triazole ring, oxygen Tetrazole ring, a thiazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring, a lactone ring.

  The “aromatic residue” means that when an aromatic compound having at least one hydroxy group in the molecule is used as a raw material for synthesizing a specific compound, the structure of this raw material compound indicates “at the time of urethane bond formation reaction”. It represents an aromatic group excluding a “hydroxy group that reacts with an isocyanate compound” and may be unsubstituted or may have a substituent. (In the case of having two or more substituents, these substituents may be the same or different.)

  The “heterocyclic residue” means that when a heterocyclic compound having at least one hydroxy group in the molecule is used as a raw material for synthesizing a specific compound, a “urethane bond formation” is derived from the structure of the raw material compound. It represents a heterocyclic group excluding the “hydroxy ring group that reacts with an isocyanate compound during the reaction” and may be unsubstituted or may have a substituent. (In the case of having two or more substituents, these substituents may be the same or different.)

  The “aliphatic residue having a heteroatom, an aromatic ring, or a heterocycle in the molecule” has at least one hydroxy group in the molecule as a raw material when the specific compound according to the present invention is synthesized, When an aliphatic compound having a heteroatom, aromatic ring, or heterocycle in the molecular structure is used, a residue obtained by removing the “hydroxy group that reacts with an isocyanate compound during urethane bond formation reaction” from the structure of this raw material compound It may be unsubstituted or may have a substituent. (When it has two or more substituents, these substituents may be the same or different). As a hetero atom, an oxygen atom, a sulfur atom, or a nitrogen atom is preferable, and an oxygen atom or a nitrogen atom is more preferable.

In the general formula (B), when X is —NR ⁴⁴ —, R ⁴⁴ is a hydrogen atom, or an ether bond, amino bond, thioether bond, or a hydrocarbon ring structure having 3 to 10 carbon atoms in the structure; It may have a partial structure selected from the group consisting of an aromatic ring, a heterocyclic ring, a urethane bond, a thiourethane bond, an ester bond, an amide bond, a urea bond, or a thiourea bond, and is saturated or unsaturated. The C1-C50 hydrocarbon residue which may be represented. The hydrocarbon residue may further have a substituent. When it has a substituent, the substituent is synonymous with the “substituent” described in R ⁴¹ of the general formula (B), and preferred examples thereof are also the same.

Among the compounds represented by the general formula (B), the “compound having at least one hydroxy group in the molecule” used as a raw material of the compound in which X is —O— is not particularly limited. For example, methanol, ethanol, propanol, butanol, pentanol, octanol, decyl alcohol, dodecanol, neopentyl alcohol, ethylene glycol, propanediol, neopentyl glycol, butanediol, hexanediol, octanediol, cyclopentanediol, cyclohexanediol, 4,4-isopropylidenedicyclohexanol, 1,3,5-cyclohexanetriol, cyclooctanediol, norbornanediol, decalindiol, inositol, 2- (hydroxymethyl) -1,3 Propanediol, threitol, glycerol, erythritol, adonitol, arabitol, xylitol, sorbitol, mannitol, iditol, dulcitol, ribose, xylose, galactose, glucose, sucrose, lactose, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,3 5-tris (2-hydroxyethyl) -cyanuric acid, hydroquinone, catechol, resorcinol, phloroglucinol, dihydroxynaphthalene, bis (4-hydroxyphenyl) methane, bisphenol A, 1,4-benzenedimethanol, dihydroxybenzophenone, flange Methanol, hydroxyindole, (hydroxymethyl) ethylene carbonate, dihydroxypyridine, Hydroxy pyridazine, cyanuric acid, dihydroxy pyrimidine,

2- (methylthio) ethanol, ethyl 2-hydroxyethyl sulfide, 3- (methylthio) -1-propanol, 4- (methylthio) -1-butanol, 3- (methylthio) -1-hexanol, 2,2′-thio Diethanol, 2-hydroxyethyl disulfide, 3,6-dithia-1,8-octanediol, 3,3′-thiodipropanol, 3-methylthio-1,2-propanediol, 3-ethylthio-1,2-propane Diol, D-glucose diethyl mercaptal, 1-thio-β-D-glucose, sodium salt dihydrate, trans-1,2-dithian-4,5-diol, 1,5-dithiacyclooctane-3-ol 1,4-dithiaspiro (4.5) decan-8-ol, 1,4-dithian-2,5-diol Triethanolamine, 2-amino-2-methyl-1,3-propanediol, bis-homotris, N, N, N ′, N′-tetrakis (2-hydroxypropyl) -ethylenediamine, 1,3-bis [tris (Hydroxymethyl) -methylamino] propane, (R)-(+)-3-pyrrolidinol, 1- [2- (2-hydroxyethoxy) ethyl] -piperazine, 4- (2-hydroxyethyl) morpholine, or publication Examples include various diols described in JP-A-2005-326556, which may be unsubstituted or may have a substituent. When it has two or more substituents, they may be the same or different.

Among the compounds represented by the general formula (B), the “compound having at least one primary amino group in the molecule” used as a raw material for the compound in which X is —NH— is not particularly limited. For example, n-alkylamine having 1 to 32 carbon atoms, 1,3-dimethylbutylamine, methylamine, methylamine hydrochloric acid, methylamine- ^13C hydrochloric acid, methylhydrazine, ethylamine, ethylamine hydrochloric acid, propylamine, propylamine hydrochloric acid, Butylamine, amylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, 1-tetradecylamine, pentadecylamine, 1-hexadecylmian, octadecylamine, isopropylamine, sec-buchi Amine, (S)-(+)-sec-butylamine, (R)-(−)-sec-butylamine, isobutylamine, tert-butylamine, tert-butylhydrazine hydrochloride, 1-methylbutylamine, 1-ethylpropylamine, (S)-(−)-2-methylbutylamine, 2-methylbutylamine, isoamylamine, 1,2-dimethylpropylamine, tert-amylamine, 1,3-dimethylbutylamine, 3,3-dimethylbutylamine, 2-amino Heptane, 3-aminoheptane, 1-methylheptylamine, 2-ethylhexylamine, 1,5-dimethylhexylamine, tert-octylamine,

Ethylenediamine, ethylenediaminedihydrochloric acid, 1,3-diaminopropane, 1,3-diaminopropanedihydrochloric acid, 1,2-diaminopropane, 1,4-diaminobutane, 1,2-diamino-2-methylpropane, DYTEK EP diamine 1,5-diaminopentane, 2,2-dimethyl-1,3-propanediamine, hexamethylenediamine, DYTEK A amine, 1,7-diaminoheptane, 1,8-diaminooctane, C, C, C-trimethyl -1,6-hexanediamine, 1,9-diaminononane, 1,10-diaminodecane, 1,12-diaminododecane, N, N-dimethylmethylenediamine, N, N-diethylethylenediamine, N, N-dibutylethylenediamine N- (2-aminoethyl) -1,3-propanediamine, , 3′-diamino-N-methyldipropylamine, N- (3-aminopropyl) -1,3-propanediamine, spermidine, 4- (aminomethyl) -1,8-octanediamine, tris (2-amino Ethyl) amine, (aminomethyl) cyclopropane, cyclobutylamine, cyclopentylamine, 5-amino-2,2,4-trimethyl-1-cyclopentanemethylamine, cyclohexylamine, 4,4′-methylenebis (cyclohexyl-amine) 4,4′-methylenebis (2-methylcyclohexylamine), 1,2-diaminocyclohexane, trans-1,4-diaminocyclohexane, cyclohexanemethylamine, 1,3-cyclohexanebis (methylamine), cyclooctylamine, EXO-2-aminonorbornane 1-adamantanamine, 2,2 '-(ethylenedioxy) -bis (ethylamine), 4,7,10-trioxa-1,13-tridecanediamine, tetrahydrofurfurylamine,

Ethanolamine, 3-amino-1-propanol, 4-amino-1-butanol, 1,4-bis (3-aminopropyl) piperazine, 4- (2-aminoethyl) morpholine, aniline, 3-aminothiophenol, 4,4'-ethylenedianiline, 3,3'-methylenedianiline, 4,4'-methylenedianiline, 4,4'-oxydianiline, 4-aminophenol, 4,4'-thiodianiline, o- Tolidine, 5,5 ′-(hexafluoroisopropylidene) -di-o-toluidine, 3,5-bis (trifluoromethyl) -aniline, 4,4′-methylenebis (2,6-diethylaniline), 4, 4′-diaminooctafluorobiphenyl, 1,3-phenylenediamine, 1,4-phenylenediamine, pararosaniline base, 2, -Diaminonaphthalene, binaphthyl-2,2'-diamine, meso-1,2-bis (4-methoxyphenyl) -ethylenediamine, 2- [2- (aminomethyl) phenylthio] benzyl alcohol, m-xylylenediamine, p -Xylylenediamine etc. are mentioned, These may be unsubstituted or may have a substituent. When it has two or more substituents, they may be the same or different.

Among the compounds represented by the general formula (B), the “compound having at least one secondary amino group in the molecule” used as a raw material for the compound in which X is —NR ⁴⁴ — is not particularly limited. For example, dimethylamine, 1,1-dimethylhydrazine, N-ethylmethylamine, diethylamine, N-methylpropylamine, N-methylisopropylamine, N-ethylisopropylamine, dipropylamine, diisopropylamine, N- Methylbutylamine, N-ethylbutylamine, N-methyl-tert-butylamine, N-tert-butylisopropylamine, dibutylamine, di-sec-butylamine, diisobutylamine, tert-amyl-tert-butylamine, dipentylamine, N-methyl Hexylamine, Hexylamine, tert- amyl -tert- octylamine, di-octylamine, bis (2-ethylhexyl) amine, didecylamine, N- methyl octadecylamine,

N-methylethylenediamine, N-ethylethylenediamine, N-propylethylenediamine, N-isopropylethylenediamine, N, N′-dimethylethylenediamine, N, N′-diethylethylenediamine, N, N′-diisopropylethylenediamine, N, N, N ′ -Trimethylethylenediamine, N, N-dimethyl-N'-ethylethylenediamine, N, N-diethyl-N'-methylethylenediamine, N, N, N'-triethylethylenediamine, N, N, N ', N'-tetramethyl Ethylenediamine, N-methyl-1,3-propanediamine, N-propyl-1,3-propanediamine, N-isopropyl-1,3-propanediamine, N, N′-diethyl-1,3-propanediamine, N , N′-Diisopropyl-1,3- Lopandiamine, N, N, N′-trimethyl-1,3-propanediamine, N, N′-dimethyl-1,6-hexanediamine, N-methylcyclohexylamine, N-ethylcyclohexylamine, N-isopropylcyclohexylamine, N-tert-butylcyclohexylamine, dicyclohexylamine, (1S, 2S) -N, N′-bis (3,3-dimethylbutyl) -1,2-cyclohexanediamine, diallylamine, N-allylcyclopentylamine, allylcyclohexylamine , Bis (2-methoxyethyl) amine, diphenylamine, N-phenylbenzylamine, 1,2-dianilinoethane and the like, which may be unsubstituted or may have a substituent. When it has two or more substituents, they may be the same or different.

  Among the compounds represented by the general formula (B), the “compound having at least one thiol group in the molecule” used as a raw material for the compound in which X is —S— is not particularly limited. For example, methanethiol, ethanethiol, 1-propanethiol, 1-butanethiol, 1-pentanethiol, 1-hexanethiol, heptyl mercaptan, 1-octanethiol, nonyl mercaptan, 1-decanethiol, 1-dodecanethiol, hexa Decyl mercaptan, octadecyl mercaptan, 2-methyl-1-propanethiol, 2-methyl-1-butanethiol, 3-methyl-1-butanethiol, 2-propanethiol, 1-methyl-1-propanethiol, 2-methyl 2-propanethiol, 2-methyl-2-butanethio , Allyl mercaptan, cyclopentyl mercaptan, cyclohexyl mercaptan, 1,2-ethanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 2,3-butanedithiol, 1,5-pentanedithiol, 1,6-hexane Dithiol, 1,8-octanedithiol, 1,9-nonanedithiol, 2,2,2-trifluoroethanethiol, 3-chloro-1-propanethiol, 2-mercaptoethanol, 1-mercapto-2-propanol, 3 -Mercapto-1-propanol, 3-mercapto-2-butanol, 3-mercapto-1,2-propanediol, 2,3-dimercapto-1-propanol, dithiothreitol, dithioerythritol, 1,4-dithio-L -Threitol, 2-mercap Ethyl ether, 2-mercaptoethyl sulfide, furfuryl mercaptan, thiophenol, thiocresol, ethylthiophenol, benzyl mercaptan, 1,2,3-propanetrithiol, 1,1-cyclohexanedithiol, 1,2-cyclohexanedithiol, Bicyclo [2,2,1] hepta-exo-cis-2,3-dithiol,

1,1-bis (mercaptomethyl) cyclohexane, diethylene glycol bis (2-mercaptoacetate), diethylene glycol bis (3-mercaptopropionate), bis (2-mercaptoethyl) ether, ethylene glycol bis (2-mercaptoacetate), Ethylene glycol bis (3-mercaptopropionate), trimethylolpropane bis (2-mercaptoacetate), trimethylolpropane bis (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis ( 3-mercaptopropionate),

1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,2-bis (mercaptomethyl) benzene, 1,3-bis (mercaptomethyl) benzene, 1,4- Bis (mercaptomethyl) benzene, 1,2-bis (2-mercaptoethyl) benzene, 1,3-bis (2-mercaptoethyl) benzene, 1,4-bis (2-mercaptoethyl) benzene, 1,2- Bis (2-mercaptoethyleneoxy) benzene, 1,3-bis (2-mercaptoethyleneoxy) benzene, 1,4-bis (2-mercaptoethyleneoxy) benzene, 1,2,3-trimercaptobenzene, 1, 2,4-trimercaptobenzene, 1,3,5-trimercaptobenzene,

1,2,3-tris (mercaptomethyl) benzene, 1,2,4-tris (mercaptomethyl) benzene, 1,3,5-tris (mercaptomethyl) benzene, 1,2,3-tris (2-mercapto Ethyl) benzene, 1,2,4-tris (2-mercaptoethyl) benzene, 1,3,5-tris (2-mercaptoethyl) benzene, 1,2,3-tris (2-mercaptoethyleneoxy) benzene, 1,2,4-tris (2-mercaptoethyleneoxy) benzene, 1,3,5-tris (2-mercaptoethyleneoxy) benzene, 1,2,3,4-tetramercaptobenzene, 1,2,3 5-tetramercaptobenzene, 1,2,4,5-tetramercaptobenzene, 1,2,3,4-tetrakis (mercaptomethyl) benzene, 1, , 3,5-tetrakis (mercaptomethyl) benzene, 1,2,4,5-tetrakis (mercaptomethyl) benzene, 1,2,3,4-tetrakis (2-mercaptoethyl) benzene, 1,2,3 5-tetrakis (2-mercaptoethyl) benzene, 1,2,4,5-tetrakis (2-mercaptoethyl) benzene, 1,2,3,4-tetrakis (2-mercaptoethyleneoxy) benzene, 1,2, 3,5-tetrakis (2-mercaptoethyleneoxy) benzene, 1,2,4,5-tetrakis (2-mercaptoethyleneoxy) benzene, 2,2′-dimercaptobiphenyl, 4,4′-thiobis-benzenethiol 4,4′-dimercaptobiphenyl, 4,4′-dimercaptobibenzyl, 2,5-toluenedithiol, 3,4 Toluenedithiol, 1,4-naphthalenedithiol, 1,5-naphthalenedithiol, 2,6-naphthalenedithiol, 2,7-naphthalenedithiol, 2,4-dimethylbenzene-1,3-dithiol, 4,5-dimethylbenzene -1,3-dithiol, 9,10-anthracene dimethanethiol,

2-bis (2-mercaptoethylthio) benzene, 1,3-bis (2-mercaptoethylthio) benzene, 1,4-bis (2-mercaptoethylthio) benzene, 1,2-bis (2-mercaptoethyl) Thiomethyl) benzene, 1,3-bis (2-mercaptoethylthiomethyl) benzene, 1,4-bis (2-mercaptoethylthiomethyl) benzene, 1,2,3-tris (2-mercaptoethylthio) benzene 1,2,4-tris (2-mercaptoethylthio) benzene, 1,3,5-tris (2-mercaptoethylthio) benzene, 1,2,3,4-tetrakis (2-mercaptoethylthio) benzene 1,2,3,5-tetrakis (2-mercaptoethylthio) benzene, 1,2,4,5-tetrakis (2-mercaptoethylthio) benzene Zen, bis (2-mercaptoethyl) sulfide, bis (2-mercaptoethylthio) methane, 1,2-bis (2-mercaptoethylthio) ethane, 1,3-bis (2-mercaptoethylthio) propane, , 2,3-tris (2-mercaptoethylthio) propane, tetrakis (2-mercaptoethylthiomethyl) methane, 1,2-bis (2-mercaptoethylthio) propanethiol, 2,5-dimercapto-1,4 -Dithiane, bis (2-mercaptoethyl) disulfide, 3,4-thiophenedithiol, 1,2-bis (2-mercaptoethyl) thio-3-mercaptopropane, bis- (2-mercaptoethylthio-3-mercaptopropane) ) Sulfides and the like. These may be unsubstituted or may have a substituent. When it has two or more substituents, they may be the same or different.

As the monoisocyanate compound having two acrylates, specifically, 1,1- (bisacryloyloxymethyl) ethyl isocyanate is used.

Next, specific examples (I-1) to (I-49) and (I-51) to (I-62) of the polyfunctional acrylate compound represented by the general formula (B) are shown. It is not limited.

  Further, urethane acrylates as described in JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, JP-B-58-49860, JP-B-56-17654 And urethane compounds having an ethylene oxide skeleton described in JP-B-62-39417 and JP-B-62-39418. Further, 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 are used. Thus, a photopolymerizable composition having an excellent photosensitive speed can be obtained.

  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, and vinylphosphonic acid compounds described in JP-A-2-25493 Etc. 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.

  The unsaturated equivalent value of the polyfunctional monomer is preferably 50 or more and 3000 or less, more preferably 70 or more and 1000 or less, and more preferably 80 or more and 600 or less from the viewpoints of dispersion stability, storage stability, and sensitivity. Is more preferable, and most preferably 85 or more and 300 or less. The unsaturated equivalent is the molecular weight of the polyfunctional monomer per unsaturated bond.

About these polymerizable compounds, the details of usage such as the structure, single use or combination, and addition amount can be arbitrarily set in accordance with the performance design of the pigment dispersion composition or curable composition. For example, it is selected from the following viewpoints.
From the viewpoint of storage stability and fine dispersibility of the pigment dispersion composition, a monofunctional monomer is polymerized alone, or a compound obtained by copolymerization using a plurality of species is pendant with an ethylenically unsaturated double bond, or polyfunctional. A monomer having a chemical form is preferable, and a polyfunctional monomer is more preferable.
From the viewpoint of sensitivity as a curable composition, a structure having a high unsaturated group content per molecule is preferred, and in many cases, a bifunctional or higher functionality is preferred. Further, in order to increase the strength of the image portion, that is, 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 type). A method of adjusting both sensitivity and strength by using a compound) is also effective. From the viewpoint of curing sensitivity and storage stability, it is preferable to use a compound containing two or more (meth) acrylic acid ester structures, more preferable to use a compound containing three or more and less than 15, and four or more. Most preferably, compounds containing less than 10 are used. Moreover, it is preferable to contain an EO modified body from a viewpoint of hardening sensitivity and the developability of an unexposed part. Moreover, it is preferable to contain a urethane bond from a viewpoint of hardening sensitivity and exposure part intensity | strength.
In addition, the selection and use method of the addition polymerization compound is also important for compatibility and dispersibility with other components (for example, resin, photopolymerization initiator, pigment) in the pigment dispersion composition or curable composition. 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.

  From the above viewpoints, bisphenol A di (meth) acrylate, bisphenol A di (meth) acrylate EO modified product, trimethylolpropane tri (meth) acrylate, trimethylolpropane tris ((meth) acryloyloxypropyl) ether, trimethylolethane Tri (meth) acrylate, tetraethylene glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipenta Erythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, sorbitol tri (meth) acrylate, sorbitol tetra (meth) acrylate, sorbitol pen (Meth) acrylate, sorbitol hexa (meth) acrylate, tris ((meth) acryloyloxyethyl) isocyanurate, pentaerythritol tetra (meth) acrylate EO modified, pentaerythritol tetra (meth) acrylate EO modified, dipentaerythritol Hexa (meth) acrylate PO-modified products, dipentaerythritol hexa (meth) acrylate PO-modified products, A-GLY series (manufactured by Shin-Nakamura Chemical Co., Ltd.) and the like are preferred, and commercially available products include urethane oligomers. UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 ( Kyoeisha Chemical Co., Ltd.), U-2PPA, U-4 A, U-6HA, U-15HA, UA-32P, U-324A, U-4H, U-6H, UA-7000, UA-7100, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.) is preferable.

  Among them, modified bisphenol A di (meth) acrylate EO, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tris (( (Meth) acryloyloxyethyl) isocyanurate, pentaerythritol tetra (meth) acrylate EO modified product, dipentaerythritol hexa (meth) acrylate EO modified product, etc. are commercially available products such as DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), U-4HA, U-6HA, U-15HA, UA-32P, U-324A, U-4H, U-6H, UA-70 00, UA-7100, and UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.) are more preferable.

  In addition, a compound having an ethylenically unsaturated double bond, which further has properties such as polymerization initiating ability, coloring ability, sensitizing ability, co-sensitizing ability, surface active ability, and substrate adsorption ability, is described later. Polymerization initiators, colorants, sensitizers, co-sensitizers, polymerization inhibitors, other additives (hereinafter sometimes referred to as “specific additives in the present invention”), etc. Examples thereof include compounds having an unsaturated double bond introduced therein.

(Example of how to introduce unsaturated double bonds)
When the specific additive in the present invention has a hydroxy group or an amino group, an unsaturated double bond can be introduced by using an ester or amide with an unsaturated carboxylic acid. In addition, when the specific additive in the present invention is a monofunctional or polyfunctional isocyanate or epoxy, an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxy group, an amino group, or a mercapto group; An unsaturated double bond can be introduced by using an addition reaction product of Further, when the specific additive in the present invention is a monofunctional or polyfunctional carboxylic acid, an unsaturated double compound can be obtained by forming a dehydration condensation reaction product with the above nucleophilic unsaturated carboxylic acid ester or amide. Bonds can be introduced.
Further, when the specific additive in the present invention is a monofunctional or polyfunctional alcohol, amine, or thiol, an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group By adding a reaction product with an unsaturated carboxylic acid ester or amide having a leaving group such as a halogen group or a tosyloxy group, an unsaturated double bond can be formed. Can be introduced.

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.
The number of ethylenically unsaturated double bonds of the specific compound in the present invention is preferably 2 or more and 12 or less, more preferably 2 or more and 8 or less, and most preferably 3 or more and 6 or less. From the viewpoint of sensitivity, the ethylenically unsaturated bond of the specific compound in the present invention is preferably a (meth) acryl group or a structure derived from styrene, and more preferably a (meth) acryl group.

In addition, the preferred hydrophilicity / hydrophobicity of the specific compound in the present invention is preferably an SP value calculated by the Okitsu method of 16.0 to 38.0 from the viewpoint of solubility in a coating solvent and developability. More preferably, it is 0.0-32.0, and most preferably 18.0-30.0.
Here, the SP value (solubility parameter) is a numerical value defined by the square root of the cohesive energy density and represents an intermolecular force. The SP value can be calculated by, for example, the Okitsu method (Toshinao Okitsu, “Journal of the Adhesion Society of Japan” 29 (3) (1993)).

  As content in the pigment dispersion composition of the specific compound in this invention, 0.001-10 times are preferable with respect to the mass of a pigment, 0.01-8 times are more preferable, 0.1 times-10 times Is more preferable, and 0.3 to 2 times is most preferable. When the content is within the above range, the pigment can be dispersed more efficiently, and the color loss prevention, exposure sensitivity, support adhesion and pattern formability (desired taper type or rectangular cross section formability) are effectively improved. Can be made.

(B) Pigment The pigment dispersion composition of the present invention contains at least one pigment. Use of a pigment as the colorant is preferable in terms of durability such as heat resistance and light resistance.

  As the pigment that can be contained in the curable composition of the present invention, conventionally known various inorganic pigments or organic pigments can be used, and high transmittance is preferable.

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

As an organic pigment, for example,
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, 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;
Examples thereof include carbon black.

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

  Examples of the pigment that can be preferably used in the present invention include the following. However, the present invention is not limited to these.

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, 32,
C. I. Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66,
C. I. Pigment Black 1

These organic pigments can be used alone or in various combinations in order to increase color purity. For example, when the curable composition of the present invention is used for forming a color pattern of a color filter, it is preferably used in combination in order to increase the color purity of the color pattern.
Specific examples of combinations of pigments are shown below. For example, as a red pigment, an anthraquinone pigment, a perylene pigment, a diketopyrrolopyrrole pigment alone or at least one of them, a disazo yellow pigment, an isoindoline yellow pigment, a quinophthalone yellow pigment or a perylene red pigment , Etc. 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 100/100 to 100/5. By setting it to 100: 5 or less, it becomes easy to suppress the light transmittance from 400 nm to 500 nm, and the color purity can be further improved. Moreover, it can suppress that a dominant wavelength becomes shorter than 100/100 or less, and the shift | offset | difference from NTSC target hue can be made smaller. In particular, the mass ratio is optimally in the range of 100/50 to 100/10. In addition, in the case of the combination of red pigments, it can adjust according to chromaticity.

  As the green pigment, a halogenated phthalocyanine pigment can be used alone, or a mixture thereof with a disazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment, or an isoindoline yellow pigment 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 100/150 to 100/5. The mass ratio is particularly preferably in the range of 100/120 to 100/30.

  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, 37 is preferred. The mass ratio of the blue pigment to the violet pigment is preferably 100/30 to 100/0, more preferably 100/10 or more.

  In addition, as a pigment used when the curable composition of the present invention is used for forming a black matrix of a color filter, carbon, titanium carbon, iron oxide, titanium oxide alone or a mixture thereof is used. A combination is preferred. The mass ratio of carbon to titanium carbon is preferably in the range of 100/60 to 100/0.

When used for a color filter, the primary particle diameter of the pigment is preferably 100 nm or less from the viewpoint of color unevenness and contrast, and is preferably 5 nm or more from the viewpoint of dispersion stability. The primary particle diameter of the pigment is more preferably 5 to 75 nm, still more preferably 5 to 55 nm, and particularly preferably 5 to 35 nm.
The primary particle diameter of the pigment can be measured by a known method such as an electron microscope.

  Among these, the pigment is preferably a pigment selected from anthraquinone, azomethine, benzylidene, cyanine, diketopyrrolopyrrole, and phthalocyanine.

  As the content of the pigment in the pigment dispersion composition, from the viewpoint of ensuring high coloring power, for example, when producing a color filter, from the viewpoint of ensuring high color density and contrast, with respect to the total solid content of the composition, It is preferable that it is 30 mass% or more, More preferably, it is the range of 40-95 mass%.

In addition, in the pigment dispersion composition of this invention, you may use a dye together in the range which does not impair the effect of this invention. There is no restriction | limiting in particular as dye, A well-known dye can be used for conventional color filters. For example, Japanese Patent Application Laid-Open No. 64-90403, Japanese Patent Application Laid-Open No. 64-91102, Japanese Patent Application Laid-Open No. 1-94301, Japanese Patent Application Laid-Open No. 6-11614, No. 2592207, US Pat. No. 4,808,501. Specification, US Pat. No. 5,667,920, US Pat. No. 5,059,500, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115 JP-A-6-194828, JP-A-8-21599, JP-A-4-249549, JP-A-10-123316, JP-A-11-302283, JP-A-7-286107, JP 2001-4823, JP-A-8-15522, JP-A-8-29771, JP-A-8-146215, JP-A-11-3434. 7, JP-A-8-62416, JP-A-2002-14220, JP-A-2002-14221, JP-A-2002-14222, JP-A-2002-14223, JP-A-8-302224 The dyes disclosed in JP-A-8-73758, JP-A-8-179120, JP-A-8-151531, and the like can be used.
The chemical structure of the dye includes pyrazole azo, anilino azo, triphenylmethane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine. , Xanthene, phthalocyanine, benzopyran, and indigo dyes can be used.

(C) Solvent The pigment dispersion composition of the present invention contains at least one solvent. By using a solvent together with the (A) compound having an unsaturated double bond and a molecular weight of less than 4000 and the (B) pigment, a pigment dispersion composition in which the pigment is favorably dispersed can be prepared.

The solvent used is not particularly limited as long as it satisfies the solubility of each component of the composition and the applicability of the curable composition, but is preferably selected in consideration of safety.
Specific examples of the solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl oxyacetate, and ethyl oxyacetate. , Butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate, methyl 3-methoxypropionate, 3-methoxypropion Ethyl acetate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, methyl 2-methoxypropionate, 2-methoxypropion Ethyl, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, 2-methoxy-2 -Methyl methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate and the like;

Ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate (ethylene glycol monomethyl ether acetate), ethyl cellosolve acetate (ethylene glycol monoethyl ether acetate), diethylene glycol monomethyl ether, diethylene glycol mono Ethyl ether, diethylene glycol monobutyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol methyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene Etc. glycol propyl ether acetate;
Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone;
Aromatic hydrocarbons such as toluene and xylene are preferred.

  Among these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimeter ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, diethylene glycol monoethyl ether Acetate, diethylene glycol monobutyl ether acetate, propylene glycol methyl ether, propylene glycol monomethyl ether acetate (PGMEA) and the like are more preferable.

  As content of the solvent in the pigment dispersion composition of this invention, 10-98 mass% is preferable, 30-95 mass% is more preferable, 50-90 mass% is the most preferable. When the content of the solvent is within the above range, the pigment can be dispersed more uniformly, which is advantageous in terms of dispersion stability after dispersion.

  The pigment dispersion composition of the present invention comprises (A) a compound having an unsaturated double bond and a molecular weight of less than 4000, (B) a pigment, and optionally other components such as a dispersant mixed with (C) a solvent. In addition, it is preferably prepared through a mixing and dispersing step of mixing and dispersing using various mixers and dispersers. The mixing and dispersing step preferably comprises kneading and dispersing followed by fine dispersion treatment, but kneading and dispersing can be omitted.

<Curable composition>
The curable composition of the present invention comprises (A) a pigment dispersion composition comprising at least a compound having an unsaturated double bond and a molecular weight of less than 4000, (B) a pigment, and (C) a solvent; and (D). It comprises using a photoinitiator. In addition, the curable composition of the present invention is preferably further composed of (E) a photopolymerizable compound, and can be composed of other components as necessary.

  In the curable composition of the present invention, the pigment is efficiently dispersed as described above by containing the specific compound in the present invention, and good storage stability can be obtained regardless of the amount of the pigment. The diffusion of pigment into the liquid and coating liquid can be suppressed, color loss is prevented, the unsaturated bond density is high, the amount of double bonds in the film when it is formed, and the exposure sensitivity is greatly increased. On the contrary, in the uncured unexposed area, the penetration of the developer becomes good and the development removability can be improved. Thereby, it is considered that a good pattern giving a desired cross-sectional shape (in particular, a taper type or a rectangle) is obtained, and the support adhesion is improved.

  Among the components constituting the curable composition of the present invention, (A) a compound having an unsaturated double bond and a molecular weight of less than 4000, (B) a pigment, and (C) a solvent, the details are as described above. This is the same as in the dispersion composition, and the preferred embodiment is also the same.

The content of the compound (A) having a unsaturated double bond in the curable composition having a molecular weight of less than 4000 is preferably 1 to 300% by mass, more preferably 3 to 100% by mass with respect to the pigment. 5 to 50% by mass is more preferable. When the content is within the above range, the pigment can be dispersed more efficiently, effectively preventing color loss, exposure sensitivity, support adhesion, and pattern formability (desired taper type or rectangular cross section formability). Can be improved.
As content in the curable composition of a pigment, 20 mass% or more is preferable with respect to the total solid of a composition, More preferably, it is 30-95 mass%, Most preferably, it is 40-90 mass%. is there. When the content of the pigment is within the above range, it is effective for securing a high coloring power, for example, when producing a color filter.
The proportion of the solvent in the curable composition is preferably 20 to 90% by mass, more preferably 30 to 85% by mass, and most preferably 40 to 80% by mass. When the amount of the solvent is within the above range, it is advantageous from the viewpoints of coating properties and storage stability.

  Hereinafter, each component other than (A) to (C) which is a constituent component of the curable composition of the present invention will be specifically described.

(D) Photopolymerization initiator The curable composition of the present invention contains at least one photopolymerization initiator. The photopolymerization initiator is a compound that is decomposed by light and initiates and accelerates polymerization of (A) a compound having an unsaturated double bond in the present invention having a molecular weight of less than 4000 and (E) a photopolymerizable compound described later. In addition, it is preferable to have absorption in a wavelength region of 300 to 500 nm.
Moreover, a photoinitiator may be used individually by 1 type and can also use 2 or more types together.

Examples of the photopolymerization initiator include organic halogenated compounds, oxydiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxide compounds, azo compounds, coumarin compounds, azide compounds, metallocene compounds, hexaaryes. Examples thereof include a rubiimidazole compound, an organic borate compound, a disulfone compound, an oxime compound, an onium salt compound, an acylphosphine compound, and an alkylamino compound.
Hereinafter, each of these compounds will be described in detail.

  Specific examples of the organic halogenated compound include Wakabayashi et al., “Bull Chem. Soc Japan” 42, 2924 (1969), US Pat. No. 3,905,815, Japanese Patent Publication No. 46-4605, JP 48-36281, JP 55-3070, JP 60-239736, JP 61-169835, JP 61-169837, JP 62-58241, JP 62 -212401, JP-A-63-70243, JP-A-63-298339, M.S. P. Hut "Journal of Heterocyclic Chemistry" 1 (No3), (1970) "The compound described in a brush is mentioned, Especially, the oxazole compound substituted by the trihalomethyl group and s-triazine compound are mentioned.

  As the s-triazine compound, more preferably, an s-triazine derivative in which at least one mono-, di-, or trihalogen-substituted methyl group is bonded to the s-triazine ring, specifically, for example, 2,4,6- Tris (monochloromethyl) -s-triazine, 2,4,6-tris (dichloromethyl) -s-triazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6- Bis (trichloromethyl) -s-triazine, 2-n-propyl-4,6-bis (trichloromethyl) -s-triazine, 2- (α, α, β-trichloroethyl) -4,6-bis (trichloro Methyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloro) Methyl) -s-triazine, 2- (3,4-epoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl)- s-triazine, 2- [1- (p-methoxyphenyl) -2,4-butadienyl] -4,6-bis (trichloromethyl) -s-triazine, 2-styryl-4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (pi-propyloxystyryl) -4,6-bis (trichloromethyl)- s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-natoxynaphthyl) -4,6-bis (trichloromethyl) s-triazine, 2-phenylthio-4,6-bis (trichloromethyl) -s-triazine, 2-benzylthio-4,6-bis (trichloromethyl) -s-triazine, 2,4,6-tris (dibromomethyl) ) -S-triazine, 2,4,6-tris (tribromomethyl) -s-triazine, 2-methyl-4,6-bis (tribromomethyl) -s-triazine, 2-methoxy-4,6- Bis (tribromomethyl) -s-triazine and the like can be mentioned.

  Examples of the oxydiazole compound include 2-trichloromethyl-5-styryl-1,3,4-oxodiazole, 2-trichloromethyl-5- (cyanostyryl) -1,3,4-oxodiazole, 2- And trichloromethyl-5- (naphth-1-yl) -1,3,4-oxodiazole, 2-trichloromethyl-5- (4-styryl) styryl-1,3,4-oxodiazole, and the like. .

  Examples of the carbonyl compound include benzophenone, Michler ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone and other benzophenone derivatives, 2,2-dimethoxy-2 -Phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl- (p-isopropylphenyl) ketone, 1-hydroxy -1- (p-dodecylphenyl) ketone, 2-methyl- (4 ′-(methylthio) phenyl) -2-morpholino-1-propanone, 1,1,1-trichloromethyl- (p-butylphenyl) , Acetophenone derivatives such as 2-benzyl-2-dimethylamino-4-morpholinobutyrophenone, thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone Thioxanthone derivatives such as 2,4-diisopropylthioxanthone, and benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate.

  Examples of the ketal compound include benzyl methyl ketal and benzyl-β-methoxyethyl ethyl acetal.

  Examples of the benzoin compound include m-benzoin isopropyl ether, benzoin isobutyl ether, benzoin methyl ether, and methyl-o-benzoylbenzoate.

  Examples of the acridine compound include 9-phenylacridine, 1,7-bis (9-acridinyl) heptane, and the like.

  Examples of the organic peroxide compound include trimethylcyclohexanone peroxide, acetylacetone peroxide, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (tert-butylperoxy) cyclohexane, 2,2-bis (tert-butylperoxy) butane, tert-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 1,1,3,3 -Tetramethylbutyl hydroperoxide, tert-butylcumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-bis (tert-butylperoxy) hexane, 2,5-oxanoyl Peroxide, succinic peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, dimethoxyisopropyl peroxycarbonate, bis ( 3-methyl-3-methoxybutyl) peroxydicarbonate, tert-butylperoxyacetate, tert-butylperoxypivalate, tert-butylperoxyneodecanoate, tert-butylperoxyoctanoate, tert-butylperoxylaurate , Tersyl carbonate, 3,3 ′, 4,4′-tetrakis (t-butylperoxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetrakis t-hexylperoxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetrakis (p-isopropylcumylperoxycarbonyl) benzophenone, carbonylbis (t-butylperoxydihydrogendiphthalate), carbonylbis (t-hexylperoxy) Dihydrogen diphthalate) and the like.

  Examples of the azo compound include azo compounds described in JP-A-8-108621.

  Examples of the coumarin compound include 3-methyl-5-amino-((s-triazin-2-yl) amino) -3-phenylcoumarin, 3-chloro-5-diethylamino-((s-triazin-2-yl). ) Amino) -3-phenylcoumarin, 3-butyl-5-dimethylamino-((s-triazin-2-yl) amino) -3-phenylcoumarin, and the like.

  Examples of the azide compound include organic azide compounds described in U.S. Pat. No. 2,848,328, U.S. Pat. No. 2,852,379 and U.S. Pat. No. 2,940,553, 2,6-bis (4-azidobenzylidene) -4-ethyl. And cyclohexanone (BAC-E).

  Examples of the metallocene compound include JP-A-59-152396, JP-A-61-151197, JP-A-63-41484, JP-A-2-249, JP-A-2-4705, Various titanocene compounds described in JP-A-5-83588 such as di-cyclopentadienyl-Ti-di-phenyl, di-cyclopentadienyl-Ti-bis-2,6-difluorophen-1-yl, di- -Cyclopentadienyl-Ti-bis-2,4-di-fluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,4,6-trifluorophen-1-yl, di- Cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluoro Phen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,6-difluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,4,6-trifluoropheny -1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4 , 5,6-pentafluorophen-1-yl, iron-arene complexes described in JP-A-1-304453 and JP-A-1-152109, and the like.

  As the hexaarylbiimidazole compound, for example, JP-B-6-29285, US Pat. Nos. 3,479,185, 4,311,783, 4,622,286, etc. And, specifically, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-bromophenyl) )) 4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o, p-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2 ′ -Bis (o-chlorophenyl) -4,4 ', 5,5'-tetrakis (m-methoxyphenyl) biimidazole, 2,2'-bis (o, o'-dichlorophenyl) -4,4', 5 5'-tetraphenyl Imidazole, 2,2′-bis (o-nitrophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-methylphenyl) -4,4 ′, 5 Examples include 5′-tetraphenylbiimidazole, 2,2′-bis (o-trifluorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, and the like.

  Examples of the organic borate compound include JP-A-62-143044, JP-A-62-1050242, JP-A-9-188865, JP-A-9-188686, JP-A-9-188710, JP-A-2000. -131837, Japanese Patent Application Laid-Open No. 2002-107916, Japanese Patent No. 2764769, Japanese Patent Application No. 2000-310808, etc., and Kunz, Martin “Rad Tech '98. Proceeding April 19-22, 1998, Chicago”. Organoboron salts described in JP-A-6-157623, JP-A-6-175564, JP-A-6-175561, JP-A-6-175554 In Japanese Patent Laid-Open No. 6-175553 Organoboron iodonium complexes, organoboron phosphonium complexes described in JP-A-9-188710, JP-A-6-348011, JP-A-7-128785, JP-A-7-140589, JP-A-7- Specific examples include organoboron transition metal coordination complexes such as those described in Japanese Patent No. 306527 and Japanese Patent Laid-Open No. 7-292014.

  Examples of the disulfone compound include compounds described in JP-A No. 61-166544 and Japanese Patent Application No. 2001-132318.

  Examples of oxime compounds include J.M. C. S. Perkin II (1979) 1653-1660), J. MoI. C. S. Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, JP-A 2000-66385, compounds described in JP-A 2000-80068, JP-T 2004-534797 Compounds and the like.

  Examples of onium salt compounds include S.I. I. Schlesinger, Photogr. Sci. Eng. , 18, 387 (1974), T.A. S. Bal et al, Polymer, 21, 423 (1980), diazonium salts described in U.S. Pat. No. 4,069,055, ammonium salts described in JP-A-4-365049, U.S. Pat. No. 4,069, No. 055, No. 4,069,056, phosphonium salts described in European Patent Nos. 104 and 143, U.S. Pat. Nos. 339,049 and 410,201, JP Examples include iodonium salts described in JP-A No. -150848 and JP-A-2-296514.

  The iodonium salt that can be suitably used in the present invention is a diaryl iodonium salt, and from the viewpoint of stability, it may be substituted with two or more electron donating groups such as an alkyl group, an alkoxy group, and an aryloxy group. preferable. In addition, as another preferable form of the sulfonium salt, an iodonium salt in which one substituent of the triarylsulfonium salt has a coumarin or an anthraquinone structure and absorption at 300 nm or more is preferable.

Examples of the sulfonium salt that can be suitably used in the present invention include European Patent Nos. 370,693, 390,214, 233,567, 297,443, 297,442, and U.S. Pat. 933,377, 161,811, 410,201, 339,049, 4,760,013, 4,734,444, 2,833,827, Germany Examples thereof include sulfonium salts described in the specifications of Patent Nos. 2,904,626, 3,604,580, and 3,604,581, and are preferably electron withdrawing groups from the viewpoint of stability. It is preferably substituted. The electron withdrawing group preferably has a Hammett value greater than zero. Preferred electron-withdrawing groups include halogen atoms and carboxylic acids.
Other preferable sulfonium salts include sulfonium salts in which one substituent of the triarylsulfonium salt has a coumarin or anthraquinone structure and absorbs at 300 nm or more. As another preferable sulfonium salt, a sulfonium salt having a triarylsulfonium salt having an aryloxy group or an arylthio group as a substituent and having absorption at 300 nm or more can be mentioned.

  Moreover, as an onium salt compound, J.M. V. Crivello et al, Macromolecules, 10 (6), 1307 (1977), J. MoI. V. Crivello et al, J.A. Polymer Sci. , Polymer Chem. Ed. , 17, 1047 (1979), a selenonium salt described in C.I. S. Wen et al, Teh, Proc. Conf. Rad. An onium salt such as an arsonium salt described in Curing ASIA, p478 Tokyo, Oct (1988) can also be used.

  Examples of the acylphosphine compound include Irgacure 819, Darocur 4265, and Darocur TPO manufactured by Ciba Specialty Chemicals.

Examples of the alkylamino compound include compounds having a dialkylaminophenyl group described in paragraph No. [0047] of JP-A-9-281698, JP-A-6-19240, JP-A-6-19249, and the like. An amine compound is mentioned. Specifically, compounds having a dialkylaminophenyl group include compounds such as ethyl p-dimethylaminobenzoate, and dialkylaminophenyl carbaldehydes such as p-diethylaminobenzcarbaldehyde and 9-julolidylcarbaldehyde. Examples of the amine compound include triethanolamine, diethanolamine, and triethylamine.

  As the photopolymerization initiator (D) used in the present invention, from the viewpoint of exposure sensitivity, a triazine compound, an alkylamino compound, a benzyldimethyl ketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound, Phosphine oxide compounds, metallocene compounds, oxime compounds, biimidazole compounds, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyl Preference is given to at least one compound selected from the group consisting of oxadiazole compounds and 3-aryl-substituted coumarin compounds.

  More preferably, they are triazine compounds, alkylamino compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, oxime compounds, biimidazole compounds, onium compounds, benzophenone compounds, acetophenone compounds, More preferred is at least one compound selected from the group consisting of triazine compounds, alkylamino compounds, oxime compounds, and biimidazole compounds.

  The content of the (D) photopolymerization initiator in the curable composition is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, based on the total solid content of the composition. %, Particularly preferably 1 to 20% by mass. In particular, when the curable composition of the present invention is used for forming a colored pattern of a color filter, the content of the (D) photopolymerization initiator is cured in terms of photosensitivity, support adhesion, and degree of cure. 1-40 mass% is preferable with respect to the total solid content contained in an adhesive composition, 2-30 mass% is more preferable, and 3-20 mass% is still more preferable.

(E) Photopolymerizable compound It is preferable that the curable composition of this invention contains the compound which has an ethylenically unsaturated double bond as a photopolymerizable compound.
The “compound having an ethylenically unsaturated double bond” that can be used in the present invention is an addition polymerizable compound having at least one ethylenically unsaturated double bond, and has at least one terminal ethylenically unsaturated bond. , Preferably selected from compounds having two or more. Such compound groups are widely known in the industrial field, and these can be used without any particular limitation in the present invention. Details of these compounds are the same as those of the compound (A) having an unsaturated double bond and having a molecular weight of less than 4000, except that the molecular weight is not limited, and preferred embodiments are also the same.
Moreover, the photopolymerizable compound in the present invention may be the same as or different from the compound (A) having an unsaturated double bond and having a molecular weight of less than 4000. Furthermore, the photopolymerizable compound in this invention can be used individually by 1 type and in combination of 2 or more types.

  The content of the photopolymerizable compound (E) is preferably 1 to 90% by mass and more preferably 5 to 80% by mass with respect to the total solid content of the curable composition of the present invention. More preferably, it is 10% to 70% by mass. In particular, when the curable composition of the present invention is used to form a colored pattern of a color filter, the content of (E) the photopolymerizable compound is further improved in terms of photosensitivity, support adhesion, and degree of cure. Is preferably 5 to 50% by mass, more preferably 7 to 40% by mass, and further preferably 10 to 35% by mass, based on the total solid content of the curable composition of the present invention. preferable.

  Further, (A) a compound having an unsaturated double bond and a molecular weight of less than 4000 (a specific compound in the present invention) and (A) a photopolymerizable compound other than the specific compound in the present invention (E) are used in combination. In this case, the content ratio [(A) / (E); mass ratio] is preferably 100/1 to 1/100, more preferably 50/1 to 1/50, from the viewpoint of sensitivity and storage stability. 10/1 to 1/10 is more preferable.

Next, other components that can be further used in the curable composition of the present invention will be described.
(F) Sensitizer The curable composition of the present invention contains (F) a sensitizer for the purpose of (D) improving the radical generation efficiency by the photopolymerization initiator and increasing the photosensitive wavelength. Also good. As the sensitizer that can be used in the present invention, a sensitizer that is sensitized by an electron transfer mechanism or an energy transfer mechanism to the above-described (D) photopolymerization initiator is preferable.

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.
Further, European Patent No. 568,993, US Patent No. 4,508,811, No. 5,227,227, Japanese Patent Application Laid-Open No. 2001-125255, Japanese Patent Application Laid-Open No. 11-271969, etc. And the like.

  More preferable examples of the sensitizer include compounds represented by the following general formulas (i) to (iv).

In general formula (i), A ¹ represents a sulfur atom or NR ⁵⁰ , R ⁵⁰ represents an alkyl group or an aryl group, and L ² represents the basic nucleus of the dye in combination with adjacent A ¹ and the adjacent carbon atom. Represents a non-metallic atomic group to be formed, R ⁵¹ and R ⁵² each independently represent a hydrogen atom or a monovalent non-metallic atomic group, and R ⁵¹ and R ⁵² are bonded to each other to form an acidic nucleus of the dye. Also good. W represents an oxygen atom or a sulfur atom.

In General Formula (ii), Ar ¹ and Ar ² each independently represent an aryl group, and are linked via a bond with —L ³ —. Here, L ³ represents —O— or —S—. W is synonymous with that shown in the general formula (i).

In general formula (iii), A ² represents a sulfur atom or NR ⁵⁹ , L ⁴ represents a nonmetallic atomic group that forms a basic nucleus of a dye in combination with adjacent A ² and a carbon atom, R ⁵³ , R ⁵⁴ , R ⁵⁵ , R ⁵⁶ , R ⁵⁷ and R ⁵⁸ each independently represent a monovalent nonmetallic atomic group, and R ⁵⁹ represents an alkyl group or an aryl group.

In general formula (iv), A ³ and A ⁴ each independently represent —S— or —NR ⁶² — or —NR ⁶³ —, wherein R ⁶² and R ⁶³ each independently represent a substituted or unsubstituted alkyl group, substituted Or an unsubstituted aryl group, and L ⁵ and L ⁶ each independently represent a nonmetallic atomic group that forms a basic nucleus of a dye together with adjacent A ³ , A ⁴ and an adjacent carbon atom; ⁶⁰ and R ⁶¹ are each independently a monovalent non-metallic atomic group, or may be bonded to each other to form an aliphatic or aromatic ring.

  Moreover, as a preferable sensitizer which can be contained in the curable composition of this invention, at least 1 type selected from the compound represented by the following general formula (IV)-(VI) other than the above thing is mentioned.

In general formula (IV) or general formula (V), R ¹ and R ² each independently represent a monovalent substituent, and R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or Represents a monovalent substituent. n represents an integer of 0 to 5, n ′ represents an integer of 0 to 5, and n and n ′ are not both 0. When n is 2 or more, a plurality of R ¹ may be the same or different. When n ′ is 2 or more, a plurality of R ² may be the same or different.

  As a compound represented by general formula (IV), it is preferable that it is a compound represented by the following general formula (IV-1) from a viewpoint of the colorability in the case of containing a sensitivity and a pigment.

In general formula (IV-1), R ¹ and R ² each independently represents a monovalent substituent. n represents an integer of 0 to 5, and n ′ represents an integer of 1 to 5. When n is 2 or more, a plurality of R ¹ may be the same or different, and when n ′ is 2 or more, a plurality of R ² are the same or different. Also good.

In the general formula (IV-1), the monovalent substituent represented by ^{R 1} and ^{R 2} are synonymous with the monovalent substituent represented by ^{R 1} and ^{R 2} in the general formula (IV) The preferable range is also the same.

The general formula (IV) or general formula (V) compounds represented by is preferably a molar extinction coefficient epsilon at a wavelength of 365nm is ^{500mol -1} · L · ^cm -1 or more, epsilon at a wavelength of 365nm is 3000 mol ^- more preferably ¹ · L · ^{cm -1} or more, and most preferably ε at a wavelength of 365nm is 20000mol ^-1 · L · ^{cm -1} or more. It is preferable that the value of the molar extinction coefficient ε at each wavelength is in the above range because the sensitivity improvement effect is high from the viewpoint of light absorption efficiency.
Here, the molar extinction coefficient ε is determined by measuring a transmission spectrum of a sample at 365 nm using a dye solution adjusted to a concentration of 0.01 g / l in a 1-methoxy-2-propanol solution, and UV-visible absorption of the sample. It is obtained by determining the absorbance from the spectrum. The measurement apparatus used was a Varian UV-Vis-MR Spectrophotometer Cary 5G spectrophotometer.

Although the preferable specific example of a compound represented by general formula (IV) or general formula (V) is illustrated below, this invention is not limited to these.
Note that in this specification, a chemical formula may be described by a simplified structural formula, and a solid line or the like that does not clearly indicate an element or a substituent particularly represents a hydrocarbon group. In the following specific examples, Me represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, n-Bu represents an n-butyl group, and Ph represents a phenyl group.

In general formula (VI), A represents an aromatic ring or a hetero ring which may have a substituent, X represents an oxygen atom, a sulfur atom, or —N (R ³ ) —, Y represents an oxygen atom, A sulfur atom or -N (R < ³ >)-is represented. R ¹ , R ² , and R ³ each independently represent a hydrogen atom or a monovalent nonmetallic atomic group, and A, R ¹ , R ² , and R ³ are each bonded to each other to form an aliphatic group Or you may form an aromatic ring.

In the general formula (VI), R ¹ , R ² and R ³ each independently represents a hydrogen atom or a monovalent nonmetallic atomic group. When R ¹ , R ² and R ³ represent a monovalent nonmetal atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aromatic group It is preferably a heterocyclic residue, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group, a hydroxy group, or a halogen atom.

In the compound represented by the general formula (VI), Y is preferably an oxygen atom or —N (R ³ ) — from the viewpoint of improving the decomposition efficiency of the photopolymerization initiator. R ³ each independently represents a hydrogen atom or a monovalent nonmetallic atomic group. Furthermore, Y is most preferably —N (R ³ ) —.

  Hereinafter, preferred specific examples (VI1) to (VI124) of the compound represented by the general formula (VI) are shown, but the present invention is not limited thereto. Further, it is not clear about an isomer by a double bond connecting an acidic nucleus and a basic nucleus, and the present invention is not limited to either isomer.

With respect to the sensitizing dye in the present invention, various chemical modifications for improving the properties of the curable composition can be further performed.
For example, sensitizing dye and addition polymerizable compound structure (for example, acryloyl group or methacryloyl group) are bonded by a method such as covalent bond, ionic bond, hydrogen bond, etc. Unnecessary precipitation suppression of the sensitizing dye from the later film can be performed.
In addition, partial structures having radical generating ability in the sensitizing dye and the above-described photopolymerization initiator (for example, reductive decomposable sites such as alkyl halide, onium, peroxide, biimidazole, borate, amine, trimethylsilylmethyl) , An oxidatively cleavable site such as carboxymethyl, carbonyl, imine, etc.), the photosensitivity can be remarkably enhanced particularly in a state where the concentration of the starting system is low.

  The compounds represented by the above general formulas (IV) to (VI) have a very high pigment concentration in the curable composition, and the light transmittance of the formed colored pattern (photosensitive layer) becomes extremely low. In this case, for example, when the curable composition of the present invention is used for forming a coloring pattern of a color filter, more specifically, 365 nm light can be transmitted through the photosensitive layer when formed without adding a sensitizing dye. By adding in a case where the rate is 10% or less, the effect is remarkably exhibited. In particular, among the above general formulas (IV) to (VI), the compound represented by the general formula (VI) is most preferable, and specifically, the compounds of (VI56) to (VI122) are most preferable.

A sensitizer may be used individually by 1 type and may use 2 or more types together.
The content of the (F) sensitizer in the curable composition of the present invention is curable from the viewpoint of light absorption efficiency to the deep part and starting decomposition efficiency, including the case where it is used for forming a color filter color pattern. It is preferable that it is 0.1-20 mass% with respect to the total solid of a composition, and 0.5-15 mass% is more preferable.

(G) Binder polymer The curable composition of the present invention may contain (G) a binder polymer for the purpose of improving film properties.
It is preferable to use a linear organic polymer as the binder polymer. As such a “linear organic polymer”, a known one can be arbitrarily used. For example, when the curable composition of the present invention is applied to an application in which a pattern is formed by removing an unexposed portion by water or alkali development after pattern exposure and curing of an exposed portion, preferably water development or weakness is used. In order to enable alkaline water development, a linear organic polymer that is soluble or swellable in water or weak alkaline water is selected. The linear organic polymer is selected and used not only as a film forming agent but also according to the type of water, weak alkaline water, or organic solvent developer. For example, when a water-soluble organic polymer is used, water development becomes possible. Examples of such linear organic polymers include radical polymers having a carboxylic acid group in the side chain, such as JP 59-44615, JP-B 54-34327, JP-B 58-12577, JP-B 54-. No. 25957, JP-A-54-92723, JP-A-59-53836, and JP-A-59-71048. That is, a resin in which a monomer having a carboxy group is singly or copolymerized, a monomer having an acid anhydride is singly or copolymerized, and an acid anhydride unit is hydrolyzed, half-esterified or half-amidated, epoxy Examples thereof include epoxy acrylate obtained by modifying a resin with an unsaturated monocarboxylic acid and an acid anhydride. Examples of the monomer having a carboxy group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, and 4-carboxystyrene. Examples of the monomer having an acid anhydride include maleic anhydride. It is done.
Similarly, an acidic cellulose derivative having a carboxylic acid group in the side chain can also be used. In addition, those obtained by adding a cyclic acid anhydride to a polymer having a hydroxyl group are useful.

  As described above, when the radical polymer having a carboxylic acid group in the side chain is a copolymer, a monomer other than the above-mentioned monomers can also be used as the compound to be copolymerized. Examples of other monomers include the following compounds (1) to (12).

(1) 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate Acrylic esters having an aliphatic hydroxyl group such as methacrylic esters.
(2) Methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, benzyl acrylate, acrylic acid-2- Alkyl acrylates such as chloroethyl, glycidyl acrylate, 3,4-epoxycyclohexylmethyl acrylate, vinyl acrylate, 2-phenylvinyl acrylate, 1-propenyl acrylate, allyl acrylate, 2-allyloxyethyl acrylate, propargyl acrylate;

(3) Methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, amyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, methacrylic acid-2- Alkyl methacrylates such as chloroethyl, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, vinyl methacrylate, 2-phenylvinyl methacrylate, 1-propenyl methacrylate, allyl methacrylate, 2-allyloxyethyl methacrylate, and propargyl methacrylate;
(4) Acrylamide, methacrylamide, N-methylolacrylamide, N-ethylacrylamide, N-hexylmethacrylamide, N-cyclohexylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N-nitrophenylacrylamide, N-ethyl- Acrylamides or methacrylamides such as N-phenylacrylamide, vinylacrylamide, vinylmethacrylamide, N, N-diallylacrylamide, N, N-diallylmethacrylamide, allylacrylamide, allylmethacrylamide.

(5) Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, and phenyl vinyl ether.
(6) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate and vinyl benzoate.
(7) Styrenes such as styrene, α-methylstyrene, methylstyrene, chloromethylstyrene, and p-acetoxystyrene.
(8) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.
(9) Olefins such as ethylene, propylene, isobutylene, butadiene, and isoprene.

(10) N-vinylpyrrolidone, acrylonitrile, methacrylonitrile and the like.
(11) Unsaturated imides such as maleimide, N-acryloylacrylamide, N-acetylmethacrylamide, N-propionylmethacrylamide, N- (p-chlorobenzoyl) methacrylamide.
(12) A methacrylic acid monomer having a hetero atom bonded to the α-position. For example, compounds described in Japanese Patent Application No. 2001-115595, Japanese Patent Application No. 2001-115598, and the like can be mentioned.

  Among these, (meth) acrylic resins having an allyl group, a vinyl ester group and a carboxyl group in the side chain, and two side chains described in JP-A Nos. 2000-187322 and 2002-62698 are included. An alkali-soluble resin having a heavy bond and an alkali-soluble resin having an amide group in the side chain described in JP-A No. 2001-242612 are preferable because of excellent balance of film strength, sensitivity and developability.

In addition, Japanese Patent Publication No. 7-2004, Japanese Patent Publication No. 7-120041, Japanese Patent Publication No. 7-120042, Japanese Patent Publication No. 8-12424, Japanese Patent Laid-Open No. 63-287944, Japanese Patent Laid-Open No. 63-287947, Japanese Patent Laid-Open No. No. 271741 and Japanese Patent Application No. 10-116232 and other urethane-based binder polymers containing acid groups described in JP-A-2002-107918 and urethanes having acid groups and double bonds in side chains Since the binder polymer is very excellent in strength, it is advantageous in terms of suitability for low exposure.
Further, the acetal-modified polyvinyl alcohol-based binder polymer having an acid group described in European Patent No. 993966, European Patent No. 1204000, Japanese Patent Application Laid-Open No. 2001-318463, etc. has an excellent balance of film strength and developability. Is preferred.
In addition, polyvinyl pyrrolidone, polyethylene oxide, and the like are useful as the water-soluble linear organic polymer. In order to increase the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are also useful.

The mass average molecular weight of the (G) binder polymer is preferably 5,000 or more, more preferably 10,000 to 300,000, and the number average molecular weight is preferably 1,000 or more. Preferably it is the range of 2,000-250,000. The polydispersity (mass average molecular weight / number average molecular weight) is preferably 1 or more, more preferably in the range of 1.1-10.
These resins may be any of random polymers, block polymers, graft polymers and the like.

(G) The binder polymer can be synthesized by a conventionally known method. Examples of the solvent used in the synthesis include tetrahydrofuran, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, diethylene glycol dimethyl ether, 1-methoxy. 2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, toluene, ethyl acetate, methyl lactate, ethyl lactate, dimethyl sulfoxide, 1-methyl-2-pyrrolidone, Water etc. are mentioned. These solvents are used alone or in combination of two or more.
Examples of the radical polymerization initiator used in synthesizing the binder polymer that can be used in the present invention include known compounds such as an azo initiator and a peroxide initiator.

  (G) The content of the binder polymer in the curable composition is such that when the curable composition of the present invention is used for forming a color pattern of a color filter, the balance between the pigment dispersion stability over time and the developability. From a viewpoint, it is preferable that it is 5-60 mass% with respect to the total solid of a curable composition, It is more preferable that it is 7-50 mass%, It is most preferable that it is 10-40 mass%.

(H) Dispersant In the curable composition of the present invention, it is preferable to add a dispersant other than the above components from the viewpoint of further improving the dispersibility of the (B) pigment.

Dispersants (pigment dispersants) include polymer dispersants [for example, polyamidoamines and salts thereof, polycarboxylic acids and salts thereof, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, modified poly (meth) acrylates, (Meth) acrylic copolymer, naphthalenesulfonic acid formalin condensate], polyoxyethylene alkyl phosphate ester, polyoxyethylene alkylamine, alkanolamine, and pigment derivatives.
The polymer dispersant can be further classified into a linear polymer, a terminal-modified polymer, a graft polymer, and a block polymer from the structure thereof.

  The polymer dispersant is adsorbed on the surface of the pigment and acts to prevent reaggregation. Therefore, a terminal-modified polymer, a graft polymer and a block polymer having an anchor site to the pigment surface can be mentioned as preferred structures. On the other hand, the pigment derivative has an effect of promoting the adsorption of the polymer dispersant by modifying the pigment surface.

  Specific examples of the pigment dispersant that can be used in the present invention include “Disperbyk-101 (polyamidoamine phosphate), 107 (carboxylic acid ester), 110 (copolymer containing an acid group), 130 (polyamide) manufactured by BYK Chemie. ), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer) ”,“ BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid) ”,“ BYK2001 ”,“ EFKA4047, manufactured by EFKA Corporation ” 4050, 4010, 4165 (polyurethane), EFKA 4330, 4340 (block copolymer), 4400, 4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester) , 6745 (phthalocyanine induction ), 6750 (azo pigment derivative) ”,“ Ajisper PB821, PB822 ”manufactured by Ajinomoto Fan Techno Co.,“ Floren TG-710 (urethane oligomer) ”manufactured by Kyoeisha Chemical Co.,“ Polyflow No. 50E, No. 300 (acrylic co-polymer). Polymer) ”,“ Disparon KS-860, 873SN, 874, # 2150 (aliphatic polycarboxylic acid), # 7004 (polyetherester), DA-703-50, DA-705, DA- 725 ", Kao's" Demol RN, N (Naphthalenesulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate) "," Homogenol L-18 (polymer polycarboxylic acid) Acid) "," Emulgen 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether) ”,“ Acetamine 86 (stearylamine acetate) ”,“ Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine), 3000, 17000, 27000 (functional part at the end) manufactured by Lubrizol 24000, 28000, 32000, 38500 (graft type polymer) "," Nikkor T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate) "manufactured by Nikko Chemical Co., Ltd., etc. Is mentioned.

  These dispersants may be used alone or in combination of two or more. In the present invention, it is particularly preferable to use a combination of a pigment derivative and a polymer dispersant.

As content of (H) dispersing agent in this invention, it is preferable that it is 1-100 mass% with respect to a pigment, 3-100 mass% is more preferable, 5-80 mass% is still more preferable.
Specifically, if a polymer dispersant is used, the amount of use thereof is preferably in the range of 5 to 100% by mass, more preferably in the range of 10 to 80% by mass with respect to the pigment. In the case of using a pigment derivative, the amount used is preferably in the range of 1 to 30% by mass, more preferably in the range of 3 to 20% by mass, based on the pigment, A range of 15% by mass is particularly preferable.

  In the present invention, when a pigment and a dispersant are used, from the viewpoint of curing sensitivity and color density, the total content of the pigment and the dispersant is 35 to 90 with respect to the total solid content constituting the curable composition. It is preferably mass%, more preferably 45 to 85 mass%, and still more preferably 50 to 80 mass%.

(I) Co-sensitizer The curable composition of the present invention preferably contains (I) a co-sensitizer. In the present invention, the co-sensitizer further improves the sensitivity of (F) sensitizer (sensitizing dye) and (D) photopolymerization initiator to active radiation, or suppresses polymerization inhibition of the polymerizable compound by oxygen. Etc.
Examples of such cosensitizers include amines such as M.I. R. Sander et al., “Journal of Polymer Society”, Vol. 10, 3173 (1972), Japanese Patent Publication No. 44-20189, Japanese Patent Publication No. 51-82102, Japanese Patent Publication No. 52-134692, Japanese Patent Publication No. 59-138205. No. 60-84305, JP-A 62-18537, JP-A 64-33104, Research Disclosure 33825, and the like. Specific examples 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 of the co-sensitizer include amino acid compounds (eg, N-phenylglycine), organometallic compounds described in JP-B-48-42965 (eg, tributyltin acetate), JP-B 55- Examples include a hydrogen donor described in Japanese Patent No. 34414, a sulfur compound (eg, trithiane) described in Japanese Patent Laid-Open No. 6-308727, and the like.

  (I) Content of a co-sensitizer is 0.1-30 mass% with respect to the mass of the total solid of a curable composition from a viewpoint of the improvement of the cure rate by the balance of a polymerization growth rate and chain transfer. The range is preferable, the range of 0.5 to 25% by mass is more preferable, and the range of 1.0 to 20% by mass is further preferable.

(J) Polymerization inhibitor In the present invention, during the production or storage of the curable composition, (A) a compound having an unsaturated double bond having a molecular weight of less than 4000 or (E) a photopolymerizable compound In order to prevent unnecessary thermal polymerization of a compound having an ethylenically unsaturated double bond in the molecule, it is desirable to add a small amount of a thermal polymerization inhibitor as a polymerization inhibitor (J).

  As thermal polymerization inhibitors, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol) 2,2′-methylenebis (4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt and the like.

(J) As for the addition amount of a polymerization inhibitor, about 0.01 to about 5 mass% is preferable with respect to the mass of a curable composition.
Further, if necessary, a higher fatty acid derivative such as behenic acid or behenic acid amide is added to prevent polymerization inhibition by oxygen, and the curable composition of the present invention is dried on the surface until it is dried. It may be unevenly distributed. The amount of the higher fatty acid derivative added is preferably about 0.5 to about 10% by mass relative to the mass of the curable composition.

[Other ingredients]
Furthermore, the curable composition of the present invention includes a filler, a plasticizer, a polymer compound other than those described above, a surfactant, an antioxidant, an ultraviolet absorber, and an aggregation inhibitor for improving the physical properties of the cured film. Etc. can be blended.
More specifically, fillers such as glass and alumina; plastics such as dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerol Agents; polymer compounds such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate; nonionic surfactants, cationic surfactants, anionic surfactants, etc .; 2,2-thiobis (4-methyl-6) -T-butylphenol), 2,6-di-t-butylphenol and other antioxidants: 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxybenzophenone, etc. purple It may be mentioned and aggregation inhibitor such as sodium polyacrylate; linear absorption agent.

Further, when the curable composition of the present invention is applied to the surface of a hard material such as a substrate, an additive for improving the adhesion to the surface of the hard material (hereinafter referred to as “substrate adhesion agent”). May be added.
As the substrate adhesion agent, known materials can be used, and it is particularly preferable to use a silane coupling agent, a titanate coupling agent, or an aluminum coupling agent.
Examples of the silane coupling agent include γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxy. Silane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyl Triethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane / hydrochloride, γ-glycidoxypro Pyrtrimethoxysilane, γ-glycidoxypropyltriethoxysilane, aminosilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, vinyltriacetoxysilane, γ- Chloropropyltrimethoxysilane, hexamethyldisilazane, γ-anilinopropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, octadecyldimethyl [3- (trimethoxysilyl) propyl ] Ammonium chloride, γ-chloropropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethyl Chlorosilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, allyltrimethoxysilane, tetraethoxysilane, bis (trimethoxysilyl) hexane, phenyltrimethoxysilane, N- (3-acryloxy-2-hydroxypropyl) ) -3-Aminopropyltriethoxysilane, N- (3-methacryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, (methacryloxymethyl) methyldiethoxysilane, (acryloxymethyl) methyldimethoxysilane, Etc.
Among them, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltri Ethoxysilane and phenyltrimethoxysilane are preferred, and γ-methacryloxypropyltrimethoxysilane is most preferred.

  Examples of titanate coupling agents include isopropyl triisostearoyl titanate, isopropyl tridecylbenzenesulfonyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis (ditridecyl phosphite). ) Titanate, tetra (2,2-diallyloxymethyl) bis (di-tridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyltrioctanoyl titanate, isopropyldi Methacrylic isostearoyl titanate, isopropyl isostearoyl diacryl titanate, Li isopropyl tri (dioctyl phosphate) titanate, isopropyl tricumylphenyl titanate, isopropyl tri (N- amidoethyl-aminoethyl) titanate, dicumyl phenyloxy acetate titanate, diisostearoyl ethylene titanate.

  Examples of the aluminum coupling agent include acetoalkoxyaluminum diisopropylate.

  The content of the substrate adhesion agent is 0.1 to 30% by mass with respect to the total solid content of the curable composition of the present invention, from the viewpoint of leaving no residue in the uncured region of the curable composition. Preferably, it is 0.5 to 20% by mass, more preferably 1 to 10% by mass.

In addition, when the curable composition of the present invention is applied to a use in which a pattern is formed by removing an unexposed portion with water or alkali development after pattern exposure and curing of an exposed portion, the alkali solubility is promoted and developed. In order to further improve the property, an organic carboxylic acid, preferably a low molecular weight organic carboxylic acid having a molecular weight of 1000 or less can be added to the curable composition.
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, cinnamylidene acetic acid, coumaric acid, other carboxylic acids such as umbellic acid.

The curable composition of the present invention comprises (A) a compound having an unsaturated double bond and a molecular weight of less than 4000, (B) a pigment, and, if necessary, (H) another component such as a dispersant (C). It is preferably prepared through a mixing and dispersing step of mixing with a solvent and mixing and dispersing using various mixers and dispersers. That is, the curable composition of the present invention is prepared by preparing a pigment dispersion (the pigment dispersion composition of the present invention) in advance by performing a mixing and dispersing step and mixing the pigment dispersion and the remaining components. Is preferably prepared.
The mixing and dispersing step preferably comprises kneading and dispersing followed by fine dispersion treatment, but kneading and dispersing can be omitted.

<Color filter and manufacturing method thereof>
Next, the color filter of the present invention and the manufacturing method thereof will be described.
The color filter of the present invention is characterized by having a colored pattern formed using the curable composition of the present invention on a support.
Hereinafter, the color filter of the present invention will be described in detail through its manufacturing method (color filter manufacturing method of the present invention).

The method for producing a color filter of the present invention comprises a colored layer forming step of forming a colored layer comprising the curable composition by applying the curable composition of the present invention on a support, and using the colored layer as a mask. And a development step of developing the colored layer after exposure to form a colored pattern.
Hereafter, each process in the manufacturing method of this invention is demonstrated.

[Colored layer forming step]
In the colored layer forming step, the curable composition of the present invention is applied on the support to form a colored layer comprising the curable composition.

Examples of the support that can be used in this step include soda glass, borosilicate glass, and quartz glass used for liquid crystal display elements and the like, and those obtained by attaching a transparent conductive film thereto, and photoelectric conversion elements used for imaging elements and the like. Examples of the substrate include a silicon substrate and a complementary metal oxide semiconductor (CMOS). These substrates may have black stripes that separate pixels.
In addition, an undercoat layer may be provided on these supports, if necessary, in order to improve adhesion with the colored layer, prevent diffusion of substances, or flatten the surface.

As a coating method of the curable composition of the present invention on the support, various coating methods such as slit coating, ink jet method, spin coating, cast coating, roll coating, screen printing method and the like can be applied.
The film thickness immediately after application of the curable composition is preferably 0.1 to 10 μm, more preferably 0.2 to 5 μm, from the viewpoint of film thickness uniformity of the coating film and ease of drying of the coating solvent. 0.2-3 micrometers is still more preferable.

  The colored layer (curable composition layer) coated on the support can be dried (prebaked) at a temperature of 50 ° C. to 140 ° C. for 10 to 300 seconds using a hot plate, oven, or the like.

The coating film thickness after drying of the curable composition (hereinafter referred to as “dry film thickness” as appropriate) can be used for LCD color filters and can be used for LCD thinning, from the viewpoint of securing color density. 0.1 μm or more and less than 2.0 μm is preferable, 0.2 μm or more and 1.8 μm or less is more preferable, and 0.3 μm or more and 1.75 μm or less is particularly preferable.
In addition, in order to use as an IS color filter, in view of securing color density, light in an oblique direction does not reach the light receiving part, and a difference in light collection rate between the end and the center of the device becomes remarkable. From the viewpoint of reducing defects, it is preferably 0.05 μm or more and less than 1.0 μm, more preferably 0.1 μm or more and 0.8 μm or less, and particularly preferably 0.2 μm or more and 0.7 μm or less.

[Exposure process]
In the exposure step, the colored layer (curable composition layer) formed in the colored layer forming step is exposed in a pattern manner through a mask having a predetermined mask pattern.
As radiation that can be used for exposure, ultraviolet rays such as g-line and i-line are particularly preferably used. Irradiation dose is preferably 5~1500mJ / cm ^2, more preferably 10~1000mJ / cm ^2, and most preferably 10 to 500 mJ / cm ^2.
If the color filter of the present invention is a liquid crystal display device, it is more preferably preferably 10~150mJ / cm ² 5~200mJ / cm ² within the above range, and most preferably 10 to 100 mJ / cm ^2. Further, when the color filter of the present invention is for a solid-state imaging device, more preferably 30~1500mJ / cm ² is preferably 50~1000mJ / cm ² within the above range, and most preferably 80~500mJ / cm ^2.

[Development process]
Next, by performing an alkali development process (development process), the unexposed part in the exposure process is eluted in the developer, and only the photocured part remains.
The development temperature is usually 20 ° C. to 30 ° C., and the development time is 20 to 90 seconds.

Examples of the alkali agent used in the developer include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5.4. Organic alkaline compounds such as 0] -7-undecene, inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, etc., and the concentration of these alkaline agents is 0.001% by mass to An alkaline aqueous solution diluted with pure water so as to be 10% by mass, preferably 0.01% by mass to 1% by mass, is preferably used as the developer. In the case where a developer composed of such an alkaline aqueous solution is used, it is generally washed (rinsed) with pure water after development.
Next, excess developer is washed away and dried.

  In addition, in the manufacturing method of this invention, after performing the colored layer formation process, exposure process, and image development process which were mentioned above, the formed colored pattern is hardened by heating (post-baking) and / or exposure as needed. A curing step may be included.

The post-baking is a heat treatment after development for complete curing, and usually a heat curing treatment at 100 ° C. to 240 ° C. is performed. When the substrate is a glass substrate or a silicon substrate, 200 ° C. to 240 ° C. is preferable in the above temperature range.
This post-bake treatment can be carried out continuously or batchwise using heating means such as a hot plate, a convection oven (hot air circulation dryer), a high-frequency heater or the like so as to satisfy the above conditions.

  By repeating the colored layer forming step, the exposing step, and the developing step (and the curing step if necessary) as described above for the desired number of hues (3 colors or 4 colors), a color filter having a desired hue is produced. The

  As described above, the application of the curable composition of the present invention has been described mainly with respect to the application to the pixels of the color filter, but it goes without saying that it can also be applied to the black matrix provided between the pixels of the color filter. . The black matrix is subjected to pattern exposure and alkali development in the same manner as in the above pixel production method except that a black pigment such as carbon black or titanium black is added to the curable composition of the present invention as a colorant. Further, after that, post-baking can be performed to promote the curing of the film.

Since the color filter of the present invention uses the curable composition of the present invention, the formed colored pattern has high adhesion to the support, and the uncured region is easily removed by the developer. Therefore, it has good adhesion to the support and has a high-resolution colored pattern having a desired cross-sectional shape (particularly a taper type or rectangular shape). Therefore, it can be suitably used for a solid-state imaging device such as a liquid crystal display device or a CCD, and is particularly suitable for a high-resolution CCD device or CMOS that exceeds 1 million pixels.
The color filter of the present invention can be used as, for example, a color filter disposed between a light receiving portion of each pixel constituting a CCD and a microlens for condensing light.

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

(Synthesis Example 1)
-Synthesis of Compound (I)-
100 g of 1-methyl-2-pyrrolidone was placed in a 1000 ml three-necked flask and heated to 90 ° C. under a nitrogen stream. A solution prepared by dissolving 84 g of the following compound (i-1), benzyl methacrylate 33 g, methacrylic acid 23 g, and V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) 15 g in 1-methyl-2-pyrrolidone 100 g was added over 2 hours. It was dripped. After completion of dropping, the mixture was further stirred for 2 hours. The reaction solution was cooled to room temperature, and then poured into 7 L of water to precipitate a solid. The precipitated solid was collected by filtration, washed with water, and dried to obtain 131 g of a solid. It was 3230 as a result of measuring a mass mean molecular weight by the gel permeation chromatography method (GPC) which used the obtained compound as the standard substance for polystyrene. Further, when the acid value was determined by titration, it was 69.7 mgKOH / g (calculated value 67.3 mgKOH / g), and it was confirmed that the polymerization was normally performed.
In addition, the following compound (i-1) was synthesize | combined according to description of paragraph number [0280] of Unexamined-Japanese-Patent No. 2003-335814.

In a 1000 ml three-necked flask, 131 g of the oligomer compound obtained as described above and 1.0 g of p-methoxyphenol were added, and 580 g of 1-methyl-2-pyrrolidone was further added and dissolved, and then in an ice bath containing ice water. Cooled down. After the temperature of the mixed solution reached 5 ° C. or lower, 150 g of 1,8-diazabicyclo [5.4.0] -7-undecene (DBU) was further added dropwise over 1 hour using a dropping funnel. After completion of dropping, the ice bath was removed and the mixture was further stirred for 8 hours. Concentrated hydrochloric acid was added to the resulting reaction solution to adjust the pH to 7, and then poured into 7 L of water to precipitate a solid (compound (I)). The precipitated solid was collected by filtration, washed with water and dried to obtain 113 g of the intended compound (I). When ¹ H-NMR of the obtained compound (I) was measured, it was confirmed that 100% of the side chain groups derived from the compound (i-1) were converted to ethylene methacrylate groups. The mass average molecular weight measured by gel permeation chromatography (GPC) using polystyrene standard was 2980. Furthermore, when the acid value was calculated | required by titration, it was 84.5 mgKOH / g (calculated value 84.2 mgKOH / g).

  In Examples 1 to 8 and Comparative Examples 1 and 2 shown below, an example in which a curable composition containing a pigment dispersion is prepared will be described for forming a color filter for a liquid crystal display element.

(Example 1)
-A1. Preparation of curable composition
[A1-1. Preparation of pigment dispersion]
C. I. Pigment Green 36 and C.I. I. 50 parts of a 40/60 (mass ratio) mixture with Pigment Yellow 150 (primary average particle size 32 nm; (B) pigment), BYK2001 (Disperbyk: manufactured by BYK) (solid content concentration 45.1%; dispersant) 60 parts (approximately 27.0 parts in terms of solid content), 3.0 parts of dipentaerythritol hexaacrylate (DPHA; (A) a compound having an unsaturated double bond and a molecular weight of less than 4000), and propylene glycol monomethyl ether (( C) Solvent) A mixed solution in which 103.5 parts were mixed was mixed and dispersed for 15 hours by a bead mill to prepare a pigment dispersion (P1).

[A1-2. Preparation of curable composition (coating liquid)]
Using the pigment dispersion P1 obtained as described above, stirring and mixing were performed to obtain the following composition to prepare a solution of the curable composition.
<Composition>
-200 parts of the above pigment dispersion (P1)-2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole ((D) photopolymerization started Agent) 4 parts ・ Dipentaerythritol hexaacrylate ((E) photopolymerizable compound) 5 parts ・ Propylene glycol monomethyl ether acetate 250 parts (PGMEA; solvent)
・ 3-Methacryloxypropyltrimethoxysilane (substrate adhesion agent) 0.5 part ・ The following compound α ((F) sensitizer) 2.5 parts ・ 2-mercaptobenzimidazole ((I) co-sensitizer) 3 Part

-A2. Color filter production
[A2-1. Formation of curable composition layer (colored layer)]
The curable composition prepared using the pigment dispersion prepared as described above was applied as a resist solution to a 550 mm × 650 mm glass substrate by slitting under the following conditions, and then allowed to stand for 10 minutes and vacuum dried. And prebaking (prebaking; 100 ° C., 80 seconds) to form a curable composition layer (colored layer).

* Slit application conditions ・ Gap of the opening at the tip of the application head: 50 μm
・ Application speed: 100 mm / second ・ Clearance between substrate and application head: 150 μm
-Dry film thickness: 1.75 μm
・ Application temperature: 23 ℃

[A2-2. Exposure and development]
Thereafter, the colored layer is exposed in a pattern using a 2.5 kW ultrahigh pressure mercury lamp using a test photomask having a line width of 20 μm. After exposure, the entire surface of the colored layer is exposed to an organic developer (trade name: CD). The film was covered with a 10% aqueous solution of FUJIFILM Electronics Materials Co., Ltd., and rested for 60 seconds for development.

[A2-3. Heat treatment]
After standing still, pure water was sprayed in the form of a shower to wash away the developer, and the colored layer that had been subjected to photocuring (exposure) and development was heated in an oven at 220 ° C. for 1 hour (post-baking). Thereby, the color filter in which the coloring pattern formed by hardening the curable composition layer on the glass substrate was obtained.

(Examples 2 to 5)
In the preparation of the pigment dispersion of Example 1, except that DPHA (a compound having an unsaturated double bond and a molecular weight of less than 4000) was used, except that each compound having an unsaturated double bond shown in Table 1 was used. A curable composition was prepared in the same manner as in Example 1 to prepare a color filter.

(Comparative Example 1)
A curable composition was prepared in the same manner as in Example 1 except that DPHA was not used in the preparation of the pigment dispersion of Example 1, and a color filter was produced.

(Comparative Example 2)
In preparing the pigment dispersion of Example 1, a curable composition was prepared in the same manner as in Example 1 except that the following compound (III) (compound having an unsaturated double bond) was used instead of DPHA. A color filter was prepared.

-A3. Performance evaluation
Storage stability of the pigment dispersion and curable composition solution (coating solution) prepared above, and exposure sensitivity and substrate adhesion of the curable composition layer formed on the glass substrate using the curable composition The developability and the pattern cross-sectional shape were evaluated as follows. The evaluation results are shown in Table 1 below.

[A3-1. Storage stability of pigment dispersion over time]
After the pigment dispersion prepared above was stored at room temperature for 1 week, the viscosity of the liquid was measured with an E-type viscometer (manufactured by Tokyo Keiki Co., Ltd.) and evaluated according to the following criteria.
-Evaluation criteria-
○: The viscosity increase was less than 5% with respect to the viscosity before storage.
Δ: An increase in viscosity of 5% or more and less than 10% with respect to the viscosity before storage was observed.
X: A viscosity increase of 10% or more with respect to the viscosity before storage was observed.

[A3-2. Fine dispersion of pigment dispersion]
For the pigment dispersion (P1), the average particle diameter of the pigment was measured by a dynamic light scattering method (measured using a Microtrac Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd. without further dilution)). The smaller the average particle diameter of the pigment, the higher the fine dispersibility.
-Evaluation criteria-
○: The average particle size was less than 70 nm Δ: The average particle size was 70 nm or more and less than 150 nm ×: The average particle size was 150 nm or more

[A3-3. Storage stability of curable composition over time]
After the curable composition (coating solution) prepared above was stored at room temperature for 1 month, the viscosity of the solution was measured with an E-type viscometer (manufactured by Tokyo Keiki Co., Ltd.) and evaluated according to the following criteria.
-Evaluation criteria-
○: The viscosity increase was less than 5% with respect to the viscosity before storage.
Δ: An increase in viscosity of 5% or more and less than 10% with respect to the viscosity before storage was observed.
X: A viscosity increase of 10% or more with respect to the viscosity before storage was observed.

[A3-4. Exposure sensitivity of curable composition layer]
The curable composition layer after coating is exposed by changing the exposure amount to various exposure amounts in the range of 10 to 200 mJ / cm ² , and the exposure amount at which the pattern line width after post-baking becomes 20 μm is defined as exposure sensitivity. evaluated. The exposure sensitivity indicates that the smaller the value, the higher the sensitivity.

[A3-5. Developability, pattern cross-sectional shape, support adhesion]
The surface of the support after post-baking and the cross-sectional shape of the pattern at each exposure sensitivity were confirmed by optical microscope and SEM photograph observation, and the developability, pattern cross-sectional shape, and substrate adhesion were evaluated as shown below. Details of the evaluation method and evaluation criteria are as follows.

<Developability>
A2-2. In exposure and development, the presence or absence of a residue in a region not irradiated with light (unexposed portion) was observed, and developability was evaluated according to the following evaluation criteria.
-Evaluation criteria-
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.

<Pattern cross-sectional shape>
The cross-sectional shape of the formed colored pattern was observed and evaluated. The pattern cross-sectional shape is most preferably a forward taper, and a rectangular shape is next preferred. Reverse taper is not preferred.

<Support adhesion>
Evaluation of support adhesion was performed according to the following evaluation criteria by observing whether or not pattern defects occurred.
-Evaluation criteria-
○: No pattern defect was observed.
Δ: Pattern defects were hardly observed, but defects were partially observed.
X: A pattern defect was remarkably observed.

In Table 1, “compound having an unsaturated double bond” is as follows. For compound (I), compound (I) in the synthesis examples described above was used.
MMA: Methyl methacrylate PETMA: Pentaerythritol tetramethacrylate HEA: 2-hydroxyethyl acrylate Compound Si-1: 3-trimethoxysilylpropyl methacrylate

  From the results of Table 1, the curable composition of each example prepared using a pigment dispersion containing a specific compound having an unsaturated double bond and a molecular weight of less than 4000 exhibits storage stability in the solution state. It turns out that it is excellent. In addition, when a colored pattern is formed on a support using this curable composition, for each comparative example not using these specific compounds, the exposure sensitivity is high and the developability is excellent. It can be seen that an excellent color filter is obtained for both support adhesion and pattern cross-sectional shape.

  Next, in Examples 9 to 16 and Comparative Examples 3 to 4 shown below, an example in which a curable composition containing a pigment is prepared for forming a color filter for use in a solid-state imaging device will be described.

Example 9
-B1. Preparation of resist solution
Components of the following composition were mixed and dissolved to prepare a resist solution.
<Composition of resist solution>
Propylene glycol monomethyl ether acetate 19.20 parts (PGMEA: solvent)
・ Ethyl lactate (solvent) 36.67 parts ・ 40% PGMEA solution of benzyl methacrylate / methacrylic acid / methacrylic acid-2-hydroxyethyl copolymer (molar ratio = 60/22/18) 30.51 parts (binder polymer) )
Dipentaerythritol hexaacrylate (DPHA) 12.20 parts (photopolymerizable compound)
・ Polymerization inhibitor (p-methoxyphenol) 0.0061 part ・ Fluorosurfactant 0.83 part (F-475, manufactured by Dainippon Ink & Chemicals, Inc.)
・ TAZ-107 0.586 parts (manufactured by Midori Chemical Co .; trihalomethyltriazine photopolymerization initiator)

-B2. Fabrication of silicon substrate with undercoat layer
A 6 inch silicon wafer was heat-treated in an oven at 200 ° C. for 30 minutes. Next, the resist solution is applied onto the silicon wafer so that the dry film thickness is 1.5 μm, and further heated and dried in an oven at 220 ° C. for 1 hour to form an undercoat layer. A silicon wafer substrate with an undercoat layer Got.

-B3. Preparation of curable composition
[B3-1. Preparation of pigment dispersion]
C. I. Pigment Green 36 and C.I. I. 50 parts of a 40/60 (mass ratio) mixture with Pigment Yellow 150 (primary average particle size 32 nm; (B) pigment), BYK2001 (Disperbyk: manufactured by BYK) (solid content concentration 45.1%; dispersant) 30 parts (approximately 13.5 parts in terms of solid content), 16.5 parts of dipentaerythritol hexaacrylate (DPHA; (A) a compound having an unsaturated double bond and a molecular weight of less than 4000), propylene glycol monomethyl ether ((C ) Solvent) A mixed liquid in which 103.5 parts were mixed was mixed and dispersed by a bead mill for 15 hours to prepare a pigment dispersion (P2).

[B3-2. Preparation of curable composition (coating liquid)]
The dispersion liquid-treated pigment dispersion (P2) was stirred and mixed to obtain the following composition to prepare a curable composition solution.
<Composition>
-(B) Colorant (the pigment dispersion (P2)) 200 parts-2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole ((D) Photopolymerization initiator) 4 parts ・ Dipentaerythritol hexaacrylate 5 parts (DPHA; (E) photopolymerizable compound)
・ 250 parts of propylene glycol monomethyl ether acetate (PGMEA; solvent)
・ 0.5 parts of 3-methacryloxypropyltrimethoxysilane (substrate adhesion agent)
・ 2.5 parts of the above compound α ((F) sensitizer)
・ 3-mercaptobenzimidazole 3 parts ((I) co-sensitizer)

-B4. Preparation of color filter with curable composition
[Formation of colored pattern]
The curable composition prepared as described above was prepared using the B2. The colored layer (curable composition layer) was formed on the undercoat layer of the silicon wafer with the undercoat layer obtained in (1). Then, heat treatment (pre-baking) was performed for 120 seconds using a hot plate at 100 ° C. so that the dry film thickness of the colored coating film became 0.7 μm.
Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), exposure was performed at various exposure doses of 50 to 500 mJ / cm ² through an Island pattern mask having a pattern of 1.5 μm square at a wavelength of 365 nm. .
Thereafter, a silicon wafer on which a colored layer after exposure is formed is placed on a horizontal rotary table of a spin shower developing machine (DW-30 type, manufactured by Chemitronics), and CD-2000 (Fuji Film Electronics Co., Ltd.). Paddle development was performed at 23 ° C. for 60 seconds using Materials Co., Ltd. to form a colored pattern on the silicon wafer.

  A silicon wafer on which a colored pattern is formed is fixed to the horizontal rotary table by a vacuum chuck method, and the silicon wafer is rotated at a rotational speed of 50 r. p. m. Then, pure water was supplied from the upper part of the rotation center in the form of a shower, and rinsed, and then spray-dried to produce a color filter.

(Examples 10 to 16)
In the preparation of the pigment dispersion of Example 9, except that DPHA (a compound having an unsaturated double bond and a molecular weight of less than 4000) was used instead of a compound having an unsaturated double bond shown in Table 2 below, A curable composition was prepared in the same manner as in Example 9 to produce a color filter.

(Comparative Example 3)
A curable composition was prepared in the same manner as in Example 9 except that DPHA was not used in preparing the pigment dispersion of Example 9, and a color filter was produced.

(Comparative Example 4)
In preparing the pigment dispersion of Example 9, a curable composition was prepared in the same manner as in Example 9 except that the above compound (III) (compound having an unsaturated double bond) was used instead of DPHA. A color filter was prepared.

-B5. Performance evaluation
[B5-1. Storage stability of pigment dispersion over time]
After the pigment dispersion prepared above was stored at room temperature for 1 week, the viscosity of the liquid was measured with an E-type viscometer (manufactured by Tokyo Keiki Co., Ltd.) and evaluated according to the following criteria.
-Evaluation criteria-
○: The viscosity increase was less than 5% with respect to the viscosity before storage.
Δ: An increase in viscosity of 5% or more and less than 10% with respect to the viscosity before storage was observed.
X: A viscosity increase of 10% or more with respect to the viscosity before storage was observed.

[B5-2. Fine dispersion of pigment dispersion]
For the pigment dispersion (P2), the average particle diameter of the pigment was measured by a dynamic light scattering method (measured without further dilution of P2 using Microtrac Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.)). The smaller the average particle diameter of the pigment, the higher the fine dispersibility.
-Evaluation criteria-
○: The average particle size was less than 70 nm Δ: The average particle size was 70 nm or more and less than 150 nm ×: The average particle size was 150 nm or more

[B5-3. Evaluation of exposure sensitivity]
The colored layer after coating is exposed by changing the exposure amount to various exposure amounts in the range of 50 to 1200 mJ / cm ² , and the color pattern after spray drying is measured with a length measurement SEM “S-9260A” (Hitachi High Technologies ( The width of the colored pattern was measured. The exposure amount at which the pattern line width was 1.5 μm was evaluated as the exposure sensitivity. The exposure sensitivity indicates that the smaller the value, the higher the sensitivity. The measurement results are shown in Table 2 below.

[B5-4. Storage stability of curable composition over time]
The storage stability of the curable composition (coating solution) prepared above over time is shown in A3. Evaluation was performed in the same manner as in the performance evaluation (A3-3.). The results are shown in Table 2 below.

[B5-4. Color unevenness]
The color unevenness was evaluated by analyzing the luminance distribution by the following method and based on the ratio of the pixels whose deviation from the average is within ± 5% to the total number of pixels. The evaluation criteria are as follows.
A method for measuring the luminance distribution will be described. First, the curable composition is mixed with the B2. It applied on the undercoat layer of the glass plate with an undercoat layer obtained by the same method, and the colored layer (coating film) was formed.
Heat treatment (pre-baking) was performed for 120 seconds using a hot plate at 100 ° C. so that the dry film thickness of the coating film became 0.7 μm. The luminance distribution of this coated glass plate was analyzed using an image taken with a microscope MX-50 (Olympus).
-Evaluation criteria-
○: Pixels whose deviation from the average is within ± 5% is 99% or more of the total number of pixels Δ: Pixels whose deviation from the average is within ± 5% is 95% or more and less than 99% of the total number of pixels × : Pixels whose deviation from the average is within ± 5% is less than 95% of the total number of pixels

[B5-5. Developability, pattern cross-sectional shape, support adhesion]
The developability in the exposure sensitivity of the colored layer formed on the silicon wafer using the curable composition prepared above, the support adhesion, and the pattern cross-sectional shape are the same as those in A3. Evaluation was performed in the same manner as in the performance evaluation (A3-5.). The results are shown in Table 2 below.
In addition, about pattern cross-sectional shape, a rectangle is preferable and a reverse taper is not preferable.

From the results of Table 2 above, the curability of each Example prepared using a pigment dispersion containing a compound having an unsaturated double bond and a molecular weight of less than 4000, used for forming a color filter for solid-state imaging devices. It can be seen that the composition (pigment type) is excellent in storage stability in the solution state. In addition, when a colored pattern is formed on a support using this curable composition, the exposure sensitivity is high and the developability is excellent for each comparative example not using a specific compound, and the substrate adheres to the substrate. It can be seen that an excellent color filter is obtained in both the properties and the pattern cross-sectional shape.
From these results, the curable compositions of the examples achieved excellent pattern formability even when producing color filters for solid-state imaging devices, as in the case of producing color filters for liquid crystal display devices. You can see that

Claims (5)

  A pigment dispersion composition comprising at least (A) a compound having an unsaturated double bond and a molecular weight of less than 4000, (B) a pigment, and (C) a solvent.   A curable composition comprising the pigment dispersion composition according to claim 1 and (D) a photopolymerization initiator.   (E) The curable composition of Claim 2 which further contains a photopolymerizable compound.   The color filter which has a coloring pattern formed with the curable composition of Claim 2 or 3 on the support body. (A) preparing a curable composition using a pigment dispersion composition containing at least a compound having an unsaturated double bond and a molecular weight of less than 4000, (B) a pigment, and (C) a solvent;
A colored layer forming step of forming a colored layer comprising the curable composition by applying the curable composition on a support;
An exposure step of exposing the colored layer in a pattern-like manner through a mask;
A development step of developing the colored layer after exposure to form a colored pattern;
A method for producing a color filter comprising: