JP2008134583A - Color filter, liquid crystal display and curable composition for use in manufacture of the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a color filter having high color purity of colored pixels and high color density of a light shielding part and capable of achieving high contrast, a liquid crystal display including the color filter, and a curable composition for pixel formation capable of forming colored pixels of high color purity and a curable composition for light shielding part formation capable of forming a light shielding part of high color density, which are useful for forming the color filter. <P>SOLUTION: The color filter includes colored pixels which are formed of the curable composition for colored pixel formation and of which the color purity under a C light source is ≥65% to the area (100) of a three-primary-color chromaticity point by the NTSC system in a CIE color system, and a light shielding part which are formed of the curable composition for light shielding part formation in a width of 5-15 μm and of which the optical density (OD value) is ≥4.5. The color filter achieves a color filter contrast ratio of ≥5,000. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a color filter used for a liquid crystal display element (LCD), a solid-state imaging element (CCD, CMOS, etc.), a liquid crystal display device including the color filter, and a curable property suitable for forming colored pixels and light shielding portions of the color filter. About the composition

The color filter is an essential component for liquid crystal displays and solid-state image sensors.
In color filter applications for liquid crystal displays (LCDs), the substrate size has been expanded for the production of large TVs, and in order to improve productivity when large substrates are used, the yield in coating by the slit method is high. There is a demand for a wide development latitude that allows exposure with low energy. In addition, liquid crystal displays for TV use are required to have higher image quality than those for conventional notebook computers and monitors. That is, improvement in contrast and color purity.
In order to improve the contrast, the curable composition used for the production of the color filter is required to have a finer particle size of the colorant (organic pigment or the like) used. (For example, refer to Patent Document 1.) Along with this, the amount of dispersant added for dispersing the pigment tends to increase. Moreover, the higher thing is calculated | required as content rate of the coloring agent (organic pigment) which occupies in solid content of a curable composition for color purity improvement. Therefore, the content of the photopolymerization initiator, the photopolymerizable monomer, and the alkali-soluble resin component for imparting alkali solubility in the solid content in the curable composition tends to decrease.
For this reason, for the purpose of improving pigment dispersibility, various novel dispersants have been proposed. For example, living anion polymerization amine-based polymer dispersants (for example, see Patent Document 2) and cationic graft polymers (for example, (See Patent Document 3), but it is difficult to say that the level is practically sufficient.

Further, in order to achieve high color purity, a technique has been proposed in which the chromaticity of RGB constituting a pixel is defined with high color purity (see, for example, Patent Documents 4 and 5). Although the color purity is improved, it does not realize a practically sufficient contrast and a wide latitude in the development process.
On the other hand, in order to achieve the optimum contrast, proposals have also been made to improve the black matrix's light-shielding properties. By increasing the shielding effect, it is possible to cause external light reflection and improve display contrast. For example, a black matrix forming technique with an OD value of 4 or more is proposed (see, for example, Patent Document 6), but at present, development of a shielding layer having a greater shielding effect is desired.
JP 2005-316439 A JP 2005-283950 A JP 2006-52410 A JP 2001-228322 A JP 2002-107525 A JP 2005-281386 A

The present invention has been made in order to improve the above-described drawbacks of the prior art, and an object of the present invention is to provide a color filter that achieves high contrast with a high color purity of the colored pixels and a high color density of the light-shielding portion. An object of the present invention is to provide a liquid crystal display device including the color filter.
A further object of the present invention is to provide a curable composition for forming a pixel capable of forming a colored pixel with high color purity, which is useful for forming the color filter of the present invention, and a light shielding portion capable of forming a light shielding portion having a high color density. It is to provide a forming curable composition.

As a result of earnest research, the present inventor can obtain a color filter excellent in contrast by including a colored pixel produced using a specific dispersant and a light-shielding portion formed using a specific light-shielding agent. As a result, the present invention has been completed.
The configuration of the present invention is as follows.
<1> Coloring formed with a curable composition for forming colored pixels and having a color purity of 65% or more with respect to the area (100) of the three primary color chromaticity points in the NTSC system in the CIE color system It is formed of a pixel and a curable composition for forming a light shielding part, has an optical density (OD value) of 4.5 or more, a light shielding part having a width of 5 to 15 μm, and a color filter contrast ratio of 5000 or more. Color filter.
<2> The color filter according to <1>, wherein a thickness of the colored pixel portion is in a range of 1.5 to 2.5 μm.
<3> The color filter according to <1>, wherein an optical density of the light shielding portion is 4.8 or more and a film thickness thereof is in a range of 0.3 to 1.0 μm.
<4> The color filter according to <1>, wherein the curable composition for forming a colored pixel contains a polymerization initiator represented by the following general formula (DA).

In the general formula (DA), R ¹ and R ² are each independently a hydrogen atom, an alkyl group, an aryl group, or the following general formula (DA-1) or general formula (DA-A- The substituent shown by 2) is represented. R ³ and R ⁴ each independently represents a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group. X and Y each independently represent -Cl and -Br, and m and n each represents 0, 1 or 2.

In general formula (D-A-1) and the general formula ^(D-A-2), R 5, R 6, R 7 each independently represent an alkyl group, or an aryl group.
<5> A colorant, a compound represented by the following general formula (1), a polymer containing a copolymer unit derived from a monomer represented by the following general formula (I), and the following general formula (a) One or more polymers selected from the group consisting of polymers containing structural units represented by the formula (1), having an acid value of 20 to 300 mg / g and a weight average molecular weight in the range of 3,000 to 100,000. Contains a dispersant, a polymerizable compound, a polymerization initiator, and a solvent. In the CIE color system, the color purity at the C light source is 65% or more with respect to the area (100) of the NTSC three primary color chromaticity points. A curable composition for forming a color filter colored pixel capable of forming a colored pixel.

In the general formula (1), A ¹ represents an organic dye structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, or 4 or more carbon atoms. Represents a monovalent organic group containing at least one portion selected from a hydrocarbon group, an alkoxysilyl group, an epoxy group, an isocyanate group, and a hydroxyl group. The n A ¹ may be the same or different.
R ¹ represents an (m + n) -valent organic linking group, where 3 <(m + n) <10. R ² represents a single bond or a divalent organic linking group. P ¹ represents a polymer skeleton.

In the general formula (I), R ⁰¹ represents a hydrogen atom or a substituted or unsubstituted alkyl group. R ⁰² represents an alkylene group. W represents -CO-, -C (= O) O-, -CONH-, -OC (= O)-, or a phenylene group. X is —O—, —S—, —C (═O) O—, —CONH—, —C (═O) S—, —NHCONH—, —NHC (═O) O—, —NHC (═O ) Represents one selected from S-, -OC (= O)-, -OCONH-, and -NHCO-. Y represents any one selected from NR ⁰³ , O, and S, and R ⁰³ represents a hydrogen atom, an alkyl group, or an aryl group. In the formula, N and Y are connected to each other to form a cyclic structure. m1 and n1 are each independently 0 or 1.

In the general formula (a), R ^1a represents hydrogen or a methyl group, R ^2a represents an alkylene group, and Z ¹ represents a nitrogen-containing heterocyclic structure.

<6> The curable composition for forming a color filter colored pixel according to <5>, wherein the polymerization initiator includes a compound represented by the following general formula (DA).

In the general formula (DA), R ¹ and R ² are each independently a hydrogen atom, an alkyl group, an aryl group, or the following general formula (DA-1) or general formula (DA-A- The substituent shown by 2) is represented. R ³ and R ⁴ each independently represents a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group. X and Y each independently represent -Cl and -Br, and m and n each represents 0, 1 or 2.

In general formula (D-A-1) and the general formula ^(D-A-2), R 5, R 6, R 7 each independently represent an alkyl group, or an aryl group.
<7> Color filter shading that contains 40 to 80% by mass of carbon black as a polymerizable compound, a polymerization initiator, and a shading agent in terms of solid content, and that can form a shading part having an optical density (OD value) of 4.5 or more. Curable composition for part formation.
<8> A color capable of forming a light-shielding portion having a polymerizable compound, a polymerization initiator, and metal fine particles as a light-shielding agent in an amount of 50 to 90% by mass in terms of solid content and an optical density (OD value) of 4.5 or more. A curable composition for forming a light shielding part of a filter.
<9><1> to <1>, wherein the colored pixel forming composition according to <5> or <6> and the light shielding part forming composition according to <7> or <8> are used. The color filter according to any one of 4>.
<10> A liquid crystal display device comprising the color filter according to any one of <1> to <4> and <9>.
<11> The liquid crystal display device according to <10>, comprising an RGB-LED light source as a backlight.

The present invention provides a high-contrast, high-purity colored pixel that has good pigment dispersion stability and can be stored for a long period of time even if the pigment particles are miniaturized in order to achieve high contrast due to the function of the polymer dispersant. Is formed. In addition, the function of the curable composition used for the light-shielding part enables the formation of a light-shielding part with a thin layer and a large shielding effect, so that it is suitable for slit coating and has high performance coloring without foreign matter, coating unevenness, and coating streaks. Since the pixel portion is formed, combined with the large light shielding effect of the light shielding layer, it is possible to provide a color filter with high contrast and good color reproducibility that does not leak light, and has high definition and good visibility. A device can be obtained.
Further, since the colored pixel region has high color purity and high light transmittance, power consumption can be reduced, and an environmentally friendly display device can be provided.
In addition, since the curable composition forming the colored pixels and the light-shielding portion can be cured with high sensitivity, it is possible to provide an inexpensive color filter with high throughput, good yield, high productivity, and low cost.
Furthermore, in a preferred embodiment of the present invention, the color filter of the present invention and the display device using an RGB-LED light source for the backlight further improve the high color reproducibility and provide high color purity and high contrast color. Filter technology can be more effectively exhibited.

ADVANTAGE OF THE INVENTION According to this invention, the color purity of the color purity of a color pixel and the color density of a light-shielding part is high, and a liquid crystal display device provided with this color filter which implement | achieves high contrast can be provided.
Furthermore, according to the present invention, the curable composition for forming a pixel that can form a colored pixel with high color purity, which is useful for forming the color filter of the present invention, and the light shielding that can form a light shielding part with a high shielding effect. A curable composition for forming a part can be provided.

Hereinafter, the curable composition for forming a colored pixel and the curable composition for forming a light shielding part, which are useful for forming the color filter, display device, and color filter of the present invention, will be described in detail.
[Color filter]
The color filter of the present invention is formed of a curable composition for forming colored pixels in the CIE color system, and the color purity at the C light source is 65% with respect to the area (100) of the NTSC three primary color chromaticity points. It has the above-described colored pixels, a light-shielding part-forming curable composition, an optical density (OD value) of 4.5 or more, a light-shielding part having a width of 5 to 15 μm, and the contrast of each monochromatic layer The ratio is 5000 or more.
Here, the color purity of the colored pixel is the size of the chromaticity (in this case, RGB color filter) with respect to the area (100) of the NTSC three primary color chromaticity points in the CIE color system. It means what is expressed, and can be measured using a commercially available colorimetric colorimeter in accordance with JIS-Z-8701. In the present invention, the color purity measured with the C light source of the backlight of the colored pixel is required to be 65% or more, and more preferably 70% or more. Such color purity can be achieved by, for example, a method using a colorant having a large absorbance at a predetermined wavelength, a method of increasing the colorant content per unit area, or the like. In addition, it can be said that use of a colorant having a large absorbance at an unnecessary wavelength is not preferable from the viewpoint of improving color purity.

The colored pixel in the color filter of the present invention preferably contains a coloring pattern containing a colorant at a high concentration, high color development and a thin film thickness, and the film thickness of the colored pixel is preferably 2.5 μm or less, More preferably, it is 2.0 μm or less. The film thickness is preferably as thin as possible as long as the color purity preferable for the pixel can be achieved, but it is preferably 1.0 μm or more in consideration of film formability, developability, pixel uniformity, etc. More preferably, it is 1.4 μm or more.
Such a colored pixel capable of realizing color purity and contrast is formed by a curable composition for forming a colored pixel described in detail below.

[Curable composition for forming colored pixels]
The curable composition used for forming the colored pixel of the color filter of the present invention is a radiation-sensitive composition, and is particularly suitable for curing with light. (A-1) Colorant, (B) Polymer dispersion An agent, (C) a polymerizable compound, (D) a photopolymerization initiator, and (E) a solvent, which may contain other components as desired.
<(A-1) Colorant>
Here, the pigment used as the colorant may be an inorganic pigment or an organic pigment, but considering that a high transmittance is preferable, it is preferable to use a pigment having a particle size as small as possible. The average particle size is preferably 10 to 100 nm, more preferably. It is the range of 10-50 nm. In the curable composition of the present invention, since the specific (B) polymer dispersant described later is used, the pigment dispersibility and dispersion stability are good even when the colorant is small in size. Even if it is thin, a colored pixel having excellent color purity can be formed.

  Examples of inorganic pigments that can be used as a colorant for pixel formation include metal compounds represented by metal oxides, metal complex salts, and the like. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, Examples thereof include metal oxides such as titanium, magnesium, chromium, zinc, and antimony, and composite oxides of the above metals.

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

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

These organic pigments can be used alone or in various combinations in order to increase color purity. Specific examples of combinations are shown below.
For example, as a red pigment, an anthraquinone pigment, a perylene pigment, a diketopyrrolopyrrole pigment alone or at least one of them, a bisazo yellow pigment, an isoindoline yellow pigment, a quinophthalone yellow pigment, or a perylene red pigment A mixture of these can be used. For example, as an anthraquinone pigment, C.I. I. Pigment Red 177, and perylene pigments include C.I. I. Pigment red 155, C.I. I. Pigment Red 224, and diketopyrrolopyrrole pigments include C.I. I. Pigment red 254, and C.I. I. Mixing with Pigment Yellow 139 is preferred. The mass ratio of the red pigment to the yellow pigment is preferably 100: 5 to 100: 50 from the viewpoint of obtaining sufficient color purity and suppressing deviation from the NTSC target hue. In particular, the mass ratio is optimally in the range of 100: 10 to 100: 30. In addition, in the case of the combination of red pigments, it can adjust according to chromaticity.

  As the green pigment, a halogenated phthalocyanine pigment can be used alone, or a mixture thereof with a bisazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment, or an isoindoline yellow pigment can be used. For example, C.I. I. Pigment Green 7, 36, 37 and C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 180 or C.I. I. Mixing with Pigment Yellow 185 is preferred. The mass ratio of the green pigment to the yellow pigment is preferably 100: 5 to 100: 150 from the viewpoint of obtaining sufficient color purity and suppressing deviation from the NTSC target hue. The mass ratio is particularly preferably in the range of 100: 30 to 100: 120.

  As the blue pigment, a phthalocyanine pigment can be used alone, or a mixture thereof with a dioxazine purple pigment can be used. For example, C.I. I. Pigment blue 15: 6 and C.I. I. Mixing with pigment violet 23 is preferred. The mass ratio of the blue pigment and the purple pigment is preferably 100: 0 to 100: 50, more preferably 100: 5 to 100: 30.

  The content of (A-1) the colorant (pigment) in the curable composition for forming colored pixels of the present invention is preferably 25 to 75% by mass with respect to the total solid content (mass) of the composition. 32 to 70% by mass is more preferable. (A-1) When the content of the colorant (pigment) is within the above range, the color density is sufficient and it is effective to ensure excellent color characteristics.

<(B) Polymer dispersant>
The polymer dispersant (B) in the present invention is required to be a resin having an acid value of 20 to 300 mg / g and a weight average molecular weight in the range of 3,000 to 100,000. Hereinafter, such a specific polymer dispersant may be simply referred to as “(B) dispersion resin”.
In the present invention, the (B) dispersion resin is a pigment dispersing agent mentioned as the colorant (A-1) or a light shielding agent (black matrix forming pigment) in the light-shielding part-forming curable composition described later. It is a compound that can function as a dispersant.
(B) Since the dispersion resin needs to have a specific acid value as described above, the dispersion resin is preferably a polymer compound having an acidic group.
Examples of the polymer skeleton of the polymer compound include polymers or copolymers of vinyl monomers, ester polymers, ether polymers, urethane polymers, amide polymers, epoxy polymers, silicone polymers, and modified products thereof. Or a copolymer [for example, a polyether / polyurethane copolymer, a copolymer of a polyether / vinyl monomer polymer, etc. (any of a random copolymer, a block copolymer, and a graft copolymer) Good). At least one selected from the group consisting of vinyl monomers, selected from the group consisting of polymers or copolymers of vinyl monomers, ester polymers, ether polymers, urethane polymers, and modified products or copolymers thereof. At least one kind is more preferable, and a polymer or copolymer of vinyl monomers is particularly preferable.

Examples of a method for introducing an acidic group into the polymer skeleton as described above include, for example, a method of copolymerizing a monomer containing an acidic group when polymerizing the polymer skeleton, and the polymer described above. There is a method of introducing a skeleton by polymer reaction after polymerization.
Examples of the monomer containing an acidic group include (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid, acrylic acid dimer, vinyl benzoic acid, styrene sulfonic acid, 2-acrylamide-2- It is obtained by reacting an alcoholic hydroxyl group-containing monomer such as methylpropanesulfonic acid, mono (meth) acryloylethyl phosphate, or 2-hydroxyethyl methacrylate with a cyclic acid anhydride such as maleic anhydride or phthalic anhydride. And monomers.
Among these, examples of preferable monomers are obtained by reacting an alcoholic hydroxyl group-containing monomer such as (meth) acrylic acid or 2-hydroxyethyl methacrylate with a cyclic acid anhydride such as maleic anhydride or phthalic anhydride. And the like. Examples of the cyclic acid anhydride used here include itaconic anhydride, maleic anhydride, phthalic anhydride, succinic anhydride, glutaric anhydride, trimetic anhydride, etc., and particularly phthalic anhydride, succinic anhydride, etc. Is preferred.

Furthermore, the polymer compound having an acidic group may further be obtained by copolymerizing a vinyl monomer component.
Although it does not restrict | limit especially as said vinyl monomer, For example, (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, (meth) acrylamides , Vinyl ethers, esters of vinyl alcohol, styrenes, (meth) acrylonitrile and the like are preferable.

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

Examples of crotonic acid esters include butyl crotonate and hexyl crotonate.
Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate, and the like.
Examples of maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.
Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.
Examples of itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

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

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

In addition to the above compounds, (meth) acrylonitrile, heterocyclic groups substituted with a vinyl group (for example, vinylpyridine, vinylpyrrolidone, vinylcarbazole, etc.), N-vinylformamide, N-vinylacetamide, N-vinylimidazole, Vinyl caprolactone can also be used.
Furthermore, for example, vinyl monomers having a functional group such as a urethane group, a urea group, a sulfonamide group, a phenol group, and an imide group can also be used. Such a monomer having a urethane group or a urea group can be appropriately synthesized using, for example, an addition reaction between an isocyanate group and a hydroxyl group or an amino group. Specifically, an addition reaction between an isocyanate group-containing monomer and a compound containing one hydroxyl group or a compound containing one primary or secondary amino group, or a hydroxyl group-containing monomer or primary or secondary amino group containing It can be appropriately synthesized by an addition reaction between a monomer and monoisocyanate.

Further, polymerizable oligomers as shown below may be used as vinyl monomers.
The polymerizable oligomer (hereinafter sometimes referred to as “macromonomer”) is an oligomer having a group having an ethylenically unsaturated double bond at the terminal. In the present invention, among the polymerizable oligomers, it is preferable to have a group having the ethylenically unsaturated double bond only at one of both ends of the oligomer.

  The molecular weight of the polymerizable oligomer is preferably a polystyrene-equivalent number average molecular weight (Mn) of 1000 to 20000, more preferably 2000 to 15000. If the number average molecular weight is less than 1000, the steric repulsion effect as a dispersant may not be sufficient, and if it exceeds 20000, it may take time to adsorb to the colorant (pigment) due to the steric effect. .

  The oligomer generally includes, for example, a homopolymer or copolymer formed from at least one monomer selected from alkyl (meth) acrylate, styrene, acrylonitrile, vinyl acetate and butadiene, Among these, alkyl (meth) acrylate homopolymers or copolymers, polystyrene, and the like are preferable. In the present invention, these oligomers may be substituted with a substituent, and the substituent is not particularly limited, and examples thereof include a hydroxyl group and a halogen atom.

The above vinyl monomers may be polymerized by only one kind, or may be copolymerized by using two or more kinds together. Such a radical polymer is prepared by a known method in accordance with a conventional method for each corresponding vinyl monomer. It is obtained by polymerizing.
For example, a method in which these vinyl monomer and chain transfer agent are dissolved in a suitable solvent, a radical polymerization initiator is added thereto and polymerized in solution at about 50 ° C. to 220 ° C. (solution polymerization method) Can be obtained using

  Examples of suitable solvents used in the solution polymerization method can be arbitrarily selected depending on the monomers used and the solubility of the resulting copolymer. For example, methanol, ethanol, propanol, isopropanol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, methoxypropyl acetate, ethyl lactate, ethyl acetate, acetonitrile, tetrahydrofuran, dimethylformamide, chloroform, toluene Can be mentioned. These solvents may be used as a mixture of two or more.

  Examples of radical polymerization initiators include azo compounds such as 2,2′-azobis (isobutyronitrile) (AIBN) and 2,2′-azobis- (2,4′-dimethylvaleronitrile), benzoyl par Peroxides such as oxides, and persulfates such as potassium persulfate and ammonium persulfate can be used.

As described above, the dispersion resin (B) in the present invention requires an acid value in the range of 20 to 300 mg / g, preferably in the range of 30 to 250 mg / g, more preferably 30. It is in the range of ~ 200 mg / g.
When the acid value of the (B) dispersion resin is within this range, the dispersibility and dispersion stability of the (A) pigment (pigment) are excellent, and the alkali developability is also excellent.

Moreover, the weight average molecular weight of (B) dispersion resin needs to be in the range of 3,000 to 100,000, preferably in the range of 3,000 to 70,000, more preferably 5, It is in the range of 000 to 50,000.
(B) When the weight average molecular weight of the dispersion resin is within this range, (A-1) shortening of the dispersion time of the pigment used as the colorant or (A-2) light-shielding agent described later, and stability over time of the dispersion From the viewpoint of

In addition, the (B) dispersion resin in the present invention has a polymer compound having 2 to 100 pigment-adsorptive groups at the polymer terminal, or a nitrogen-containing heterocyclic ring, and an ethylenically unsaturated group. A polymer compound containing a monomer as a copolymer unit is preferable.
Hereinafter, these two polymer compounds will be specifically described.

(B) The polymer compound having 2 to 100 pigment-adsorptive groups as the dispersion resin at the polymer terminal has a specific acid value and a weight average molecular weight as described above, and the pigment-adsorptive group has Although it will not restrict | limit especially if it is a high molecular compound which has 2-100 in the polymer terminal, It is preferable that it is the following.
That is, a polymer compound having 4 to 70 pigment adsorbing groups at the polymer terminal is preferable, and a polymer compound having 5 to 50 pigment adsorbing groups at the polymer terminal is more preferable. The pigment adsorbing group is preferably an organic dye structure, a heterocyclic structure, an acidic group, a basic group, or the like. Among these, a polymer compound represented by the general formula (1) described later is preferable.

(B) As a polymer compound having a nitrogen-containing heterocycle as a dispersion resin and a monomer having an ethylenically unsaturated group as a copolymer unit, the specific acid value and weight average as described above The polymer compound is not particularly limited as long as it is a polymer compound having a molecular weight, a nitrogen-containing heterocyclic ring, and a monomer having an ethylenically unsaturated group as a copolymerization unit. What has is preferable.
Preferred nitrogen-containing heterocycles include pyrrole, pyrroline, pyrrolidine, pyrazole, pyrazoline, pyrazolidine, imidazole, triazole, pyridine, piperidine, morpholine, pyridazine, pyrimidine, piperazine, triazine, isoindoline, isoindolinone, benzimidazolone, benzo Examples include thiazole, succinimide, phthalimide, naphthalimide, hydantoin, and carbazole.
Especially, it is preferable that it is a polymer containing the copolymer unit derived from the monomer represented by general formula (I) mentioned later, or the polymer containing the structural unit represented by general formula (a).

  Hereinafter, (B-1) a polymer compound represented by the general formula (1) and (B-2) a monomer represented by the general formula (I) suitable as the (B) dispersion resin in the present invention. The polymer containing the derived copolymer unit and (B-3) the polymer containing the structural unit represented by the general formula (a) will be described.

[(B-1) Polymer Compound Represented by General Formula (1): (B-1) Specific Dispersion Resin]
First, a polymer compound represented by the following general formula (1) (hereinafter, appropriately referred to as “(B-1) specific dispersion resin”) will be described.

In the general formula (1), A ¹ represents an organic dye structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, or 4 or more carbon atoms. Represents a monovalent organic group containing at least one portion selected from a hydrocarbon group, an alkoxysilyl group, an epoxy group, an isocyanate group, and a hydroxyl group. The n A ¹ may be the same or different.

That is, the A ¹ has a structure capable of adsorbing to a pigment such as an organic dye structure or a heterocyclic structure, an acid group, a group having a basic nitrogen atom, a urea group, a urethane group, or a coordinating oxygen atom. And a monovalent organic group containing at least one functional group capable of adsorbing to a pigment, such as a group, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, and a hydroxyl group.
Hereinafter, the site having the ability to adsorb to the pigment (the above structure and functional group) will be collectively referred to as “adsorption site” as appropriate.

The adsorption sites are in one A ^1, it may be contained at least one, may contain two or more kinds.
Further, in the present invention, the “monovalent organic group containing at least one kind of adsorption site” means the above-mentioned adsorption site, 1 to 200 carbon atoms, 0 to 20 nitrogen atoms, 0 to It is a monovalent organic group formed by bonding up to 100 oxygen atoms, 1 to 400 hydrogen atoms, and an organic linking group consisting of 0 to 40 sulfur atoms. In the case where adsorption sites themselves may constitute a monovalent organic group, adsorption sites itself may be a monovalent organic group represented by A ^1.
First, the adsorption site constituting A ¹ will be described below.

  Examples of the “organic dye structure” include phthalocyanine, insoluble azo, azo lake, anthraquinone, quinacridone, dioxazine, diketopyrrolopyrrole, anthrapyridine, anthanthrone, indanthrone, flavan. Examples of preferable dye structures of throne, perinone, perylene, and thioindigo are phthalocyanine, azo lake, anthraquinone, dioxazine, and diketopyrrolopyrrole, and phthalocyanine and anthraquinone. A diketopyrrolopyrrole dye structure is particularly preferred.

  Examples of the “heterocyclic structure” include thiophene, furan, xanthene, pyrrole, pyrroline, pyrrolidine, dioxolane, pyrazole, pyrazoline, pyrazolidine, imidazole, oxazole, thiazole, oxadiazole, triazole, thiadiazole, pyran, pyridine. , Piperidine, dioxane, morpholine, pyridazine, pyrimidine, piperazine, triazine, trithiane, isoindoline, isoindolinone, benzimidazolone, benzothiazole, succinimide, phthalimide, naphthalimide, hydantoin, indole, quinoline, carbazole, acridine, acridone, Anthraquinone is mentioned as a preferred example, pyrroline, pyrrolidine, pyrazole, pyrazoline, pyrazolidine, imidazole, Riazor, pyridine, piperidine, morpholine, pyridazine, pyrimidine, piperazine, triazine, isoindoline, isoindolinone, benzimidazolone, benzothiazole, succinimide, phthalimide, naphthalimide, hydantoin, carbazole, acridine, acridone, anthraquinone are more preferable.

  The “organic dye structure” or “heterocyclic structure” may further have a substituent. Examples of the substituent include alkyl groups having 1 to 20 carbon atoms such as a methyl group and an ethyl group. An acyloxy group having 1 to 6 carbon atoms, such as an aryl group having 6 to 16 carbon atoms such as a hydroxyl group, a phenyl group or a naphthyl group, a hydroxyl group, an amino group, a carboxyl group, a sulfonamide group, an N-sulfonylamide group or an acetoxy group. Alkoxy groups having 1 to 20 carbon atoms such as methoxy group and ethoxy group, halogen atoms such as chlorine and bromine, alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group and cyclohexyloxycarbonyl group , A cyano group, a carbonate group such as t-butyl carbonate, and the like. Here, these substituents may be bonded to the organic dye structure or the heterocyclic ring through the following structural unit or a linking group constituted by combining the structural units.

  Preferred examples of the “acidic group” include a carboxylic acid group, a sulfonic acid group, a monosulfate group, a phosphoric acid group, a monophosphate group, and a boric acid group. Sulfuric acid ester groups, phosphoric acid groups, and monophosphoric acid ester groups are more preferable, and carboxylic acid groups, sulfonic acid groups, and phosphoric acid groups are particularly preferable.

Examples of the “group having a basic nitrogen atom” include an amino group (—NH ₂ ), a substituted imino group (—NHR ⁸ , —NR ⁹ R ¹⁰ , wherein R ⁸ , R ⁹ , and R ¹⁰ Each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms), a guanidyl group represented by the following formula (a1), Preferred examples include the amidinyl group represented by a2).

In formula (a1), R ¹¹ and R ¹² each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms.
In formula (a2), R ¹³ and R ¹⁴ each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms.

Among these, an amino group (—NH ₂ ), a substituted imino group (—NHR ⁸ , —NR ⁹ R ¹⁰ , wherein R ⁸ , R ⁹ , and R ¹⁰ each independently has 1 to 10 carbon atoms. An alkyl group, a phenyl group, and a benzyl group.), A guanidyl group represented by the formula (a1) [in the formula (a1), R ¹¹ and R ¹² are each independently an alkyl group having 1 to 10 carbon atoms. Represents a phenyl group or a benzyl group. ] An amidinyl group represented by the formula (a2) [in the formula (a2), R ¹³ and R ¹⁴ each independently represents an alkyl group having 1 to 10 carbon atoms, a phenyl group, or a benzyl group. ] Is more preferable.
In particular, an amino group (—NH ₂ ), a substituted imino group (—NHR ⁸ , —NR ⁹ R ¹⁰ , wherein R ⁸ , R ⁹ , and R ¹⁰ are each independently an alkyl group having 1 to 5 carbon atoms. , A phenyl group and a benzyl group), a guanidyl group represented by the formula (a1) [in the formula (a1), R ¹¹ and R ¹² are each independently an alkyl group having 1 to 5 carbon atoms, phenyl Represents a benzyl group. Amidinyl group represented by the formula (a2) [in the formula (a2), R ¹³ and R ¹⁴ each independently represents an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a benzyl group. Etc. are preferably used.

Examples of the “urea group” include —NR ¹⁵ CONR ¹⁶ R ¹⁷ (wherein R ¹⁵ , R ¹⁶ , and R ¹⁷ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a carbon number) Preferred examples include 6 or more aryl groups and an aralkyl group having 7 or more carbon atoms. —NR ¹⁵ CONHR ¹⁷ (wherein R ¹⁵ and R ¹⁷ are each independently a hydrogen atom or 1 carbon atom) More preferably an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 or more carbon atoms, and an aralkyl group having 7 or more carbon atoms), -NHCONHR ¹⁷ (wherein R ¹⁷ represents a hydrogen atom or 1 to 10 carbon atoms). An alkyl group, an aryl group having 6 or more carbon atoms, and an aralkyl group having 7 or more carbon atoms are particularly preferable.

Examples of the “urethane group” include —NHCOOR ¹⁸ , —NR ¹⁹ COOR ²⁰ , —OCONHR ²¹ , —OCONR ²² R ²³ (wherein R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² and R ²³ are Each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms), and the like. -NHCOOR ¹⁸ , -OCONHR ²¹ (here And R ¹⁸ and R ²¹ each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms), and the like, more preferably —NHCOOR ¹⁸ , -OCONHR ^{21 (wherein,} R ^{18, R 21} each independently represents an alkyl group having from 1 to 10 carbon atoms, 6 or more arylene carbon Group, the number 7 or aralkyl group having a carbon.), Etc. are particularly preferred.

  Examples of the “group having a coordinating oxygen atom” include an acetylacetonato group and a crown ether.

  Preferred examples of the “hydrocarbon group having 4 or more carbon atoms” include an alkyl group having 4 or more carbon atoms, an aryl group having 6 or more carbon atoms, an aralkyl group having 7 or more carbon atoms, and the like. More preferred are an alkyl group, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an alkyl group having 4 to 15 carbon atoms (for example, an octyl group, a dodecyl group, etc.), and an aryl having 6 to 15 carbon atoms. A group (for example, phenyl group, naphthyl group, etc.), an aralkyl group having 7 to 15 carbon atoms (for example, benzyl group, etc.) and the like are particularly preferable.

  Examples of the “alkoxysilyl group” include a trimethoxysilyl group and a triethoxysilyl group.

The organic linking group bonded to the adsorption site may be a single bond or 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200. An organic linking group consisting of up to 20 hydrogen atoms and 0 to 20 sulfur atoms is preferred, and this organic linking group may be unsubstituted or may further have a substituent.
Specific examples of the organic linking group include the following structural units or groups constituted by combining the structural units.

  When the organic linking group has a substituent, examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, and a carbon group having 6 to 16 carbon atoms such as a phenyl group and a naphthyl group. C1-C6 alkoxy such as aryl group, hydroxyl group, amino group, carboxyl group, sulfonamide group, N-sulfonylamide group, acetoxy group, etc., C1-C6 acyloxy group, methoxy group, ethoxy group, etc. Group, halogen atoms such as chlorine and bromine, alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group and cyclohexyloxycarbonyl group, carbonate groups such as cyano group and t-butyl carbonate, etc. Can be mentioned.

In the above, as A ¹ , at least one site selected from an organic dye structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, and a hydrocarbon group having 4 or more carbon atoms is used. It is preferable that it is a monovalent organic group to contain.

The A ¹ is more preferably a monovalent organic group represented by the following general formula (4).

In the general formula (4), B ¹ represents the adsorption site (that is, an organic dye structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, or a group having a coordinating oxygen atom). , A moiety selected from a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, and a hydroxyl group), and R ²⁴ represents a single bond or an (a + 1) -valent organic linking group. a represents an integer of 1 to 10, and a number of B ¹ may be the same or different.

Examples of the adsorption site represented by B ¹ include those similar to the adsorption site constituting A ¹ in the general formula (1) described above, and preferred examples are also the same.
Among these, a site selected from an organic dye structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, and a hydrocarbon group having 4 or more carbon atoms is preferable.

R ²⁴ represents a single bond or an (a + 1) -valent organic linking group, and a represents 1 to 10. Preferably, a is 1-7, more preferably, a is 1-5, and particularly preferably, a is 1-3.
(A + 1) valent organic linking group includes 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, And a group consisting of 0 to 20 sulfur atoms, which may be unsubstituted or further substituted.

  Specific examples of the (a + 1) -valent organic linking group include the following structural units or groups formed by combining the structural units (which may form a ring structure).

R ²⁴ may be a single bond, or 1 to 50 carbon atoms, 0 to 8 nitrogen atoms, 0 to 25 oxygen atoms, 1 to 100 hydrogen atoms, and An (a + 1) valent organic linking group consisting of 0 to 10 sulfur atoms is preferred, a single bond, or 1 to 30 carbon atoms, 0 to 6 nitrogen atoms, 0 to 15 More preferred are (a + 1) valent organic linking groups consisting of up to 1 oxygen atom, 1 to 50 hydrogen atoms, and 0 to 7 sulfur atoms, a single bond, or 1 to 10 (A + 1) valence consisting of 0 to 5 nitrogen atoms, 0 to 10 oxygen atoms, 1 to 30 hydrogen atoms, and 0 to 5 sulfur atoms The organic linking group is particularly preferred.

  Among the above, when the (a + 1) -valent organic linking group has a substituent, examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, a phenyl group, a naphthyl group, and the like. Such as an aryloxy group having 6 to 16 carbon atoms, a hydroxyl group, an amino group, a carboxyl group, a sulfonamide group, an N-sulfonylamide group, an acetoxy group and the like, an acyloxy group having 1 to 6 carbon atoms, a methoxy group, an ethoxy group, Alkoxy groups having 1 to 6 carbon atoms, halogen atoms such as chlorine and bromine, alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl groups, ethoxycarbonyl groups, and cyclohexyloxycarbonyl groups, cyano groups, and t-butyl carbonate And the like, and the like.

In the general formula (1), R ² represents a single bond or a divalent organic linking group. n R ² may be the same or different.
Divalent organic linking groups include 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 Groups comprising from 20 to 20 sulfur atoms are included and may be unsubstituted or further substituted.

  Specific examples of the divalent organic linking group include the following structural units or groups formed by combining the structural units.

R ² may be a single bond or 1 to 50 carbon atoms, 0 to 8 nitrogen atoms, 0 to 25 oxygen atoms, 1 to 100 hydrogen atoms, and A divalent organic linking group consisting of 0 to 10 sulfur atoms is preferred, a single bond, or 1 to 30 carbon atoms, 0 to 6 nitrogen atoms, 0 to 15 And more preferably a divalent organic linking group comprising 1 to 50 hydrogen atoms and 0 to 7 sulfur atoms, a single bond or 1 to 10 carbon atoms, A divalent organic linking group consisting of 0 to 5 nitrogen atoms, 0 to 10 oxygen atoms, 1 to 30 hydrogen atoms, and 0 to 5 sulfur atoms, in particular preferable.

  Among the above, when the divalent organic linking group has a substituent, examples of the substituent include carbon having 1 to 20 carbon atoms such as a methyl group and an ethyl group, a carbon such as a phenyl group and a naphthyl group. Carbon number such as acyloxy group having 1 to 6 carbon atoms such as aryl group, hydroxyl group, amino group, carboxyl group, sulfonamido group, N-sulfonylamido group, acetoxy group, etc., methoxy group, ethoxy group, etc. Alkoxy groups having 1 to 6 carbon atoms, halogen atoms such as chlorine and bromine, alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group, cyclohexyloxycarbonyl group, cyano group, t-butyl carbonate, etc. And carbonate ester groups.

In the general formula (1), R ¹ represents an (m + n) -valent organic linking group. m + n satisfies 3-10.
The (m + n) -valent organic linking group represented by R ¹ includes 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to Groups consisting of up to 200 hydrogen atoms and 0 to 20 sulfur atoms are included, which may be unsubstituted or further substituted.

  Specific examples of the (m + n) -valent organic linking group include the following structural units or groups formed by combining the structural units (which may form a ring structure).

  (M + n) -valent organic linking group includes 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 40 oxygen atoms, 1 to 120 hydrogen atoms, And groups consisting of 0 to 10 sulfur atoms are preferred, 1 to 50 carbon atoms, 0 to 10 nitrogen atoms, 0 to 30 oxygen atoms, 1 to 100 More preferred are groups consisting of up to 5 hydrogen atoms and 0 to 7 sulfur atoms, 1 to 40 carbon atoms, 0 to 8 nitrogen atoms, 0 to 20 oxygen atoms. Particularly preferred are groups consisting of 1 to 80 hydrogen atoms and 0 to 5 sulfur atoms.

  Among the above, when the (m + n) -valent organic linking group has a substituent, examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, a phenyl group, and a naphthyl group. Such as an aryloxy group having 6 to 16 carbon atoms, a hydroxyl group, an amino group, a carboxyl group, a sulfonamide group, an N-sulfonylamide group, an acetoxy group and the like, an acyloxy group having 1 to 6 carbon atoms, a methoxy group, an ethoxy group, etc. Alkoxy groups having 1 to 6 carbon atoms, halogen atoms such as chlorine and bromine, alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl groups, ethoxycarbonyl groups, and cyclohexyloxycarbonyl groups, cyano groups, and t-butyl carbonate And the like, and the like.

Specific examples (specific examples (1) to (17)) of the (m + n) -valent organic linking group represented by R ¹ are shown below. However, the present invention is not limited to these.

  Among the above specific examples, the most preferable (m + n) -valent organic linking group is the following group from the viewpoint of availability of raw materials, ease of synthesis, and solubility in various solvents.

In said general formula (1), m represents 1-8. As m, 1-5 are preferable, 1-4 are more preferable, and 1-3 are especially preferable.
Moreover, in said general formula (1), n represents 2-9. As n, 2-8 are preferable, 2-7 are more preferable, and 3-6 are especially preferable.

In the general formula (1), P ¹ represents a polymer skeleton and can be selected from known polymers according to the purpose and the like. The m P ¹ may be the same or different.
Among polymers, in order to constitute a polymer skeleton, a polymer or copolymer of vinyl monomers, ester polymers, ether polymers, urethane polymers, amide polymers, epoxy polymers, silicone polymers, and these Modified product or copolymer [for example, polyether / polyurethane copolymer, copolymer of polyether / vinyl monomer, etc. (any of random copolymer, block copolymer, graft copolymer) May be included). At least one selected from the group consisting of vinyl monomers, selected from the group consisting of polymers or copolymers of vinyl monomers, ester polymers, ether polymers, urethane polymers, and modified products or copolymers thereof. At least one kind is more preferable, and a polymer or copolymer of vinyl monomers is particularly preferable.
Furthermore, the polymer is preferably soluble in an organic solvent. If the affinity with the organic solvent is low, for example, when used as a pigment dispersant, the affinity with the dispersion medium is weakened, and it may not be possible to secure a sufficient adsorption layer for stabilizing the dispersion.

Although it does not restrict | limit especially as said vinyl monomer, For example, (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, (meth) acrylamides Styrenes, vinyl ethers, vinyl ketones, olefins, maleimides, (meth) acrylonitrile, vinyl monomers having an acidic group, and the like are preferable.
Hereinafter, preferable examples of these vinyl monomers will be described.

  Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate. , Isobutyl (meth) acrylate, t-butyl (meth) acrylate, amyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, (Meth) acrylic acid 2-ethylhexyl, (meth) acrylic acid t-octyl, (meth) acrylic acid dodecyl, (meth) acrylic acid octadecyl, (meth) acrylic acid acetoxyethyl, (meth) acrylic acid phenyl, (meth) 2-hydroxyethyl acrylate, (meth) acrylic acid-2-hydroxypropyl, (meth ) Acrylic acid-3-hydroxypropyl, (meth) acrylic acid-4-hydroxybutyl, (meth) acrylic acid 2-methoxyethyl, (meth) acrylic acid 2-ethoxyethyl, (meth) acrylic acid 2- (2- Methoxyethoxy) ethyl, 3-methoxy-2-hydroxypropyl (meth) acrylate, 2-chloroethyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylic acid-3,4-epoxycyclohexylmethyl, (Meth) vinyl acrylate, (meth) acrylic acid-2-phenylvinyl, (meth) acrylic acid-1-propenyl, (meth) acrylic acid allyl, (meth) acrylic acid-2-allyloxyethyl, (meth) Propargyl acrylate, benzyl (meth) acrylate, diethylene glycol (meth) acrylate Methyl ether, (meth) acrylic acid diethylene glycol monoethyl ether, (meth) acrylic acid triethylene glycol monomethyl ether, (meth) acrylic acid triethylene glycol monoethyl ether, (meth) acrylic acid polyethylene glycol monomethyl ether, (meth) acrylic Polyethylene glycol monoethyl ether, β-phenoxyethoxyethyl (meth) acrylate, nonylphenoxy polyethylene glycol (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, (meth ) Trifluoroethyl acrylate, octafluoropentyl (meth) acrylate, perfluorooctyl ethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, Meth) acrylic acid tribromophenyl, (meth) tribromophenyl oxyethyl acrylate, and (meth) acrylic acid -γ- butyrolactone.

Examples of crotonic acid esters include butyl crotonate and hexyl crotonate.
Examples of vinyl esters include vinyl acetate, vinyl chloroacetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate and the like.
Examples of maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.
Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.
Examples of itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

  (Meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and Nn-butyl. Acrylic (meth) amide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N -Diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-nitrophenyl acrylamide, N-ethyl-N-phenyl acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholine, diacetone acrylamide, N- Methylo Acrylamide, N- hydroxyethyl acrylamide, vinyl (meth) acrylamide, N, N- diallyl (meth) acrylamide, such as N- allyl (meth) acrylamide.

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

Examples of vinyl ethers include methyl vinyl ether, ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, octyl vinyl ether, methoxyethyl vinyl ether, and phenyl vinyl ether.
Examples of vinyl ketones include methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.
Examples of olefins include ethylene, propylene, isobutylene, butadiene, isoprene and the like.
Examples of maleimides include maleimide, butyl maleimide, cyclohexyl maleimide, and phenyl maleimide.

  (Meth) acrylonitrile, heterocyclic groups substituted with vinyl groups (for example, vinylpyridine, N-vinylpyrrolidone, vinylcarbazole, etc.), N-vinylformamide, N-vinylacetamide, N-vinylimidazole, vinylcaprolactone, etc. are also used. it can.

  In addition to the above compounds, for example, vinyl monomers having a functional group such as a urethane group, a urea group, a sulfonamide group, a phenol group, and an imide group can also be used. Such a monomer having a urethane group or a urea group can be appropriately synthesized using, for example, an addition reaction between an isocyanate group and a hydroxyl group or an amino group. Specifically, an addition reaction between an isocyanate group-containing monomer and a compound containing one hydroxyl group or a compound containing one primary or secondary amino group, or a hydroxyl group-containing monomer or primary or secondary amino group containing It can be appropriately synthesized by an addition reaction between a monomer and monoisocyanate.

Examples of the vinyl monomer having an acidic group include a vinyl monomer having a carboxyl group and a vinyl monomer having a sulfonic acid group.
Examples of the vinyl monomer having a carboxyl group include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and acrylic acid dimer. Further, addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride, or cyclohexanedicarboxylic anhydride, ω-carboxy-polycaprolactone Mono (meth) acrylates can also be used. Moreover, you may use anhydride containing monomers, such as maleic anhydride, itaconic anhydride, and citraconic anhydride, as a precursor of a carboxyl group. Of these, (meth) acrylic acid is particularly preferred from the viewpoints of copolymerizability, cost, solubility, and the like.

  Examples of the vinyl monomer having a sulfonic acid group include 2-acrylamido-2-methylpropanesulfonic acid, and examples of the vinyl monomer having a phosphoric acid group include phosphoric acid mono (2-acryloyloxyethyl ester) and phosphoric acid mono (1-methyl-2-acryloyloxyethyl ester) and the like.

  Furthermore, a vinyl monomer containing a phenolic hydroxyl group or a vinyl monomer containing a sulfonamide group can be used as the vinyl monomer having an acidic group.

  Among the polymer compounds represented by the general formula (1), the polymer compound represented by the following general formula (2) is preferable.

In the general formula (2), A ² represents an organic dye structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, or 4 or more carbon atoms. Represents a monovalent organic group containing at least one portion selected from a hydrocarbon group, an alkoxysilyl group, an epoxy group, an isocyanate group, and a hydroxyl group. The n A ² may be the same or different.
Incidentally, A ² has the same meaning as the A ¹ in the general formula (1), a preferable embodiment thereof is also the same.

In the general formula (2), R ⁴ and R ⁵ each independently represents a single bond or a divalent organic linking group. The n R ^{4 s} may be the same or different. The m R ^{5 s} may be the same or different.
As the divalent organic linking group represented by R ⁴ and R ⁵ , the same ones as those mentioned as the divalent organic linking group represented by R ² in the general formula (1) are used, The preferred embodiment is also the same.

In the general formula (2), R ³ represents an (m + n) -valent organic linking group. m + n satisfies 3-10.
Examples of the (m + n) -valent organic linking group represented by R ³ include 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to Groups comprising up to 100 hydrogen atoms and 0 to 20 sulfur atoms are included, which may be unsubstituted or further substituted.
Specifically, the (m + n) -valent organic linking group represented by R ³ is the same as the (m + n) -valent organic linking group represented by R ¹ in the general formula (1). The preferred embodiments are the same.

In said general formula (2), m represents 1-8. As m, 1-5 are preferable, 1-4 are more preferable, and 1-3 are especially preferable.
Moreover, in said general formula (2), n represents 2-9. As n, 2-8 are preferable, 2-7 are more preferable, and 3-6 are especially preferable.

Further, P ² in the general formula (2) represents a polymer skeleton and can be selected from known polymers according to the purpose and the like. the m P ² can be the same or different. The preferred embodiment of the polymer is the same as P ¹ in Formula (1).

Among the polymer compounds represented by the general formula (2), those satisfying all of R ³ , R ⁴ , R ⁵ , P ² , m, and n shown below are most preferable.
R ³ : Specific examples (1), (2), (10), (11), (16), or (17)
R ⁴ : A single bond or the following structural unit or a combination of the structural units: “1 to 10 carbon atoms, 0 to 5 nitrogen atoms, 0 to 10 oxygens” A divalent organic linking group comprising an atom, 1 to 30 hydrogen atoms, and 0 to 5 sulfur atoms (which may have a substituent, for example, C1-C20 alkyl group such as methyl group and ethyl group, aryl group having 6 to 16 carbon atoms such as phenyl group and naphthyl group, hydroxyl group, amino group, carboxyl group, sulfonamide group, N-sulfonylamide Groups, acyloxy groups having 1 to 6 carbon atoms such as acetoxy groups, alkoxy groups having 1 to 6 carbon atoms such as methoxy groups and ethoxy groups, halogen atoms such as chlorine and bromine, methoxycarbonyl groups, etho Aryloxycarbonyl group, an alkoxycarbonyl group having from 2 to 7 carbon atoms such as cyclohexyl oxycarbonyl group, a cyano group, carbonate group, such as t- butyl carbonate, and the like.)

R ⁵ : single bond, ethylene group, propylene group, the following group (a), or the following group (b)
In the following groups, R ¹² represents a hydrogen atom or a methyl group, and l represents 1 or 2.

P ² : Polymer or copolymer of vinyl monomer, ester polymer, ether polymer, urethane polymer, and modified products thereof m: 1 to 3
n: 3-6

(Synthesis method)
The polymer compound represented by the general formula (1) (including those represented by the general formula (2)) is not particularly limited, but can be synthesized by the following method.
1. A polymer in which a functional group selected from a carboxyl group, a hydroxyl group, an amino group, or the like is introduced at the terminal; an acid halide having a plurality of the adsorption sites; an alkyl halide having a plurality of the adsorption sites; or a plurality of the adsorption sites. A method of polymerizing the isocyanate and the like.
2. A method in which a polymer having a carbon-carbon double bond introduced at a terminal thereof and a mercaptan having a plurality of the adsorption sites are subjected to a Michael addition reaction.
3. A method of reacting a polymer having a carbon-carbon double bond introduced at a terminal thereof and a mercaptan having the adsorption site in the presence of a radical generator.
4). A method in which a polymer having a plurality of mercaptans introduced at its terminal is reacted with a compound having a carbon-carbon double bond and the adsorption site in the presence of a radical generator.
5. A method of radical polymerizing a vinyl monomer in the presence of a mercaptan compound having a plurality of the adsorption sites.

  Among the above, the (B-1) specific dispersion resin in the present invention is preferably a synthesis method of 2, 3, 4, 5 and more preferably a synthesis method of 3, 4, 5 because of ease of synthesis. In particular, when (B-1) the specific dispersion resin has a structure represented by the general formula (2), it is most preferable to synthesize by the synthesis method 5 in view of ease of synthesis.

  More specifically, the synthesis method 5 is preferably a method in which a vinyl monomer is radically polymerized in the presence of a compound represented by the following general formula (3).

In the general formula (3), R ⁶ , R ⁷ , A ³ , m, and n have the same meanings as R ³ , R ⁴ , A ² , m, and n in the general formula (2), respectively. The preferred embodiment is also the same.

The compound represented by the general formula (3) can be synthesized by the following method or the like, but the following method 7 is more preferable because of ease of synthesis.
6). A method of converting a halide compound having a plurality of adsorption sites into a mercaptan compound (a method of reacting with thiourea and hydrolyzing, a method of reacting directly with NaSH, a method of reacting with CH ₃ COSNa and hydrolyzing, etc.) )
7). Method of addition reaction of a compound having 3 to 10 mercapto groups in one molecule and a compound having the adsorption site and having a functional group capable of reacting with a mercapto group

Preferable examples of the “functional group capable of reacting with a mercapto group” in the synthesis method 7 include acid halides, alkyl halides, isocyanates, and carbon-carbon double bonds.
It is particularly preferable that the “functional group capable of reacting with a mercapto group” is a carbon-carbon double bond, and the addition reaction is a radical addition reaction. The carbon-carbon double bond is more preferably a mono- or di-substituted vinyl group in terms of reactivity with the mercapto group.

  Specific examples of the compound having 3 to 10 mercapto groups in one molecule [specific examples (18) to (34)] include the following compounds.

  Among the above, the following compounds are particularly preferable from the viewpoints of availability of raw materials, ease of synthesis, and solubility in various solvents.

  A compound having the adsorption site and having a carbon-carbon double bond (specifically, an organic dye structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a coordination group) A group having a coordinated oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, and a hydroxyl group; and a carbon-carbon double bond Although it does not restrict | limit especially as a compound which has, The following are mentioned.

  The radical addition reaction product of the “compound having 3 to 10 mercapto groups in one molecule” and the “compound having the adsorption site and having a carbon-carbon double bond” is, for example, The above-mentioned “compound having 3 to 10 mercapto groups in one molecule” and “compound having the adsorption site and having a carbon-carbon double bond” are dissolved in a suitable solvent, It is obtained using a method (thiol-ene reaction method) in which a radical generator is added and added at about 50 ° C. to 100 ° C.

Examples of suitable solvents used in the thiol-ene reaction method include “compound having 3 to 10 mercapto groups in one molecule”, “having the adsorption site, and carbon-carbon double. It can be arbitrarily selected according to the solubility of the “compound having a bond” and the “radical addition reaction product to be produced”.
For example, methanol, ethanol, propanol, isopropanol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, methoxypropyl acetate, ethyl lactate, ethyl acetate, acetonitrile, tetrahydrofuran, dimethylformamide, chloroform, toluene Can be mentioned. These solvents may be used as a mixture of two or more.

  In addition, as radical generators, 2,2′-azobis (isobutyronitrile) (AIBN), 2,2′-azobis- (2,4′-dimethylvaleronitrile), dimethyl 2,2′-azobisisobutyrate An azo compound such as benzoyl peroxide, a peroxide such as benzoyl peroxide, and a persulfate such as potassium persulfate and ammonium persulfate can be used.

The vinyl monomer used in the synthesis method of 5 is not particularly limited, for example, those similar to the vinyl monomers used in obtaining the polymer skeleton represented by P ¹ of the general formula (1) is used It is done.

The above vinyl monomers may be polymerized alone or in combination of two or more.
Further, (B-1) the specific dispersion resin is more preferably copolymerized with a vinyl monomer having one or more acidic groups and a vinyl monomer having no one or more acidic groups.

[(B-2) Polymer containing copolymer units derived from the monomer represented by formula (I): (B-2) Specific dispersion resin]
Next, a polymer containing a copolymer unit derived from a monomer represented by the following general formula (I) (hereinafter, appropriately referred to as “(B-2) specific dispersion resin”) will be described.

In the general formula (I), R ⁰¹ represents a hydrogen atom or a substituted or unsubstituted alkyl group. R ⁰² represents an alkylene group. W represents -CO-, -C (= O) O-, -CONH-, -OC (= O)-, or a phenylene group. X is —O—, —S—, —C (═O) O—, —CONH—, —C (═O) S—, —NHCONH—, —NHC (═O) O—, —NHC (= O) S-, -OC (= O)-, -OCONH-, or -NHCO-. Y represents —NR ⁰³ —, —O—, —S—, or —N═, and is linked to an N atom via an adjacent atomic group to form a cyclic structure. R ⁰³ represents a hydrogen atom, an alkyl group, or an aryl group. m1 and n1 each independently represents 0 or 1.

  Hereinafter, the monomer represented by formula (I), which is an essential copolymer unit of (B-2) the specific dispersion resin in the present invention, will be described in detail.

In the general formula (I), R ⁰¹ represents a hydrogen atom or a substituted or unsubstituted alkyl group.
The alkyl group represented by R ⁰¹ is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and particularly preferably an alkyl group having 1 to 4 carbon atoms.
When the alkyl group represented by R ⁰¹ is a substituted alkyl group, examples of the substituent that can be introduced include a hydroxy group, an alkoxy group, an aryloxy group, an acyloxy group, and a halogen group.
Specifically, preferred examples of the alkyl group represented by R ⁰¹ include methyl group, ethyl group, propyl group, n-butyl group, i-butyl group, t-butyl group, n-hexyl group, cyclohexyl group, 2-hydroxy group. Examples thereof include an ethyl group, a 3-hydroxypropyl group, a 2-hydroxypropyl group, and a 2-methoxyethyl group.

R ⁰² represents an alkylene group.
The alkylene group represented by R ⁰² is preferably an alkylene group having 1 to 12 carbon atoms, more preferably an alkylene group having 1 to 8 carbon atoms, and particularly preferably an alkylene group having 1 to 4 carbon atoms.
The alkylene group represented by R ⁰² may have a substituent when it can be introduced, and examples of the substituent include a hydroxy group, an alkoxy group, an aryloxy group, an acyloxy group, and the like. It is done.
Specific examples of the preferable alkylene group represented by R ⁰² include a methylene group, an ethylene group, a propylene group, a trimethylene group, and a tetramethylene group.

  W represents —CO—, —C (═O) O—, —CONH—, —OC (═O) —, or a phenylene group, and is —C (═O) O— or —CONH—. Is preferred.

Y represents —NR ⁰³ —, —O—, —S—, or —N═, and is linked to an N atom via an adjacent atomic group to form a cyclic structure.
R ⁰³ represents a hydrogen atom, an alkyl group, or an aryl group, and is preferably a hydrogen atom or a methyl group.
Y is particularly preferably -S-, -NH-, or -N =.

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

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

  m1 and n1 each independently represents 0 or 1, and it is particularly preferable that both m1 and n1 are 1.

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

  The specific dispersion resin (B-2) in the present invention is further ethylenically terminated with a copolymer unit derived from the monomer represented by the general formula (I) from the viewpoint of imparting dispersion stability of the pigment. A graft copolymer containing a copolymer unit derived from a polymerizable oligomer having an unsaturated bond is particularly preferred.

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

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

Moreover, it is preferable that this macromonomer has the number average molecular weight (Mn) of polystyrene conversion in the range of 1000-10000, and the range of 2000-9000 is especially preferable.
The polymer chain portion is a homopolymer or copolymer formed from at least one monomer selected from the group consisting of alkyl (meth) acrylate, styrene and derivatives thereof, acrylonitrile, vinyl acetate and butadiene, or polyethylene oxide. Polypropylene oxide and polycaprolactone are generally used.

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

In general formula (II), R ¹¹ and R ¹³ each independently represent a hydrogen atom or a methyl group.
R ¹² represents a linking group containing an alkylene group having 1 to ¹² carbon atoms, and the linking group may be an alkylene group having 1 to 12 carbon atoms, or a plurality of the alkylene groups may be ester bonds or ethers. It may be linked via a bond, an amide bond or the like. R ¹² is preferably a group in which an alkylene group having 1 to 4 carbon atoms or an alkylene group having 1 to 4 carbon atoms is linked by breaking an ester bond. The alkylene group represented by R ¹² may further have a substituent (for example, a hydroxyl group).
Y ¹¹ represents a phenyl group having no substituent, a phenyl group having one alkyl group having 1 to 4 carbon atoms, or —COOR ¹⁴ . Here, R ¹⁴ represents an alkyl group having 1 to 6 carbon atoms, a phenyl group, or an arylalkyl group having 7 to 10 carbon atoms. Y is preferably a phenyl group or —COOR ¹⁴ where R ¹⁴ represents an alkyl group having 1 to 12 carbon atoms.
q represents an integer of 20 to 200.

  Preferred examples of the polymerizable oligomer (macromonomer) that can be used in the synthesis of the (B-2) specific dispersion resin in the present invention include polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and poly-i-. A polymer in which a (meth) acryloyl group is bonded to one molecular end of butyl (meth) acrylate or polystyrene can be exemplified. As such polymerizable oligomers available on the market, one-end methacryloylated polystyrene oligomer (Mn = 6000, trade name: AS-6, manufactured by Toagosei Chemical Co., Ltd.), one-end methacryloylated polymethyl methacrylate oligomer ( Mn = 6000, trade name: AA-6, manufactured by Toa Gosei Chemical Co., Ltd.) and one-terminal methacryloylated poly-n-butyl acrylate oligomer (Mn = 6000, trade name: AB-6, Toa Gosei Chemical Co., Ltd.) ) Made).

In order to obtain a specific acid value, the (B-2) specific dispersion resin according to the present invention preferably further includes a copolymer unit derived from a monomer having an acid group.
Monomers having an acid group include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid; maleic acid, maleic anhydride, fumaric acid, itaconic acid, anhydrous Unsaturated dicarboxylic acids such as itaconic acid, citraconic acid, citraconic anhydride and mesaconic acid or their anhydrides; trivalent or higher unsaturated polycarboxylic acids or their anhydrides; succinic acid mono (2-acryloyloxyethyl) ), Succinic acid mono (2-methacryloyloxyethyl), phthalic acid mono (2-acryloyloxyethyl), phthalic acid mono (2-methacryloyloxyethyl) mono [2- (Meth) acryloyloxyalkyl] esters; ω-carboxy-polycaprolactone monoacrylate, ω-carboxy-polycaprolactone monoacrylate Mono (meth) acrylates such as both terminal carboxy polymers methacrylate and the like.

The (B-2) specific dispersion resin according to the present invention may further contain a copolymerizable vinyl monomer as a copolymer component as long as the effect is not impaired.
Although it does not restrict | limit especially as a vinyl monomer which can be used here, For example, (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, ( Preference is given to (meth) acrylamides, vinyl ethers, esters of vinyl alcohol, styrenes, (meth) acrylonitrile and the like. Specific examples of such vinyl monomers include the following compounds.

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

  Specific examples (B-2) of specific dispersion resins [Exemplary Compound 1 to Exemplified Compound 16] that can be suitably used in the colored pattern forming composition of the present invention are listed below together with their weight average molecular weights. It is not limited to.

Exemplary compound (1): monomer M-2 / methacrylic acid / terminated methacryloylated polymethyl methacrylate copolymer (10/25/65 mass%, weight average molecular weight 50000, acid value 163 mg / g)
Exemplary compound (2): Monomer M-2 / methacrylic acid / terminated methacryloylated polymethyl methacrylate copolymer (10/15/75% by mass, weight average molecular weight 35000, acid value 98 mg / g)
Exemplary compound (3): monomer M-3 / methacrylic acid / 2-hydroxyethyl methacrylate / terminal methacryloylated polymethyl methacrylate copolymer (5/5/10/80 mass%, weight average molecular weight 40000, acid (Value 33 mg / g)
Illustrative compound (4): monomer M-3 / methacrylic acid / benzyl methacrylate copolymer / terminal methacryloylated polymethyl methacrylate copolymer (15/10/10/65 mass%, weight average molecular weight 60000, acid (Value 65 mg / g)
Exemplary compound (5): monomer M-4 / methacrylic acid / terminated methacryloylated polymethyl methacrylate copolymer (10/30/60 mass%, weight average molecular weight 80000, acid value 195 mg / g)

Exemplary compound (6): monomer M-4 / methacrylic acid / terminated methacryloylated polymethyl methacrylate copolymer (10/15/75 mass%, weight average molecular weight 20000, acid value 98 mg / g)
Exemplary compound (7): Monomer M-5 / acrylic acid / terminal methacryloylated polymethyl methacrylate copolymer (25/15/60 mass%, weight average molecular weight 60000, acid value 117 mg / g)
Exemplary compound (8): Monomer M-5 / acrylic acid / terminated methacryloylated polybutyl acrylate copolymer (15/5/80 mass%, weight average molecular weight 45000, acid value 39 mg / g)
Illustrative compound (9): monomer M-6 / acrylic acid / 2-hydroxyethyl methacrylate / terminal methacryloylated polymethyl methacrylate copolymer (15/10/5/70 mass%, weight average molecular weight 80,000, acid (Value 78 mg / g)
Exemplary Compound (10): Monomer M-6 / Acrylic acid / Terminal methacryloylated polymethyl methacrylate copolymer (12/18/70 mass%, weight average molecular weight 50000, acid value 140 mg / g)

Exemplary compound (11): monomer M-7 / methacrylic acid / terminated methacryloylated polymethyl methacrylate copolymer (10/18/72% by mass, weight average molecular weight 15000, acid value 117 mg / g)
Illustrative compound (12): monomer M-7 / methacrylic acid / benzyl methacrylate / methoxypolyethylene glycol methacrylate copolymer (10/10/50/30 mass%, weight average molecular weight 50000, acid value 65 mg / g)
Illustrative compound (13): monomer M-10 / acrylic acid / 2-hydroxyethyl methacrylate / terminal methacryloylated polystyrene copolymer (5/35/10/50 mass%, weight average molecular weight 20000, acid value 272 mg) / G)
Exemplary compound (14): monomer M-10 / methacrylic acid / terminated methacryloylated polymethyl methacrylate copolymer (10/12/78 mass%, weight average molecular weight 10,000, acid value 78 mg / g)
Exemplary compound (15): monomer M-10 / acrylic acid / methoxypolyethylene glycol methacrylate copolymer (15/3/82 mass%, weight average molecular weight 15000, acid value 23 mg / g)
Exemplary compound (16): monomer M-13 / methacrylic acid / terminated methacryloylated polymethyl methacrylate copolymer (10/25/65 mass%, weight average molecular weight 20000, acid value 163 mg / g)

[(B-3) Polymer containing structural unit represented by general formula (a): (B-3) specific dispersion resin]
Subsequently, a polymer containing a structural unit represented by the following general formula (a) (hereinafter, appropriately referred to as “(B-3) specific dispersion resin”) will be described.

In the general formula (a), R ^1a represents hydrogen or a methyl group, R ^2a represents an alkylene group, and Z ¹ represents a nitrogen-containing heterocyclic structure.
^Examples of the alkylene group represented by R ^2a include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a hexamethylene group, a 2-hydroxypropylene group, a methyleneoxy group, an ethyleneoxy group, a methyleneoxycarbonyl group, a methylenethio group, Among them, a methylene group, a methyleneoxy group, a methyleneoxycarbonyl group, and a methylenethio group are preferable.

In the general formula (a), Z ¹ represents a nitrogen-containing heterocyclic structure, specifically, for example, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyrrole ring, an imidazole ring, a triazole ring, a tetrazole ring, an indole ring, Examples thereof include quinoline ring, acridine ring, phenothiazine ring, phenoxazine ring, acridone ring, anthraquinone ring, benzimidazole structure, benztriazole structure, benzthiazole structure, cyclic amide structure, cyclic urea structure, and cyclic imide structure.
Among these, the nitrogen-containing heterocyclic structure represented by Z ¹ is preferably a structure represented by the following general formula (b) or general formula (c).

In the general formula (b), X ¹ represents a single bond, an alkylene group (for example, a methylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, etc.), —O—, —S—, —NR—, and , -C (= O)-. Here, R represents a hydrogen atom or an alkyl group, and examples of the alkyl group when R represents an alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and an n-butyl group. , T-butyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, n-octadecyl group and the like.
Among these, X ¹ is preferably a single bond, a methylene group, —O— or —C (═O) —, and particularly preferably —C (═O) —.

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

  Preferred specific examples of the structural unit represented by the general formula (a) [Exemplary structural units (M′-1) to (M′-7)] are listed below, but the present invention is not limited thereto. .

The structural unit represented by the general formula (a) is preferably contained in the specific dispersed resin (B-3) in an amount of 2 to 50% by mass, more preferably 4 to 30% by mass, and more preferably 5 to 20%. It is particularly preferable that it be contained by mass%.
The (B-3) specific dispersion resin in the present invention is a graft containing, in addition to the structural unit represented by the general formula (a), a polymerizable oligomer having an ethylenically unsaturated double bond at the terminal as a copolymer unit. A copolymer is particularly preferred.
Examples of the polymerizable oligomer having an ethylenically unsaturated double bond at the terminal include those similar to the polymerizable oligomer used as a copolymerization component in the above-mentioned (B-2) specific dispersion resin. The same applies to (oligomer represented by formula (II)) and preferred examples (specific examples).

In order to obtain a specific acid value, the (B-3) specific dispersion resin in the present invention preferably further contains a monomer having an acid group (structural unit) as a copolymerization component.
Examples of the monomer having an acid group include (meth) acrylic acid, p-vinylbenzoic acid, maleic acid, fumaric acid, itaconic acid, succinic anhydride adduct of 2-hydroxyethyl (meth) acrylate, (meth) And phthalic anhydride adduct of 2-hydroxyethyl acrylate.

The (B-3) specific dispersion resin in the present invention may further contain a copolymerizable vinyl monomer as a copolymer component as long as the effect is not impaired.
Examples of the vinyl monomer that can be used here include the same vinyl monomers used as the copolymerization component in the above-mentioned (B-2) specific dispersion resin, and preferred examples thereof are also the same.

  In addition, as a preferable aspect of the specific dispersion resin according to the present invention, polymerization containing 2 to 50% by mass of the structural unit represented by the general formula (a) and further having an ethylenically unsaturated double bond at the terminal Preferred examples include a copolymer containing 10 to 90% by mass of a functional oligomer, 1 to 30% by mass of a structural unit having an acid group, and 0 to 20% by mass of a vinyl monomer.

  Specific examples (B-3) of specific dispersion resins [Exemplary compounds (I) to (XV)] that can be suitably used for the colored pattern forming composition of the present invention are listed below together with their weight average molecular weights. Is not limited to these.

Exemplary Compound (I): Monomer / Methacrylic Acid / Terminal Methacryloylated Polymethyl Methacrylate Copolymer (Copolymerization Ratio = 10/4/86 Mass%, Weight) that can Form the Exemplary Structural Unit (M′-1) (Average molecular weight 50000, acid value 26 mg / g)
Exemplary Compound (II): Monomer / Methacrylic Acid / Terminal Methacryloylated Polymethyl Methacrylate Copolymer (10/33/57% by Mass, Weight Average Molecular Weight 30000, Forming the Exemplary Structural Unit (M′-1)) Acid value 214mg / g)
Exemplary Compound (III): Monomer / Methacrylic Acid / 2-Hydroxyethyl Methacrylate / Terminal Methacryloylated Polymethyl Methacrylate Copolymer (5/28/10 /) that can Form the Exemplary Structural Unit (M′-1) 57 mass%, weight average molecular weight 40000, acid value 182 mg / g)
Exemplary compound (IV): monomer capable of forming the exemplary structural unit (M′-1) / methacrylic acid / benzyl methacrylate copolymer / terminal methacryloylated polymethyl methacrylate copolymer (15/5/10 / 70 mass%, weight average molecular weight 60000, acid value 33 mg / g)
Exemplary Compound (V): Monomer / Methacrylic Acid / Terminal Methacryloylated Polymethyl Methacrylate Copolymer (20/20/60% by Mass, Weight Average Molecular Weight 80000, Forming the Exemplary Structural Unit (M′-5) Acid value 130mg / g)

Exemplary Compound (VI): Monomer / Methacrylic Acid / Terminal Methacryloylated Polymethyl Methacrylate Copolymer (10/20/70% by Mass, Weight Average Molecular Weight 30000, Forming the Exemplary Structural Unit (M′-5) Acid value 130mg / g)
Exemplary compound (VII): monomer / acrylic acid / terminal methacryloylated polymethyl methacrylate copolymer (25/20/55 mass%, weight average molecular weight 60000, which can form the exemplary structural unit (M′-5) Acid value 156 mg / g)
Exemplary compound (VIII): monomer / acrylic acid / terminated methacryloylated polybutyl acrylate copolymer (15/15/70% by mass, weight average molecular weight 40000, which can form the exemplary structural unit (M′-5) Acid value 117mg / g)
Exemplary Compound (IX): Monomer / Acrylic Acid / 2-Hydroxyethyl Methacrylate / Terminal Methacryloylated Polymethyl Methacrylate Copolymer (15/5/5 /) capable of Forming the Exemplary Structural Unit (M′-5) 75% by mass, weight average molecular weight 80000, acid value 39 mg / g)
Exemplary Compound (X): Monomer / Methacrylic Acid / Terminal Methacryloylated Polymethyl Methacrylate Copolymer (12/17/71% by Mass, Weight Average Molecular Weight 50000, Forming the Exemplary Structural Unit (M′-6)) Acid value 110mg / g)

Exemplary Compound (XI): Monomer / Methacrylic Acid / Terminal Methacryloylated Polymethyl Methacrylate Copolymer (10/12/78% by Mass, Weight Average Molecular Weight 20000, which can Form Exemplary Structural Unit (M′-6)) Acid value 78 mg / g)
Exemplary Compound (XII): Monomer / Methacrylic Acid / Benzyl Methacrylate / Methoxypolyethylene Glycol Methacrylate Copolymer (10/10/50/30% by Weight, Can Form the Exemplary Structural Unit (M′-6)) (Average molecular weight 35000, acid value 65 mg / g)
Exemplary Compound (XIII): Monomer / Acrylic Acid / 2-Hydroxyethyl Methacrylate / Terminal Methacryloylated Polystyrene Copolymer (5/5/10/80 Mass) that can Form the Exemplary Structural Unit (M′-6) %, Weight average molecular weight 20000, acid value 39 mg / g)
Exemplary Compound (XIV): Monomer / Methacrylic Acid / Methyl Methacrylate / Terminal Methacryloylated Polymethyl Methacrylate Copolymer (8/12/10/70% by Mass) that can Form the Exemplary Structural Unit (M′-7) , Weight average molecular weight 70000, acid value 78 mg / g)
Exemplary compound (XV): monomer / acrylic acid / methoxypolyethylene glycol methacrylate copolymer (15/20/65% by mass, weight average molecular weight 15000, acid value) capable of forming the exemplary structural unit (M′-7) 156 mg / g)

  The copolymer as described above, which is (B-3) the specific dispersion resin in the present invention, is a monomer that can be a structural unit represented by the general formula (a), a polymerizable oligomer used in combination as desired, Other monomers can be obtained by radical polymerization in a solvent. In this radical polymerization, the same radical polymerization initiator and chain transfer agent as those used when (B-2) the specific dispersion resin is synthesized are used.

  As content of (B) polymer dispersing agent in the curable composition for colored pixel formation of this invention, 5-35 mass% is preferable with respect to the total solid (mass) of this composition, 10- 30 mass% is more preferable. (B) When the content of the polymer dispersant is within the above range, (A-1) the dispersion time of the pigment used as the colorant can be shortened, and the stability after dispersion is kept long. Therefore, it is preferable.

[Other dispersants]
The composition for forming a colored pattern of the present invention can be used in combination with a conventionally known dispersant (pigment dispersant) in addition to the (B) dispersion resin.

Known dispersants (pigment dispersants) include polymer dispersants [for example, polyamidoamines and salts thereof, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, modified poly (meth) acrylates, (meth) acrylic types. Copolymers], polyoxyethylene alkyl phosphate esters, polyoxyethylene alkyl amines, alkanol amines, pigment derivatives, and the like.
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 known dispersants (pigment dispersants) that can be used in the present invention include "Disperbyk-107 (carboxylic acid ester), 130 (polyamide), 161, 162, 163, 164, 165, 166" manufactured by BYK Chemie. , 170 (polymer copolymer) ”,“ EFKA 4047, 4050, 4010, 4165 (polyurethane type), EFKA 4330, 4340 (block copolymer), 4400, 4402 (modified polyacrylate), 5010 (polyesteramide) manufactured by EFKA ), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative) "," Ajisper PB821, PB822 "manufactured by Ajinomoto Fine Techno Co., Ltd.," Floren TG-710 (urethane oligomer) "manufactured by Kyoeisha Chemical Co., Ltd., Poly Low No. 50E, No. 300 (acrylic copolymer) ”,“ Dispalon # 7004 (polyetherester), DA-703-50, DA-705, DA-725 ”manufactured by Enomoto Kasei Co., Ltd.,“ “Emulgen 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether)”, “acetamine 86 (stearylamine acetate)”, “Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyester) manufactured by Lubrizol Corporation Amine), 3000, 17000, 27000 (polymer having a functional part at the end), 24000, 28000, 32000, 38500 (graft type polymer) "," Nikkor T106 (polyoxyethylene sorbitan monooleate) "manufactured by Nikko Chemical Co., Ltd. , M YS-IEX (polyoxyethylene monostearate) ”and the like.

  The above-mentioned known dispersing agent can be used in the range of 10 to 100% by mass, that is, 1/10 to 1/1 (equivalent) with respect to the dispersion resin (B) as necessary.

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

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

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

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

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

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

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

^{_{CH 2 = C (R 4)}} COOCH 2 CH (R 5) OH (V)
(However, R ⁴ and R ⁵ represent H or CH _3. )

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

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

About these polymerizable compounds, the details of usage such as the structure, single use or combination, addition amount, etc. can be arbitrarily set according to the performance design of the final photosensitive material. For example, it is selected from the following viewpoints.
From the viewpoint of sensitivity, a structure having a large unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. Further, in order to increase the strength of the 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, it is preferable to use a compound containing two or more (meth) acrylic acid ester structures, more preferably a compound containing three or more, and most preferably a compound containing four or more. preferable. 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 an important factor for compatibility and dispersibility with other components in the polymerizable layer (for example, binder polymer, initiator, colorant (pigment, dye, etc.)). For example, the compatibility may be improved by using a low-purity compound or a combination of two or more types, and a specific structure may be used for the purpose of improving the adhesion of the substrate and an overcoat layer described later. It can also be selected.

  From the above viewpoints, bisphenol A diacrylate, modified bisphenol A diacrylate EO, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate Acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxy D (I) Isocyanurate, pentaerythritol tetraacrylate EO modified product, dipentaerythritol hexaacrylate EO modified product, etc. are mentioned as preferable ones. Also, as commercially available products, urethane oligomer UAS-10, UAB-140 (Sanyo Kokusaku Pulp Co., Ltd.) Manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, and AI-600 (manufactured by Kyoeisha) are preferred.

  Among them, bisphenol A diacrylate EO modified product, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, pentaerythritol tetraacrylate EO modified product, Dipentaerythritol hexaacrylate EO modified products such as DPHA (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (Kyoeisha) Manufactured) is more preferable.

  (C) The content of the polymerizable compound is preferably 5 to 50% by mass and more preferably 7 to 40% by mass in the total solid content of the curable composition for forming colored pixels of the present invention. More preferably, it is 10-35 mass%.

<(D) Photopolymerization initiator>
The curable composition for forming colored pixels of the present invention contains (D) a photopolymerization initiator.
The photopolymerization initiator in the present invention is a compound that is decomposed by light and initiates and accelerates the polymerization of the polymerizable compound (C), and preferably has absorption in a wavelength region of 300 to 500 nm. Moreover, a photoinitiator can be used individually or in combination of 2 or more types.

  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 include rubiimidazole compounds, organic boric acid compounds, disulfonic acid compounds, oxime ester compounds, onium salt compounds, and acylphosphine (oxide) compounds.

  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. Hutt “Journal of Heterocyclic Chemistry” 1 (No 3), (1970) ”, and the oxazole compound and s-triazine compound substituted with a trihalomethyl group.

Hereinafter, the s-triazine compound which is a preferable polymerization initiator in the present invention will be described in detail.
More preferably, the s-triazine compound is 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, 4- (o-bromo-pN) , N- (diethoxycarbonylamino) -phenyl) -2,6-di (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, etc. It is done.

  As a photopolymerization initiator of a halomethyl-s-triazine compound, 4- (p-aminophenyl) -2 as represented by the following general formula (DA) described in JP-A-11-323057 is further included. , 6-Di-halomethyl-s-triazine compound, vinyl-halomethyl-s-triazine compound represented by the following general formula (D-B) described in JP-B-59-1281, and JP-A-53 Suitable examples include 2- (naphth-1-yl) -4,6-bis-halomethyl-s-triazine compound represented by the following general formula (DC) described in JP-A-133428.

In the general formula (DA), R ¹ and R ² are each independently a hydrogen atom, an alkyl group, an aryl group, or the following general formula (DA-1) or general formula (DA-A- The substituent shown by 2) is represented. R ³ and R ⁴ each independently represents a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group. X and Y each independently represent -Cl and -Br, and m and n each represents 0, 1 or 2.

In general formula (D-A-1) and the general formula ^(D-A-2), R 5, R 6, R 7 each independently represent an alkyl group, or an aryl group.
In the general formula (DA) to general formula (DA-2), the alkyl group and aryl group represented by R ^{1 to} R ⁷ may further have a substituent and can be introduced. Examples of such substituents include aryl groups such as phenyl groups, halogen atoms, alkoxy groups, carboalkoxy groups, carboaryloxy groups, acyl groups, nitro groups, dialkylamino groups, and sulfonyl derivatives.
In the general formula (DA), R ¹ and R ² may form a ring structure composed of a nonmetallic atom together with the nitrogen atom bonded thereto, and the ring structure formed in that case is shown below. Things.

  Specific examples of the compound represented by the general formula (DA) include 4- [pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-. Triazine, 4- [o-methyl-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [pN, N-di ( Chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-methyl-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -S-triazine, 4- (p-N-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (p-N-ethoxycarbonylmethylaminophenyl) -2,6- (Trichloromethyl) -s-triazine, 4- [pN, N-di (phenyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (pN-chloroethylcarbonyl) Aminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- [pN- (p-methoxyphenyl) carbonylaminophenyl] 2,6-di (trichloromethyl) -s-triazine, 4 -[M-N, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-bromo-pN, N-di (ethoxycarbonylmethyl) ) Aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-chloro-pN, N-di (ethoxycarbonylmethyl) aminophenyl -2,6-di (trichloromethyl) -s-triazine, 4- [m-fluoro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s- Triazine, 4- [o-bromo-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-chloro-pN, N-di (ethoxycarbonylmethyl) aminophenyl-2,6-di (trichloromethyl) -s-triazine,

4- [o-fluoro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-bromo-pN, N- Di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-chloro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloro Methyl) -s-triazine, 4- [o-fluoro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-bromo-p -N, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-chloro-pN, N-di (chloroethyl) aminophenyl] -2, 6-di (trick (Romethyl) -s-triazine, 4- [m-fluoro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (m-bromo-p -N-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-chloro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) ) -S-triazine, 4- (m-fluoro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN-ethoxy) Carbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-chloro-pN-ethoxycarbonylmethylamino) Nyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-fluoro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4 -(M-bromo-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-chloro-pN-chloroethylaminophenyl) -2,6 -Di (trichloromethyl) -s-triazine, 4- (m-fluoro-p-N-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-p -N-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-chloro-pN-chloroethylaminophenyl) -2,6-di (trichloro Methyl) -s-triazine, 4- (o-fluoro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, and the like.

In the general formula (D-B), Q ³ represents Br or Cl, and P represents —CQ ³ , —NH ₂ , —NHR, —N (R) ₂ , or —OR (where R is a phenyl group or Alkyl group). W represents an aromatic ring, a heterocyclic ring, or a substituent represented by the following general formula (DB-1), which may further have a substituent, and in the general formula (DB-1), Z Is —O— or —S—, and R represents a phenyl group or an alkyl group.
Specific examples of the compound represented by the general formula (D-B) include 2,4-bis (trichloromethyl) -6-p-methoxystyryl-s-triazine, 2,4-bis (trichloromethyl). ) -6- (1-p-dimethylaminophenyl-1,3-butadienyl) -s-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyryl-s-triazine, and the like.

In general formula (D-C), X and Y each independently represent -Br or -Cl, and m and n are integers of 0 to 3. R ′ is a substituent represented by the general formula (D-C-1), wherein R ¹ represents a hydrogen atom or —OR ^c , where R ^c is an alkyl group, a cycloalkyl group, an alkenyl Represents a group or an aryl group. R ² represents —Cl, —Br, an alkyl group, an alkenyl group, an aryl group, or an alkoxy group.

  Specific examples of the compound represented by the general formula (D-C) include 2- (naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-methoxy). -Naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-ethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-Butoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2-methoxyethyl) -naphth-1-yl] -4,6-bis- Trichloromethyl-s-triazine, 2- [4- (2-ethoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2-butoxyethyl) -Naphtho-1-yl] -4,6-bis Trichloromethyl-s-triazine, 2- (2-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-methoxy-5-methyl-naphth-2-yl) ) -4,6-bis-trichloromethyl-s-triazine, 2- (6-methoxy-naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (5-methoxy-naphtho) -1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4,7-dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-Ethoxy-naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4,5-dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl- s-to Azine, and the like.

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

  In addition, preferred examples of other triazine-based initiators include compounds represented by the following general formula (DD).

In General Formula (DD), R ¹ represents a hydrogen atom, a hydroxy group, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms, and m is an integer of 1 to 3. Here, when m is 2 or 3, a plurality of R ¹ may be the same or different from each other.
Specific examples of the compound represented by the general formula (DD) include, for example, 1,3-bistrichloromethyl-5-benzooxorantriadine, 1,3-bistrichloromethyl-5- (5-methylbenzo). Oxolane) triazine, 1,3-bistrichloromethyl-5- (6-methoxybenzooxolane) triazine, 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 phenylketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl- (p-isopropylphenyl) ketone, 1-hydroxy -1- (p-dodecylphenyl) ketone, 2-methyl-1- (4 ′-(methylthio) phenyl) -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-mol Forinophenyl) -butanone-1,2,4,6 trimethylbenzoyl-diphenyl-phosphine oxide, 1,1,1-trichloromethyl- (p-butylphenyl) ketone, 2-benzyl-2-dimethylamino-4 -Acetophenone derivatives such as morpholinobyrophenone, thioxanthone derivatives such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, Examples thereof include benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate.

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

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

  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-butylperoxide). Oxy) cyclohexane, 2,2-bis (tert-butylperoxy) butane, tert-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroper Oxide, 1,1,3,3-tetramethylbutyl hydroperoxide, tert-butylcumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, 2 , -Oxanoyl peroxide, succinic peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate , Dimethoxyisopropyl peroxycarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, tert-butyl peroxyacetate, tert-butyl peroxypivalate, tert-butyl peroxyneodecanoate, tert- Butyl peroxyoctanoate, tert-butyl peroxylaurate, tersyl carbonate, 3,3 ′, 4,4′-tetra- (t-butylperoxycarbonyl) benzophenone, 3,3 ′, 4 '-Tetra- (t-hexylperoxycarbonyl) benzophenone, 3,3', 4,4'-tetra- (p-isopropylcumylperoxycarbonyl) benzophenone, carbonyldi (t-butylperoxydihydrogen diphthalate) , Carbonyldi (t-hexylperoxydihydrogen 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-bis-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-pentaful Lophen-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'-tetra (m-methoxyphenyl) biidazole, 2,2'-bis (o, o'-dichlorophenyl) -4,4', 5,5 '-Tetraphenylbi Dazole, 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 ester 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. Specific examples include Irgacure OXE-01 and OXE-02 manufactured by Ciba Specialty Chemicals.

  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 is preferably substituted with two or more electron donating groups such as an alkyl group, an alkoxy group, and an aryloxy group from the viewpoint of stability. . 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 in which the triarylsulfonium salt has an allyloxy group or an arylthio group as a substituent and has 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. Curing ASIA, p478 Tokyo, Oct (1988), and onium salts such as arsonium salts.

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

  As the photopolymerization initiator (D) used in the present invention, from the viewpoint of exposure sensitivity, a trihalomethyltriazine compound, a benzyldimethyl ketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound, phosphine Oxide compounds, metallocene compounds, oxime compounds, triallylimidazole dimers, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyl oxa Compounds selected from the group consisting of diazole compounds and 3-aryl substituted coumarin compounds are preferred.

  More preferred are trihalomethyltriazine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, oxime compounds, triallylimidazole dimers, onium compounds, benzophenone compounds, acetophenone compounds, and trihalo compounds. Most preferred is at least one compound selected from the group consisting of a methyltriazine compound, an α-aminoketone compound, an oxime compound, a triallylimidazole dimer, and a benzophenone compound.

  The content of the (D) photopolymerization initiator contained in the curable composition of the present invention is preferably 0.1 to 50% by mass, more preferably 0, based on the total solid content of the curable composition. 0.5 to 30% by mass, particularly preferably 1 to 20% by mass. Within this range, good sensitivity and pattern formability can be obtained.

<(E) Solvent>
The colored pixel forming curable composition of the present invention can be generally prepared using a solvent.
Solvents include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, lactic acid Ethyl, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. 3-oxypropionic acid alkyl esters (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate), methyl 2-oxypropionate, -2-oxypropionic acid alkyl esters such as ethyl oxypropionate and propyl 2-oxypropionate (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 2-ethoxypropion) Acid methyl, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2-methyl Ethyl propionate, etc.), and methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, 1,3-butanediol diacetate and the like;
Ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl Ether acetate, propylene glycol propyl ether acetate, diethylene glycol diethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, propylene glycol n -Propyl ether acetate, propylene glycol diacetate, propylene glycol n-butyl ether acetate, propylene glycol phenyl ether, propylene glycol phenyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol n-propyl ether acetate, dipropylene glycol n-butyl ether Acetate, tripropylene glycol mono n-butyl ether, tripropylene glycol methyl ether acetate, etc .;
Ketones such as acetone, methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone;
Alcohols such as ethanol, isopropyl alcohol, propylene glycol methyl ether, propylene glycol mono n-propyl ether, propylene glycol mono n-butyl ether,
Aromatic hydrocarbons such as toluene, xylene and the like can be mentioned.

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

[Curable composition for light shielding part and light shielding part formation]
Next, the light shielding part (black matrix) in the color filter of the present invention will be described.
The light shielding part preferably has an optical density (OD value) of 4.5 or more and 8.0 or less, more preferably 4.8 or more, and still more preferably 5.0 to 7.0. When the optical density is less than 4.5, the display quality of the display device such as a reduction in contrast is lowered. In addition, the optical density said here means the optical density (OD value) measured by the method of an Example description.
Moreover, it is preferable from a viewpoint of the brightness ensuring by high aperture ratio that a light-shielding part is 5-15 micrometers in width. The thickness of the light shielding part is 0.2 to 1.5 μm, more preferably 0.3 to 1.0 μm, and still more preferably 0.3 to 0.8 μm. In this thickness range, the unevenness of the substrate provided with the light shielding portion, that is, the step between the formation region of the light shielding portion and the non-formation region is appropriately maintained. In addition, pixels can be formed with high accuracy.

[Curable composition for light shielding part formation]
The light-shielding part in the color filter of the present invention contains (A-2) a light-shielding agent, (B) a polymer dispersant, (C) a polymerizable compound, (D) a polymerization initiator, and (E) a solvent. As a solid filter, it is formed of a curable composition for forming a color filter light-shielding part containing 40 to 80% by mass in terms of solid content or 50 to 90% by mass of metal-based fine particles.
<(A-2) Shading agent>
Here, as the (A-2) light-shielding agent, carbon black, titanium black, metal fine particles, metal oxides, sulfide fine particles and the like are preferably mentioned.
These are used singly or in combination as required. For example, carbon black alone, metal fine particles alone, a combination of both, or a mode in which other coloring pigments and titanium carbon are used in combination with these are also included.
As a light-shielding material, conventionally, a black colorant has been used in combination with at least two pigments so as to shield the visible light region. Examples of these pigments include the pigments described in JP-A-2005-17716 [0038] to [0040] and JP-A-2005-17521 [0080] to [0088]. The formation of the used light shielding layer is disclosed in JP-A-7-271020. However, when the pigment was used for the light shielding layer, sufficient shielding properties could not be obtained.
In order to increase the light shielding effect, in Japanese Patent Application Laid-Open Nos. 2000-147240, 2000-143985, 2005-338328, and 2006-1544949, carbon black, titanium black, graphite, or the like is preferable as the light-shielding material. Has been developed. In the present invention, carbon black is preferable as one of the light shielding materials from the viewpoint of light shielding properties and cost.

  As an example of carbon black, pigment black 7 (carbon black) is preferable. Examples of the carbon black include carbon black # 2400, # 2350, # 2300, # 2200, # 1000, # 980, # 970, # 960, # 950, # 900, # 850, MCF88, #M manufactured by Mitsubishi Chemical Corporation. 650, MA600, MA7, MA8, MA11, MA100, MA220, IL30B, IL31B, IL7B, IL11B, IL52B, # 4000, # 4010, # 55, # 52, # 50, # 47, # 45, # 44, # 40 , # 33, # 32, # 30, # 20, # 10, # 5, CF9, # 3050, # 3150, # 3250, # 3750, # 3950, Diamond Black A, Diamond Black N220M, Diamond Black N234, Diamond Black I, Diamond Black LI, Diamond Black II, Diamond Black N33 , Diamond black SH, diamond black SHA, diamond black LH, diamond black H, diamond black HA, diamond black SF, diamond black N550M, diamond black E, diamond black G, diamond black R, diamond black N760M, diamond black LP; company made of carbon black Color black FW200, Color black FW2, Color black FW1, Color black FW18, Color black S170, Color black S160, Special Black6, Special Black5, Special Black4, Special Black4A, Printex U, PrintexV, Printex 140U, Printe 140V: Carbon black REGAL 400, REGAL 400R, REGAL XC72, VULCAN XC72R, MOGUL L, MONARCH 1400, MONARCH 1000, BLACK PEARLS 1400; BLACK PEARLS 1400; 910, 930, 930 970, etc. can be mentioned. Also preferred are those coated with a polymer compound in order to increase the electric resistance. The preferred single particle size of these carbon blacks is 10 to 100 nm, more preferably 10 to 50 nm.

As an example of titanium black, TiO ₂ , TiO, TiN and a mixture thereof are preferable. Examples of commercially available products include (trade names) 12S and 13M manufactured by Mitsubishi Materials Corporation. The average particle size of titanium black is preferably 10 to 100 nm.
As an example of graphite, the use of graphite having a major axis of 1 μm or less as a light shielding material for a color filter makes the contour shape of the light shielding pattern uniform and improves the sharpness. 20 nm or more and 500 nm or less are more preferable. Moreover, it is preferable that the abundance ratio of particles having a particle diameter of 100 nm or less is 70% or more.

The above-described titanium black is also a metal-based fine particle, but as a light-shielding property, Japanese Patent Application Laid-Open No. 2005-17322, Japanese Patent Application Laid-Open No. 2005-179632, Japanese Patent Application Laid-Open No. 2005-263920, etc. (Hereinafter, sometimes referred to as “metallic fine particles”) has been developed.
Examples of preferred metals constituting these metal-based fine particles include copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium, iron, calcium, ruthenium, osmium, manganese, molybdenum, tungsten, niobium. , Tantel, bismuth, antimony, and alloys thereof. Further preferred metals are at least one selected from copper, silver, gold, platinum, palladium, tin, calcium, and alloys thereof, and particularly preferred metals are copper, silver, gold, platinum, tin, and alloys thereof. A compound with other elements other than metals is also preferable. Examples of the compound of metal and other elements include metal oxides, sulfides, sulfates, carbonates, and the like, and these particles are preferable as the metal compound particles. Of these, sulfide particles are preferred because of their color tone and ease of fine particle formation. Moreover, a metal, its alloy, and a metal compound may be used together, and 2 or more types may be sufficient as it. Among these, silver or an alloy thereof and a sulfide thereof are particularly preferable because of their high shielding effect. As an example of an alloy, a silver tin alloy is mentioned as a preferable example.

In addition, composite particles in which a metal and a metal compound are combined into one particle are also suitable, such as those having different compositions between the inside and the surface of the particle, and those having two types of particles combined. be able to. As specific examples, composite fine particles of silver and silver sulfide, composite fine particles of silver and copper (II) oxide, and the like are suitable.
The metal-based fine particles may be core-shell type composite particles (core-shell particles). Core-shell type composite particles (core-shell particles) are obtained by coating the surface of a core material with a shell material, and specific examples thereof include paragraph numbers [0024] to [0027] of JP-A-2006-18210. And core / shell fine particles described in the above.

  These metal-based fine particles have a high black density, can exhibit excellent light-shielding performance in a small amount or in a thin film, and have high thermal stability, so at high temperatures (eg, 200 degrees or more) without impairing the black density. Heat treatment is possible, and a high degree of light shielding property can be secured stably. For example, it is suitable for a color filter light-shielding film (so-called black matrix) that requires a high degree of light-shielding properties and is generally subjected to a baking process.

The metal-based fine particles in the present invention can be commercially available, and can be prepared by a chemical reduction method of metal ions, an electroless plating method, a metal evaporation method, or the like. For example, for rod-shaped silver fine particles, spherical silver fine particles are used as seed particles, then a silver salt is further added, and a reducing agent having a relatively low reducing power such as ascorbic acid is used in the presence of a surfactant such as cetyltrimethylammonium bromide. By this, a silver bar and a wire are obtained. This is described in Advanced Materials 2002, 14, 80-82. Similar descriptions are made in Materials Chemistry and Physics 2004, 84, 197-204, Advanced Functional Materials 2004, 14, 183-189.
In the present invention, the number average particle size of the metal-based fine particles is preferably 5 to 100 nm, more preferably 5 to 80 nm, and particularly preferably 5 to 50 nm. When the number average particle diameter of the particles is 100 nm or less, there is an advantage that the surface smoothness is good and the failure due to coarse particles is reduced.
The content of the metal-based fine particles in the light-shielding part-forming curable composition of the present invention is considered to prevent the metal-based fine particles from being fused during post-baking, for example, during the production of a color filter. On the other hand, considering the light shielding effect, it is preferable to adjust the total light content of the formed curable composition for forming a light shielding part to about 50 to 90% by mass, preferably 50 to 85% by mass.
In addition, the content of the metal-based fine particles is preferably performed in consideration of a change in optical density due to an average particle diameter. Depending on the metal-based fine particles used, the pigment, carbon, etc. can be used in combination for hue correction.

  In the curable composition for forming a light shielding part of the present invention, 40 to 80% by mass of carbon black or 50 to 90% by mass of metal-based fine particles as a light shielding agent in the total solid content of the curable composition for forming a light shielding part. % Content is preferable.

<(B) Dispersant>
The metal-based fine particles in the present invention are preferably present in a stable dispersed state, for example, more preferably in a colloidal state. In the colloidal state, for example, it is preferable that the metal-based fine particles are dispersed in a substantially fine particle state. Here, “substantially dispersed” refers to a state in which primary particles are dispersed independently without being aggregated or softly aggregated.
Examples of the additive that may be added to the dispersant or composition for dispersing the metal-based fine particles include the dispersants and additives described in paragraphs [0027] to [0031] of JP-A-2005-17322. Also preferred in the present invention.

  The dispersant used here is the specific dispersion resin mentioned in the curable composition for forming colored pixels, that is, (B) an acid value of 20 to 300 mg / g and a weight average molecular weight of 3,000 to 100. , 000, and more specifically, the dispersion resins listed as the specific resin dispersion resin (B-1) to the dispersion resin (B-3) are preferably used. Preferred embodiments of the composition are also the same as described above.

  As a dispersant for metal-based fine particles, a hydrophilic group such as a carboxyl group, OH group, sulfonic acid group, phosphoric acid group, amino group, carbonyl group, thiol group, polyoxyalkylene part, and phenyl group (including a naphthalene ring), A compound having a lipophilic part such as an alicyclic ring, an alkyl group, and a substituted group thereof is generally used as a dispersant. For example, the following compounds can be used as commercially available products. However, it is not limited to these compounds.

EFKA-1101, 1120, 1125, 4008, 4009, 4046, 4047, 4520, 4010, 4015, 4020, 4050, 4055, 4060, 4080, 4300, 4330, 4400, 4401, 4402, 4403, 4406, 4800, 5010, 5044, 5244, 5054, 5055, 5063, 5064, 5065, 5066, 5070, 5207 (manufactured by EFKA ADDITIVES),
Anti-Terra-U, Anti-Terra-U100, Anti-Terra-204, Anti-Terra-205, Anti-Terra-P, Disperbyk-101, 102, 103, 106, 108, 109, 110, 111, 112, 151, P-104, P-104S, P105, 220S, 203, 204, 205, 9075, 9076, 9077 (manufactured by BYK),
Disparlon 7301, 325, 374, 234, 1220, 2100, 2200, KS260, KS273N, 1210, 2150, KS860, KS873N, 7004, 1813, 1860, 1401, 1200, 550, EDAPLAN 470, 472, 480, 482, K-SPERSE 131, 152,152MS (manufactured by Enomoto Kasei Co., Ltd.),

Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 22000, 24000, 26000, 28000, etc. (manufactured by AVECIA),
Carribon B, L-400, Eleminor MBN-1, Sunspearl PS-2, PS-8, Ionette S-20 (manufactured by Sanyo Chemical)
Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 (manufactured by San Nopco) and the like can be used.
These specific dispersion resins may be used alone or in combination of two or more. The addition amount of the dispersant is 3 to 30 parts by mass, preferably 5 to 20 parts by mass with respect to the pigment (light-shielding agent).

  In addition to the specific dispersion resin according to the present invention, a polymer dispersant can be used as necessary. Dispersion stability and storage stability are improved by using a polymer dispersant. Dispersing resins that can be used as dispersing agents are described in, for example, “Encyclopedia of Pigments” (edited by Seijiro Ito, published by Asakura Shoin Co., Ltd., 2000).

<(C-2) polymerizable compound>
As the polymerizable compound in the curable composition for forming a light shielding part, the polymerizable compounds used in the curable composition for forming a colored pixel are also preferable, but the following are particularly preferable.
The polymerizable compound in the curable composition for forming a light shielding part of the present invention is preferably a monomer or oligomer that has two or more ethylenically unsaturated double bonds and undergoes addition polymerization upon irradiation with light. Examples of such monomers and oligomers include compounds having at least one addition-polymerizable ethylenically unsaturated group in the molecule and having a boiling point of 100 ° C. or higher at normal pressure. Examples include monofunctional acrylates and monofunctional methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) ) Acrylate, trimethylolethane triacrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane diacrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, di Pentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, hexane All di (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin tri (meth) acrylate; multifunctional such as trimethylolpropane and glycerin Polyfunctional acrylates and polyfunctional methacrylates such as those obtained by adding ethylene oxide or propylene oxide to alcohol and then (meth) acrylated can be mentioned.

An acidic polyfunctional photocurable compound is also a preferred compound. Examples of the acidic polyfunctional photocurable compound include (1) a monomer or oligomer having a hydroxyl group and three or more photocurable functional groups, which is modified with a dibasic acid anhydride to introduce a carboxyl group, (2) Introducing a carboxyl group by adding a compound having both a glycidyl group or an isocyanate group and a COOH group to a monomer or oligomer having a hydroxyl group and three or more photocurable functional groups, or (3) three or more Those having a sulfonic acid group introduced by modifying an aromatic compound having a photocurable functional group with concentrated sulfuric acid or fuming sulfuric acid can be used. Moreover, you may use the oligomer which contains the monomer which is an acidic polyfunctional photocurable compound itself as a repeating unit as an acidic polyfunctional photocurable compound.
As an example of an acidic polyfunctional photocurable compound, what is represented by the following general formula (i) and general formula (ii) is preferable. In general formula (i) and general formula (ii), when T or G is an oxyalkylene group, the terminal on the carbon atom side is bonded to R, X, and W.

In formula (i), R represents a (meth) acryloyloxy group, X represents a -COOH group, -OPO ₃ H ₂ group. T represents an oxyalkylene group, wherein the alkylene group has 1 to 4 carbon atoms. n is 0-20.
In general formula (ii), W represents R or X in general formula (i), and 3 or more Ws are R among 6 Ws. G has the same meaning as T in formula (i). Z represents —O— or —OC═ONH (CH ₂ ) qNHCOO—. p is 0-20 and q is 1-8. A plurality of R, X, T, and G present in one molecule may be the same or different. )
As a commercial item of the acidic polyfunctional photocurable compound represented by general formula (i) and general formula (ii), for example, TO-756, which is a carboxyl group-containing trifunctional acrylate manufactured by Toagosei Co., Ltd., and carboxyl And TO-1382 which is a group-containing pentafunctional acrylate.

  Further, urethane acrylates described in JP-B-48-41708, JP-B-50-6034 and JP-A-51-37193; JP-A-48-64183, JP-B-49-43191 And polyester acrylates described in Japanese Patent Publication No. 52-30490; polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid. Among these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, the above carboxyl group-containing pentafunctional acrylate, etc. Is preferred. In addition, “polymerizable compound B” described in JP-A-11-133600 can also be mentioned as a preferable example.

  As content of the polymeric compound in the curable composition for light-shielding part formation, it is preferable that it is 5-50 mass% in the total solid of the curable composition for light-shielding part formation of this invention, and 7-40 masses. % Is more preferable, and 10 to 35% by mass is even more preferable.

The (D) polymerization initiator, (E) solvent, and the like used in the light-shielding part-forming curable composition are the same as those in the above-described colored pixel-forming curable composition, and the preferred contents are also the same.
In addition to the above essential components, various known additives can be used in the curable composition for forming a colored pixel and the curable composition for forming a light shielding part of the present invention depending on the purpose.
Hereinafter, such additives will be described.

<Alkali-soluble resin>
In each of the curable compositions of the present invention, an alkali-soluble resin can be used as a binder polymer for the purpose of improving film properties.
The alkali-soluble resin used in the present invention is a linear organic polymer, and at least one molecule in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). It can be appropriately selected from alkali-soluble resins having a group that promotes alkali solubility (for example, carboxyl group, phosphoric acid group, sulfonic acid group, hydroxyl group, etc.).

More preferable as the alkali-soluble resin is a polymer having a carboxylic acid in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54-25957, A methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid, as described in JP-A-59-53836 and JP-A-59-71048 Acrylic copolymers such as acid copolymers, partially esterified maleic acid copolymers, etc., acidic cellulose derivatives having a carboxylic acid in the side chain, and acid anhydrides added to polymers having a hydroxyl group Can be mentioned.
The acid value is preferably in the range of 20 to 200 mgKOH / g, preferably 30 to 180 mgKOH / g, more preferably 50 to 150 mgKOH / g.

As a specific structural unit of the alkali-soluble resin, a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is particularly suitable. Examples of other monomers copolymerizable with the (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds. Here, the hydrogen atom of the alkyl group and the aryl group may be substituted with a substituent.
Examples of the alkyl (meth) acrylates and aryl (meth) ^{_{acrylate, CH 2 = C (R 1}} ) (COOR 3) [wherein, ^{R 1} represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, ^{R 2} Represents an aromatic hydrocarbon ring having 6 to 10 carbon atoms, and R ³ represents an alkyl group having 1 to 8 carbon atoms or an aralkyl group having 6 to 12 carbon atoms. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) ) Acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, hydroxyalkyl (meth) acrylate (alkyl is an alkyl group having 1 to 8 carbon atoms) ), Hydroxyglycidyl methacrylate, tetrahydrofurfuryl methacrylate and the like.

A resin having a polyalkylene oxide chain in the molecular side chain is also preferred. The polyalkylene oxide chain may be a polyethylene oxide chain, a polypropylene oxide chain, a polytetramethylene glycol chain, or a combination thereof, and the terminal is a hydrogen atom or a linear or branched alkyl group.
1-20 are preferable and, as for the repeating unit of a polyethylene oxide chain and a polypropylene oxide chain, 2-12 are more preferable. Acrylic copolymers having a polyalkylene oxide chain in these side chains include, for example, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, poly (ethylene glycol-propylene glycol) mono (meth) acrylate, and the like. A compound in which these terminal OH groups are alkyl-blocked, such as methoxypolyethylene glycol mono (meth) acrylate, ethoxypolypropylene glycol mono (meth) acrylate, methoxypoly (ethylene glycol-propylene glycol) mono (meth) acrylate, etc. is used as a copolymerization component. Acrylic copolymer.

As the vinyl compound, CH ₂ = CR ¹ R ² [wherein R ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ² represents an aromatic hydrocarbon ring having 6 to 10 carbon atoms. , R ³ represents an alkyl group having 1 to 8 carbon atoms or an aralkyl group having 6 to 12 carbon atoms. Specific examples include styrene, α-methylstyrene, vinyl toluene, acrylonitrile, vinyl acetate, N-vinyl pyrrolidone, polystyrene macromonomer, polymethyl methacrylate macromonomer, and the like.
Other monomers that can be copolymerized can be used singly or in combination of two or more. Of these, benzyl (meth) acrylate / (meth) acrylic acid copolymers and multi-component copolymers composed of benzyl (meth) acrylate / (meth) acrylic acid / other monomers are particularly suitable.

As already described, the acrylic resin has an acid value in the range of 20 to 200 mgKOH / g. When the acid value exceeds 200, the acrylic resin becomes too soluble in alkali and the appropriate development range (development latitude) becomes narrow. On the other hand, if it is too small, such as less than 20, the solubility in alkali is so small that it takes too much time for development, which is not preferable.
Also, the mass average molecular weight Mw (polystyrene conversion value measured by GPC method) of the acrylic resin is used to realize a viscosity range that is easy to use in the process of applying a color resist, etc. It is preferable that it is 2,000-100,000, More preferably, it is 3,000-50,000.

  In order to improve the crosslinking efficiency of the curable composition in the present invention, a resin having a polymerizable group in an alkali-soluble resin may be used alone or in combination with an alkali-soluble resin having no polymerizable group. Polymers containing a (meth) acryl group, an aryloxyalkyl group or the like in the side chain are useful. The alkali-soluble resin having a polymerizable double bond can be developed with an alkali developer, and is further provided with photocurability and thermosetting. Examples of the polymer containing these polymerizable groups are shown below, but the polymer is not limited to the following as long as it contains an alkali-soluble group such as a COOH group and an OH group and a carbon-carbon unsaturated bond in one molecule.

(1) Urethane modification obtained by reacting an isocyanate group and an OH group in advance, leaving one unreacted isocyanate group and reacting at least one (meth) acryloyl group with an acrylic resin containing a carboxyl group A polymerizable double bond-containing acrylic resin,
(2) an unsaturated group-containing acrylic resin obtained by a reaction between an acrylic resin containing a carboxyl group and a compound having both an epoxy group and a polymerizable double bond in the molecule;
(3) Acid pendant type epoxy acrylate resin,
(4) A polymerizable double bond-containing acrylic resin obtained by reacting an acrylic resin containing an OH group with a dibasic acid anhydride having a polymerizable double bond.
Of the above, the resins (1) and (2) are particularly preferable.

As a specific example, a copolymer of an OH group such as 2-hydroxyethyl acrylate, a COOH group such as methacrylic acid, and a monomer such as an acrylic or vinyl compound copolymerizable with these, an OH group A compound obtained by reacting an epoxy ring having reactivity with a compound having a carbon-carbon unsaturated bond group (for example, a compound such as glycidyl acrylate) can be used. In the reaction with the OH group, a compound having an acid anhydride, an isocyanate group, or an acryloyl group in addition to the epoxy ring can be used.
Further, a compound obtained by reacting an unsaturated carboxylic acid such as acrylic acid with a compound having an epoxy ring described in JP-A-6-102669 and JP-A-6-1938 is saturated or unsaturated polybasic. A reaction product obtained by reacting an acid anhydride can also be used.

Examples of compounds having both an alkali solubilizing group such as a COOH group and an intercarbon unsaturated group include, for example, Dainar NR series (manufactured by Mitsubishi Rayon Co., Ltd.); Ltd .; Biscort R-264, KS resist 106 (both manufactured by Osaka Organic Chemical Industry Co., Ltd.); Cyclomer P series, Plaxel CF200 series (both manufactured by Daicel Chemical Industries, Ltd.); Ebecryl 3800 (Daicel) And UCB Co., Ltd.).
As addition amount of alkali-soluble resin, it is preferable that it is the range of 3-30 mass% in the total solid of the curable composition of this invention, and 5-20 mass% is more preferable.

In preparing the resist, it is preferable to add the following epoxy resin in addition to the alkali-soluble resin. The epoxy resin is a compound having two or more epoxy rings in the molecule such as bisphenol A type, cresol novolac type, biphenyl type, and alicyclic epoxy compound.
For example, as bisphenol A type, Epototo YD-115, YD-118T, YD-127, YD-128, YD-134, YD-8125, YD-7011R, ZX-1059, YDF-8170, YDF-170 and the like ( As described above, manufactured by Tohto Kasei Co., Ltd.), Denacol EX-1101, EX-1102, EX-1103 etc. In addition, bisphenol F type and bisphenol S type epoxy resins similar to these can also be used.
Epoxy acrylates such as Ebecryl 3700, 3701, and 600 (manufactured by Daicel UC) can also be used. As cresol novolak type, Epototo YDPN-638, YDPN-701, YDPN-702, YDPN-703, YDPN-704, etc. (above made by Tohto Kasei), Denacol EM-125, etc. (above made by Nagase Kasei), biphenyl type Examples of cycloaliphatic epoxy compounds such as 3,5,3 ′, 5′-tetramethyl-4,4′-diglycidylbiphenyl include Celoxide 2021, 2081, 2083, 2085, Epolide GT-301, GT-302, GT. -401, GT-403, EHPE-3150 (manufactured by Daicel Chemical), Santo Tote ST-3000, ST-4000, ST-5080, ST-5100, etc. (manufactured by Toto Kasei), Epilon 430, 673, 695, 850S, 4032 (made by Dainippon Ink and Co., Ltd.) It is possible. Also 1,1,2,2-tetrakis (p-glycidyloxyphenyl) ethane, tris (p-glycidyloxyphenyl) methane, triglycidyltris (hydroxyethyl) isocyanurate, o-phthalic acid diglycidyl ester, terephthalic acid diester In addition, glycidyl esters such as Epototo YH-434 and YH-434L, which are amine-type epoxy resins, and glycidyl esters obtained by modifying dimer acid in the skeleton of bisphenol A-type epoxy resins can also be used.

Among these, “molecular weight / number of epoxy rings” is preferably 100 or more, and more preferably 130 to 500. If the “molecular weight / number of epoxy rings” is small, the curability is high, the shrinkage at the time of curing is large, and if it is too large, the curability is insufficient and the reliability is poor or the flatness is poor.
Specific preferred compounds include Epototo YD-115, 118T, 127, YDF-170, YDPN-638, YDPN-701, Plaxel GL-61, GL-62, 3,5,3 ', 5'-tetramethyl. -4,4 'diglycidyl biphenyl, celoxide 2021, 2081, epolide GT-302, GT-403, EHPE-3150, etc. are mentioned.

In addition, increasing the pigment concentration to create high color purity generally increases the thixotropy of the coating solution, which tends to cause film thickness unevenness after coating. It is important to ring to form a uniform thickness coating. For this reason, it is preferable to contain an appropriate surfactant in the colored photosensitive resin composition. Preferred examples of the surfactant include surfactants disclosed in JP-A Nos. 2003-337424 and 11-133600.
Nonionic surfactants, fluorine-based surfactants, silicon-based surfactants, and the like are added as surfactants for improving coating properties.

  Nonionic surfactants include, for example, polyoxyethylene glycols, polyoxypropylene glycols, polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, polyoxypropylene alkyl ethers. Nonionic surfactants such as polyoxypropylene alkyl aryl ethers, polyoxypropylene alkyl esters, sorbitan alkyl esters and monoglyceride alkyl esters are preferred.

  Specifically, polyoxyalkylene glycols such as polyoxyethylene glycol and polyoxypropylene glycol; polyoxyalkylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxypropylene stearyl ether and polyoxyethylene oleyl ether; polyoxy Polyoxyethylene aryl ethers such as ethylene octyl phenyl ether, polyoxyethylene polystyryl ether, polyoxyethylene tribenzyl phenyl ether, polyoxyethylene-propylene polystyryl ether, polyoxyethylene nonylphenyl ether; polyoxyethylene dilaurate , Polyoxyalkylene dialkyl esters such as polyoxyethylene distearate, sorbitan fatty acid ester There are nonionic surfactants such as stealth and polyoxyalkylene sorbitan fatty acid esters.

  Specific examples of these include, for example, Adeka Pluronic series, Adecanol series i, Tetronic series (above made by ADEKA), Emulgen series, Rheodor series (above made by Kao Corporation), Eleminor series, Nonipole series, The Octopole series, Dodecapol series, Newpole series (Sanyo Kasei Co., Ltd.), Pionein series (Takemoto Yushi Co., Ltd.), Nissan Nonion series (Nippon Yushi Co., Ltd.), etc. These commercially available products can be used as appropriate. A preferable HLB value is 8 to 20, more preferably 10 to 17.

As the fluorosurfactant, a compound having a fluoroalkyl or fluoroalkylene group in at least one of the terminal, main chain and side chain can be suitably used.
Specific commercial products include, for example, MegaFuck F142D, F172, F173, F176, F176, F177, F183, 780, 781, R30, R08 (Dainippon Ink Co., Ltd.), Florard FC -135, FC-170C, FC-430, FC-431 (Sumitomo 3M), Surflon S-112, S-113, S-131, S-141, S-145 S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-105, SC-106 (manufactured by Asahi Glass Co., Ltd.), Ftop EF351, 352, 801 and 802 (manufactured by JEMCO).

  Examples of the silicone-based surfactant include Torre Silicone DC3PA, DC7PA, SH11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH-190, SH-193, SZ-6032, and SF-8428. DC-57, DC-190 (above, manufactured by Toray Dow Corning Silicone Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4442 (above GE Toshiba Silicone Co., Ltd.).

  These surfactants are preferably used in an amount of 5 parts by weight or less, more preferably 2 parts by weight or less with respect to 100 parts by weight of the resist solution. When the amount of the surfactant exceeds 5 parts by weight, surface roughness is likely to occur during coating and drying, and the smoothness tends to deteriorate.

  In order to promote alkali solubility of the uncured portion and further improve the developability of the photocurable composition, an organic carboxylic acid, preferably a low molecular weight organic carboxylic acid having a molecular weight of 1000 or less is added. be able to. 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 Others such as phenoxyacetic acid, methoxyphenoxyacetic acid, hydroatropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetic acid, coumaric acid, umberic acid Carboxylic acid is mentioned.

<Alkoxysilane compound>
Each curable composition of the present invention is preferably used in combination with an alkoxysilane compound, especially a silane coupling agent, from the viewpoint of improving adhesion to the substrate.
The silane coupling agent preferably has an alkoxysilyl group as a hydrolyzable group that can be chemically bonded to an inorganic material, and (meth) acryloyl or phenyl that exhibits affinity by interacting or forming a bond with an organic resin. , Mercapto and epoxysilane, and (meth) acryloylpropyltrimethoxysilane is more preferable among them.
In the case of using a silane coupling agent, the addition amount is preferably in the range of 0.2 to 5.0% by mass in the total solid content of the curable composition of the present invention, 0.5 to 3.0 The mass% is more preferable.

<Co-sensitizer>
Each curable composition of the present invention preferably contains a co-sensitizer if desired. In the present invention, the co-sensitizer has functions such as further improving the sensitivity of the sensitizing dye and initiator to actinic radiation or suppressing the inhibition of polymerization of the polymerizable compound by oxygen.
Examples of such 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.

0001
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.

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

<Polymerization inhibitor>
In the present invention, a small amount of a thermal polymerization inhibitor may be added in order to prevent unnecessary thermal polymerization of a compound having an ethylenically unsaturated double bond that can be polymerized during the production or storage of the curable composition. desirable.
Examples of the thermal polymerization inhibitor that can be used in the present invention include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6). -T-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt and the like.

  The addition amount of the thermal polymerization inhibitor is preferably about 0.01% by mass to about 5% by mass with respect to the mass of the entire composition. If necessary, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to prevent polymerization inhibition due to oxygen, and it may be unevenly distributed on the surface of the photosensitive layer in the course of drying after coating. . The amount of the higher fatty acid derivative added is preferably about 0.5% by mass to about 10% by mass of the total composition.

<Other additives>
Furthermore, in the present invention, a known additive such as an inorganic filler, a plasticizer, or a sensitizer capable of improving the ink inking property on the surface of the photosensitive layer may be added to improve the physical properties of the cured film. Good.
Examples of plasticizers include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, and triacetyl glycerin. 10 mass% or less can be added with respect to the total mass of the compound which has an ionic unsaturated double bond, and binder.

  The curable composition of the present invention is cured with high sensitivity and has good storage stability. Moreover, the high adhesiveness to hard material surfaces, such as a board | substrate which applies a curable composition, is shown. Accordingly, the curable composition of the present invention can be preferably used in the fields of image forming materials such as three-dimensional stereolithography, holography, and color filters, inks, paints, adhesives, and coating agents.

[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 a light-shielding formed on a support using a colored pattern (colored pixel) using the curable composition for forming colored pixels of the present invention and a curable composition for forming a light shielding part. Part (black matrix).
Hereinafter, the color filter of the present invention will be described in detail through its manufacturing method.

A step of forming the curable composition layer by applying each of the curable compositions of the present invention on a support (hereinafter, abbreviated as “curable composition layer forming step” as appropriate) and the curable property. A step of exposing the composition layer through a mask (hereinafter, abbreviated as “exposure step” where appropriate), and a step of developing the curable composition layer after exposure to form a colored pattern (hereinafter, appropriately) Abbreviated as “development step”). These steps are the same when forming colored pixels and when forming a light shielding portion. In general, first, a light shielding portion is formed, and then colored pixels of each hue of RGB are formed.
Hereafter, each process in the manufacturing method of this invention is demonstrated.

<Curable composition layer forming step>
In the curable composition layer forming step, the curable composition of the present invention is applied on the support to form a curable composition layer.

Examples of the support that can be used in this step include non-alkali glass, soda glass, Pyrex (registered trademark) glass, quartz glass, and those obtained by attaching a transparent conductive film to these, and solid-state imaging. Examples of the photoelectric conversion element substrate used for the element include a silicon substrate. Furthermore, a plastic substrate is also possible. In these substrates, first, a light shielding portion is formed in a lattice shape so as to isolate each pixel, and colored pixels are formed in a portion where the lattice is vacant.
Further, an undercoat layer may be provided on these supports, if necessary, in order to improve adhesion to the upper layer, prevent diffusion of substances, or flatten the substrate 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.
Moreover, as a method of forming a curable composition film on a support, in addition to the above application method, a method of transferring a coating film formed by applying the above method on a temporary support in advance onto a substrate is applied. You can also
Regarding the transfer method, the production methods described in paragraph numbers [0023] and [0036] to [0051] of JP-A-2006-23696 and paragraph numbers [0096] to [0108] of JP-A-2006-47592 are used. It can be suitably used in the present invention.

  The coating film thickness of the curable composition is appropriately prepared depending on the design value of the thickness of the light-shielding part and the colored pixel to be formed, but generally 0.1 to 10 μm is preferable. In the present invention, the colored layer Is more preferably in the range of 1.5 to 2.5 μm, and the light shielding portion is in the range of 0.3 to 1.0 μm.

  Drying (prebaking) of the curable composition layer applied on the substrate can be performed at a temperature of 50 ° C. to 140 ° C. for 10 to 300 seconds using a hot plate, an oven or the like.

<Exposure process>
In the exposure step, the curable composition layer formed in the curable composition layer forming step is exposed through a mask having a predetermined mask pattern.
In this step, the pattern of the coating film is exposed through a predetermined mask pattern, only the coating film portion irradiated with light is cured, developed with a developer, and each color (three colors or four colors). This can be done by forming a pattern-like film consisting of these pixels. As radiation that can be used for exposure, ultraviolet rays such as g-line, h-line, and i-line are particularly preferably used. Irradiation dose is more preferably preferably ^{10~1000mJ / cm 2 5~1500mJ / 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. The exposure machine can be a proximity type exposure machine, a mirror projection system or a stepper system.
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. In this case, an i-line stepper type exposure machine is preferable.

<Development process>
Next, by performing an alkali development treatment, the light-irradiated portion is eluted in the alkaline aqueous solution by the exposure, and only the photocured portion remains. When the developer is for a solid-state image sensor, an organic alkali developer that does not damage the underlying circuit or the like is desirable. In the case of a color filter for a liquid crystal display device, an inorganic alkaline developer is used. 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 sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxy. And organic alkaline compounds such as tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene, and the concentration of these alkaline agents is 0.001 to 0.001. An alkaline aqueous solution diluted with pure water so as to be 10% by mass, preferably 0.01 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, followed by heat treatment (post-bake). Thus, the said process can be repeated sequentially for every color, and a cured film can be manufactured.
Thereby, a color filter is obtained.
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 is performed continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulation dryer), a high-frequency heater, or the like so that the coating film after development is in the above-described condition. be able to.

  In the production method of the present invention, after the curable composition layer forming step, the exposure step, and the development step described above are performed, the formed light shielding portion and the colored pixels are heated and / or exposed as necessary. A curing step for curing may be included.

  The curable composition layer forming step, the exposure step, and the developing step (and the curing step if necessary) described above are performed. First, after forming the light-shielding portion, the desired number of hues is formed to form the colored pixels. By repeating these steps, a color filter including a light shielding portion and a colored pixel having a desired hue is manufactured.

<Liquid crystal display device with color filter>
The display device of the present invention refers to a display device such as a liquid crystal display device, a plasma display display device, an EL display device, or a CRT display device. For the definition of display devices and explanation of each display device, refer to “Electronic Display Devices (Akio Sasaki, published by Industrial Research Institute 1990)”, “Display Devices (Junaki Ibuki, Industrial Books Co., Ltd.) Issue)).

Among the display devices of the present invention, a liquid crystal display device is particularly preferable. The liquid crystal display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by Kogyo Kenkyukai 1994)”. The liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to various types of liquid crystal display devices described in, for example, the “next generation liquid crystal display technology”.
Among these, the present invention is particularly effective for a color TFT liquid crystal display device. The color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”. Further, the present invention is applied to a liquid crystal display device with a wide viewing angle such as a lateral electric field driving method such as IPS and a pixel division method such as MVA, STN, TN, VA, IPS, OCS, FFS, and R-OCB. Applicable. These methods are described, for example, on page 43 of "EL, PDP, LCD display-latest technology and market trends-(issued in 2001 by Toray Research Center Research Division)". In addition to the color filter, the liquid crystal display device includes various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle guarantee film. The substrate with a light-shielding film of the present invention can be applied to a liquid crystal display device composed of these known members.
For example, “'94 Liquid Crystal Display Peripheral Materials / Chemicals Market (Kentaro Shima, Ltd. issued by CMC 1994)”, “2003 Liquid Crystal Related Market Status and Future Prospects (Volume 2)” (Table Yoshiyoshi) Fuji Chimera Research Institute, published in 2003) ”.

  Regarding backlights, see SID meeting Digest 1380 (2005) (A. Konno et.al), Monthly Display December 2005, pages 18-24 (Yasuhiro Shima), pages 25-30 (Takaaki Yagi), etc. Although described, the color filter of the present invention can achieve high contrast when combined with a conventionally known three-wavelength cold-cathode tube, but it also supports red, green, and blue LED light sources (RGB-LED). By using a light, it is possible to provide a liquid crystal display device with high luminance and high color purity and good color reproducibility.

The high optical density black matrix itself formed using the composition of the present invention has an effect of shadowing the backlight and sharpening the transmitted light of each colored pixel portion (shadow effect). When the OD value of the light-shielding part is low, the black-colored display does not become jet black, and the visually recognized image becomes blurred.
On the other hand, if the depolarization of the colored pixel portion (hereinafter referred to as the pixel portion) is low, the backlight is not shielded by scattering within the pixel, stray light is generated, and the phenomenon of so-called “light leakage” and “color leakage” occurs. To do. (= Low contrast) In this case, the entire screen appears colored even if black display is performed. For example, when the contrast of the red pixel portion is low, it looks red, and when the contrast of the blue pixel portion is low, it looks blue and the color reproducibility is poor. For this reason, it has been desired to improve the contrast of the pixel portion.

In the present invention, as described above, by using a curable composition containing a specific polymer dispersant, pigment fine particles used in the colored pixel portion can be highly dispersed, thereby improving the contrast of the pixel portion. Achieved. Only when this contrast improvement and a high OD value in the light-shielding portion are compatible, sufficient effects are achieved even when viewed as a whole display device as in the present invention, and a higher contrast as a display device is realized. It is.
That is, by making the light shielding portion have a high OD value, the light shielding portion suppresses the transmission of the backlight, and also discovers the effect of blocking stray light incident on the light shielding portion from the colored pixel portion, and the synergy between the pixel portion and the light shielding portion. As a result, a high-definition display device with extremely good color reproducibility is obtained.
Furthermore, more natural color reproduction is required for display devices. For this reason, it is desired to further improve the ratio of NTSC to 70%, which is equivalent to CRT, which is an index of color reproducibility, but color reproduction is achieved by using the color filter and RGB-LED of the present invention for the backlight. Can greatly improve performance.

  On the other hand, the performance required for the liquid crystal display device is to improve the response speed of the image. In order to improve the response speed, the liquid crystal alignment speed has been improved. On the other hand, from the structural aspect of the cell, it is necessary to reduce the thickness of the liquid crystal layer in terms of cost reduction. Another technique necessary for reducing the thickness of the liquid crystal layer is to reduce the alignment disorder of the liquid crystal at the boundary between the pixel portion and the light shielding portion. For this purpose, it is required to reduce the step at the boundary portion. By reducing the disturbance at the boundary, the visibility of the pixel portion and the light shielding portion is improved. Since the colored layer of the present invention has appropriate alkali solubility and hydrophobicity, the overlapping portion of each colored pixel tends to be flat. In particular, this effect is remarkable when the thickness of the light shielding portion is small, and when combined with the light shielding portion of the present invention, the linearity of the pattern of the light shielding portion and the flattening due to the overlapping of the colored portions on the BM are improved. When the flatness is improved, it is not necessary to make the liquid crystal layer thin or to provide a flattening layer before laying the transparent electrode ITO, which can contribute to streamlining of the process and cost reduction and mass productivity. This is the realization of a thin light-shielding layer, which is another feature of the present invention, and in combination with this, the high contrast performance of the colored portion, which is a major element of the present invention, can be exhibited.

EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, it is not limited to a following example. Unless otherwise specified, “%” and “part” are based on mass.
[Example 1]
<1. Adjustment of curable composition for light shielding>
1-1. Preparation of dispersion of particles having silver tin alloy part (dispersion K-1) In 1000 ml of pure water, 23.1 g of silver (I) acetate, 65.1 g of tin (II) acetate, 54 g of gluconic acid, 45 g of sodium pyrophosphate Then, 2 g of polyethylene glycol (molecular weight 3,000) and 5 g of PVP-K30 (manufactured by IPS Japan Ltd .; polyvinylpyrrolidone polymer) were dissolved to obtain a solution 1. Separately, 46.1 g of hydroxyacetone was dissolved in 500 ml of pure water to obtain a solution 2.

  While the solution 1 obtained above was vigorously stirred while maintaining at 25 ° C., the above solution 2 was added thereto over 2 minutes, and the stirring was continued gently for 6 hours. The mixed liquid turned black, and metal particles having a silver-tin alloy part (hereinafter, sometimes referred to as “silver-tin alloy part-containing particles”) were obtained. Next, this mixed solution was centrifuged to precipitate silver-tin alloy part-containing particles. Centrifugation is subdivided into a volume of 150 ml, and a table centrifuge H-103n (manufactured by Kokusan Co., Ltd.) is used. p. m. For 30 minutes. The supernatant was discarded and the total liquid volume was 150 ml. To this was added 1350 ml of pure water, and the mixture was stirred for 15 minutes to disperse the silver-tin alloy part-containing particles again. This re-dispersed liquid was centrifuged in the same manner as described above to precipitate silver-tin alloy part-containing particles. This operation (pure water addition and centrifugation) was repeated twice to wash the silver-tin alloy part-containing particles.

  The silver-tin alloy part-containing particles obtained above were again used as a dispersion, and the dispersion was further centrifuged to precipitate the silver-tin alloy part-containing particles again. Centrifugation was performed under the same conditions as described above. After centrifugation, the supernatant was discarded as described above to make the total liquid volume 150 ml, and 850 ml of pure water and 500 ml of normal propyl alcohol were added thereto, and the mixture was further stirred for 15 minutes to disperse the silver-tin alloy part-containing particles again.

  Centrifugation was performed again in the same manner as described above to precipitate the silver-tin alloy part-containing particles. Then, the supernatant was discarded in the same manner as described above to make the liquid volume 150 ml, and 150 ml of pure water and 1200 ml of normal propyl alcohol were added thereto. The mixture was stirred for a minute to disperse the silver-tin alloy part-containing particles again. Again, centrifugation was performed. The centrifugation conditions at this time are the same as described above except that the time is extended to 90 minutes. Thereafter, the supernatant was discarded to make the total liquid volume 70 ml, and 30 ml of normal propyl alcohol was added thereto. This was dispersed for 6 hours using an Eiger mill (Eiger mill M-50 type (media: diameter 0.65 mm zirconia beads 130 g, manufactured by Eiger Japan Co., Ltd.)), and silver-tin alloy part-containing particles (silver-tin particle concentration 25% by mass) A dispersion (dispersion K-1) of PVP-K30 remaining amount 1.0% by mass was prepared.

  When the silver-tin alloy part-containing particles obtained above were analyzed using HD-2300 manufactured by Hitachi, Ltd. and EDS (energy dispersive X-ray analyzer) manufactured by Noran, an AgSn alloy was obtained. It was confirmed by X-ray scattering that the composite was composed of (2θ = 39.5 °) and Sn metal (2θ = 30.5 °). Here, the numbers in parentheses are the scattering angles of the respective (III) planes. The number average particle size of the silver-tin alloy part-containing particles in this dispersion K-1 was about 40 nm.

  The number average particle diameter was measured as follows using a photograph obtained with a transmission electron microscope JEM-2010 (manufactured by JEOL Ltd., magnification: 100,000 times, acceleration voltage: 200 kV). 100 particles were selected, the diameter of a circle having the same area as each particle image was defined as the particle diameter, and the average value of the particle diameters of 100 particles was defined as the number average particle diameter.

1-2. Preparation of Dispersion Liquid of Particles Having Silver Sulfide Fine Particles (Dispersion Liquid K-2) 25.2 g of silver acetate was dissolved in 100 ml of diethylaminoethanol (Solution 3). Separately, 25.8 g of ammonium sulfide was dissolved in 100 ml of ethanol (solution 4). Solution 4 was added to solution 3 kept at 25 ° C. while vigorously stirring. Thereafter, stirring was continued for 15 minutes. The liquid mixture turned black and silver sulfide was produced. Thereafter, the mixture was allowed to stand for 8 hours to precipitate silver sulfide, and the supernatant was discarded. Next, 100 ml of methyl ethyl ketone was added and stirred for 15 minutes, and then allowed to stand for 8 hours to precipitate silver sulfide, and the supernatant was discarded. This operation was repeated again. Methyl ethyl ketone was added to the silver sulfide slurry thus obtained to make a total volume of 50 ml.
This silver sulfide dispersion was placed in a glass bottle with a capacity of 100 ml together with 40 g of zirconia beads having a diameter of 0.3 mm and dispersed with a paint shaker for 6 hours. After the dispersion, the glass beads were removed to obtain a silver sulfide fine particle dispersion K-2. The obtained liquid volume was 47 mL and the amount of silver sulfide was 17.2 g. When the fine particles were observed with a transmission electron microscope, the average particle size was about 20 nm.

1-3. Preparation of carbon black dispersion liquid (K-3) Carbon black dispersion liquid K-3 was prepared according to the following formulation.
・ Carbon black (Color Black FW2 manufactured by Degussa Co., Ltd.) 26.7 parts ・ Dispersant (Desparon DA7500 manufactured by Enomoto Kasei Co., Ltd. Acid value 26 Amine value 40)
... 3.3 parts benzyl methacrylate / methacrylic acid (= 72/28 molar ratio) copolymer,
Mw10000, 50 wt% solution of propylene glycol monomethyl ether acetate
・ ・ ・ 10 parts ・ Propylene glycol monomethyl ether acetate ・ ・ ・ 60 parts

  The above composition was stirred for 1 hour using a homogenizer at 3000 rpm. The obtained mixed solution was finely dispersed for 8 hours with a bead disperser (trade name: Dispermat, manufactured by GETZMANN) using 0.3 mm zirconia beads to obtain a dispersion.

1-4. Preparation of light-shielding curable composition Using the obtained light-shielding dispersion, a curable composition was prepared according to the formulation shown in Table 1 below. The numbers in the table indicate the mass ratio.

Details of each compound used in the week are as follows.
Compound C-1: A compound in which a = 1, b = 13, c = 30, d = 12, and e = 44 in the chemical formula (JS-1). In addition, the number in a table | surface shows copolymerization mass%.
Resin solution C-2: benzyl methacrylate / methacrylic acid (= 85/15 molar ratio) copolymer, (Mw10000, 50 wt% solution of propylene glycol monomethyl ether acetate)
UV curable resin C-3: trade name Cyclomer P ACA-250, manufactured by Daicel Chemical Industries, Ltd. [Acrylic copolymer with alicyclic, COOH, and acryloyl groups in the side chain, propylene glycol monomethyl ether acetate solution (solid content: 50 mass%)]
Polymerizable compound C-4: Dipentaerythritol penta-hexaacrylate (trade name: DPHA Nippon Kayaku)
Polymerizable compound C-5: Trade name TO-1382 Toagosei Co., Ltd. A monomer having a pentafunctional acryloyl group in which a part of the terminal OH group of dipentaerythritol pentaacrylate is substituted with a COOH group is a main component.
・ Initiator C-6: Product name “Irgacure 379” Ciba Specialty Chemicals ・ Initiator C-7: Product name “OXE-02” Ciba Specialty Chemicals ・ Surfactant C-8: Product Name "Mega-Fak R30" Made by Dainippon Ink / Solvent: MEK = Methyl ethyl ketone PGMEA = Propylene glycol monomethyl ether acetate EEP = 3-Ethoxyethyl propionate

<2-1. Formation of black matrix (BM) by coating>
The obtained light-blocking curable composition CK-2 to CK-4 was used in a glass substrate (Corning Millennium 0.7 mm thickness) with a slit coating device provided with a slit head having a slit interval of 100 μm and an effective coating width of 500 mm. Thus, the suitability for slit coating was evaluated. Coating was performed at a coating speed of 100 mm / second by adjusting the interval between the slit and the glass substrate and the discharge amount so that the film thickness after post-baking was 0.5 μm to 1.5 μm.
Next, after heating (pre-baking treatment) at 100 ° C. for 120 seconds using a hot plate, the proximity gap is set to 300 μm with a mask having a line width of 10 μm using a HITACHI exposure machine LE5565 (all wavelengths), and 100 mJ / Cm ² (illuminance: 20 mW / cm ² ).
Thereafter, development was performed with a 1.0% developer (25 ° C.) of potassium hydroxide developer CDK-1 (manufactured by FUJIFILM Electronics Materials Co., Ltd.) and washed with pure water. Next, post baking was performed in a 220 ° C. clean oven for 30 minutes to form a grid-like black matrix substrate having a light shielding layer with a line width of about 13 μm so that the opening of the colored pixel formation region was 90 μm × 200 μm.

<2-2. Formation of black matrix (BM) by transfer>
2-2-1. Production of photosensitive transfer material On a 75 μm thick polyethylene terephthalate film temporary support (PET temporary support), using a slit nozzle, the following coating solution for a thermoplastic resin layer is applied and dried to be thermoplastic. A resin layer was formed.
[Prescription of coating solution for thermoplastic resin layer]
Methanol: 11.1 parts Propylene glycol monomethyl ether acetate: 6.36 parts Methyl ethyl ketone: 52.4 parts Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (co-polymer) Polymerization ratio [molar ratio] = 55 / 11.7 / 4.5 / 28.8, weight average molecular weight = 90,000, Tg≈70 ° C.) 5.83 parts Styrene / acrylic acid copolymer 13.6 parts (copolymerization ratio [molar ratio] = 63/37, weight average molecular weight = 10,000, Tg≈100 ° C.)
・ 2,2-bis [4- (methacryloxypolyethoxy) phenyl] propane (manufactured by Shin-Nakamura Chemical Co., Ltd .; compound obtained by dehydration condensation of 2 equivalents of bisphenol A and pentaethylene glycol monomethacrylate) 9.1 Part ・ Surfactant C-8 ・ ・ ・ 0.54 part

  Next, an intermediate layer coating solution having the following formulation was further applied onto the thermoplastic resin layer and dried to laminate the intermediate layer. Subsequently, the light-blocking curable composition CK-1 was applied on the intermediate layer and dried to further laminate a black photosensitive composition layer. As described above, a thermoplastic resin layer having a dry layer thickness of 14.6 μm, an intermediate layer having a dry layer thickness of 1.6 μm, and an optical density (OD) of 4.5 are formed on the PET temporary support. And a protective film (polypropylene film having a thickness of 12 μm) is pressure-bonded to the surface of the photosensitive composition layer, and a temporary support / thermoplastic resin layer / intermediate layer / photosensitive composition layer is laminated. A photosensitive transfer material having a structure was prepared. Hereinafter, this is referred to as a photosensitive transfer material for BM.

[Prescription of coating solution for intermediate layer]
・ Polyvinyl alcohol (PVA-105, manufactured by Kuraray Co., Ltd.) ・ ・ ・ 3.0 parts ・ Carboxymethylcellulose (TC-5E, manufactured by Shin-Etsu Chemical Co., Ltd.) ・ ・ ・ 0.15 parts ・ Surfactant 2 (Surflon) S-131, Seimi Chemical Co., Ltd.) ... 0.01 parts-Distilled water ... 524 parts-Methanol ... 429 parts

2-2-2. Formation of black matrix (BM) A glass substrate (Corning Millennium 0.7 mm thick) was washed with a rotating brush having nylon hair while spraying a glass detergent solution adjusted to 25 ° C. for 20 seconds with a shower, and purified water After shower washing, a silane coupling solution (N-β (aminoethyl) γ-aminopropyltrimethoxysilane 0.3 mass% aqueous solution; trade name: KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.) was sprayed for 20 seconds with a shower, Washed with pure water shower. Then, this board | substrate was heated for 2 minutes at 100 degreeC with the board | substrate preheating apparatus, and it sent to the laminator.
The protective film is peeled off from the BM photosensitive transfer material obtained above from the glass substrate after the silane coupling treatment, and the surface of the photosensitive composition layer exposed after the removal is in contact with the surface of the glass substrate. Lamination was carried out using a laminator type Lamic II (manufactured by Hitachi Industries, Ltd.) under the conditions of a rubber roller temperature of 130 ° C., a linear pressure of 100 N / cm, and a conveying speed of 2.2 m / min.

Subsequently, the PET temporary support was peeled off at the interface with the thermoplastic resin layer, and the temporary support was removed. After peeling off the temporary support, use a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) equipped with an ultra-high pressure mercury lamp to vertically stand the substrate and mask (quartz exposure mask with image pattern) In this state, the distance between the mask surface and the photosensitive composition layer was set to 200 μm, and pattern exposure was performed with an exposure amount of 30 mJ / cm ² .
Next, a triethanolamine developer (containing 30% by mass of triethanolamine, trade name: T-PD2, manufactured by Fuji Photo Film Co., Ltd.) 12 times with pure water (1 part by mass of T-PD2 and pure water) The mixture was mixed at a ratio of 11 parts by mass (30 ° C.) and subjected to shower development with a flat nozzle at a pressure of 0.04 MPa for 50 seconds to remove the thermoplastic resin layer and the intermediate layer. Subsequently, air was blown onto the substrate to drain the liquid, and then pure water was sprayed for 10 seconds by a shower to perform pure water shower cleaning, and air was blown to reduce the liquid pool on the substrate.

Subsequently, a sodium carbonate-based developer (0.38 mol / liter sodium bicarbonate, 0.47 mol / liter sodium carbonate, 5% by weight sodium dibutylnaphthalenesulfonate, an anionic surfactant, an antifoaming agent, and Stabilizer-containing; trade name: T-CD1, manufactured by Fuji Photo Film Co., Ltd.) diluted 5 times with pure water (29 ° C.) for 30 seconds, shower with cone type nozzle at pressure of 0.15 MPa Development was performed to develop and remove the photosensitive composition layer to obtain a pattern image.
Subsequently, a detergent (containing phosphate, silicate, nonionic surfactant, antifoaming agent, and stabilizer; trade name: T-SD1, manufactured by Fuji Photo Film Co., Ltd.) was diluted 10 times with pure water. The liquid (33 ° C.) was used as a shower with a cone type nozzle at a pressure of 0.02 MPa for 20 seconds, and the residue was removed by rubbing the pattern image with a rotating brush having nylon bristles to obtain a black matrix. .

After that, the substrate on which the black matrix was formed was post-exposed from both sides with an ultrahigh pressure mercury lamp at an exposure amount of 500 mJ / cm ² and then heat-treated (baked) at 220 ° C. for 15 minutes to form a light-shielding layer having a line width of 14 μm. The formed black matrix substrate was produced.
The light shielding property was measured by optical density (OD value) in visual mode using a transmission densitometer X-RITE 310T. The thickness of the substrate after post-baking was measured with a stylus-type film thickness meter DECTAC-3 manufactured by ULVAC.
Hereinafter, a glass substrate on which a black matrix is formed by coating and / or transfer is referred to as “BM substrate”, and the obtained BM substrates are summarized in Table 2.

<3. Preparation of colored photosensitive resin composition>
3-1. Preparation of Red Curable Composition The following RED dispersion composition R-1 was stirred for 1 hour using a homogenizer under the condition of 3000 rpm. The obtained mixed solution was subjected to fine dispersion treatment for 4 hours with a bead disperser (trade name: Dispermat, manufactured by GETZMANN) using 0.3 mm zirconia beads to obtain dispersion R-1.
(RED R-1 dispersion)
Pigment Red 254 (average particle size 20 nm in SEM observation)
・ ・ ・ 11 parts ・ Pigment Red 177 (average particle diameter 18 nm by SEM observation) ・ ・ ・ 4 parts ・ Dispersion resin A-1 ・ ・ ・ 5 parts [Monomer M-4 / Methacrylic acid / Terminal methacryloylated poly Methyl methacrylate copolymer (10/15/75% by mass, weight average molecular weight 20000,
Acid value 98 mg / g) Dispersion resin: Exemplified compound (6)]
Dispersant (trade name: Disperbyk-161, manufactured by Big Chemie) 3 parts propylene glycol monomethyl ether acetate 30% solution Alkali soluble resin: benzyl methacrylate / methacrylic acid copolymer 4 parts = 75 / 25 [mass ratio] copolymer, weight average molecular weight Mw: 5000) propylene glycol monomethyl ether acetate solution (solid content: 50 mass%)
Solvent B: propylene glycol monomethyl ether acetate 73 parts

(RED CR-1 coating solution)
-RED R-1 dispersion-100 parts-Epoxy resin: (trade name EHPE3150, manufactured by Daicel Chemical)-2 parts-Polymerizable compound: Dipentaerythritol penta-hexaacrylate-8 parts-Start of polymerization Agent: 4- (o-bromo-pN, N-di (ethoxycarbonylmethyl)
Amino-phenyl) -2,6-di (trichloromethyl) -s-triazine 1 part Polymerization initiator: 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 -1 part-Polymerization initiator: Diethylthioxanthone-0.5 part-Polymerization inhibitor: p-methoxyphenol-0.001 part-Fluorosurfactant (trade name: Megafac R30, manufactured by Dainippon Ink )
・ ・ ・ 0.01 parts ・ Nonionic surfactant (trade name: Tetronic R150 made by ADEKA)
・ ・ ・ 0.2 parts ・ Solvent: Propylene glycol n-butyl ether acetate ・ ・ ・ 30 parts ・ Solvent: Propylene glycol monomethyl ether acetate ・ ・ ・ 100 parts Mixing and stirring the above composition, CR-1 of curable coloring composition A coating solution was obtained.

3-2. Preparation of Green Curable Composition A dispersion was obtained by changing the R-1 composition of Example 1 to the following G-1 dispersion composition.
(GREEN G-1 dispersion)
・ Pigment Green 36 (average particle size 19 nm in SEM observation)
... 11 parts Pigment Yellow 150 (average particle diameter of 22 nm by SEM observation)
... 7 parts / dispersed resin A-2 ... 5 parts [Monomer / Methacrylic acid / Terminal methacryloylated polymethyl methacrylate copolymer capable of forming exemplified structural unit (M'-6) (12 / 17/71% by mass, weight average molecular weight 50000, acid value 110 mg / g) Dispersion resin: exemplary compound (X)]
・ Dispersant (trade name: Disperbyk-161, 30% solution manufactured by Big Chemie)
... 3 parts, alkali-soluble resin: benzyl methacrylate / methacrylic acid copolymer ... 4 parts = 85/15 [mass ratio] copolymer, weight average molecular weight Mw: 5000) propylene glycol monomethyl ether acetate solution ( Solid content: 50% by mass)
・ Solvent: Propylene glycol monomethyl ether acetate 70 parts

(GREEN CG-1 coating solution)
GREEN G-1 dispersion: 100 parts Epoxy resin: (trade name: EHPE3150, manufactured by Daicel Chemical): 2 parts Polymerizable compound: dipentaerythritol pentahexaacrylate: 6 parts Polymerizable compound : Tetra (ethoxy acrylate) of pentaerythritol ... 2 parts-Polymerization initiator: 1,3-bistrihalomethyl-5-benzooxolantolyazine
... 2 parts-Polymerization initiator: 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 ... 1 part-Polymerization initiator: Diethylthioxanthone ... 0.5 Part / polymerization inhibitor: p-methoxyphenol 0.001 part / fluoro-based surfactant (trade name: Megafac R08, manufactured by Dainippon Ink)
... 0.02 parts, nonionic surfactant (trade name: Emulgen A-60, manufactured by Kao) ... 0.5 parts, solvent: propylene glycol monomethyl ether acetate, 120 parts, solvent: propylene glycol n -Propyl ether acetate 30 parts The above composition was mixed and stirred to obtain a coating solution of curable coloring composition CG-1.

3-3. Preparation of green curable composition 3-2. In the preparation of the green curable composition, the polymerization initiator used for (GREEN CG-1 coating solution): 1,3-bistrihalomethyl-5-benzooxolantolyazine, and the polymerization initiator: 4- (o-bromo -P-N, N-di (ethoxycarbonylmethyl) amino-phenyl) -2,6-di (trichloromethyl) -s-triazine A curable composition for forming colored pixels (GREEN CG-2 coating solution) was obtained.

3-4. Preparation of Blue Curable Composition A dispersion was obtained by changing the R-1 composition of Example 1 to the following BLUE B-1 dispersion composition.
(BLUE B-1 dispersion)
Pigment Blue 15: 6 (average particle diameter by SEM observation: 15 nm)
... 14 parts ・ Pigment Violet 23 (average particle diameter by SEM observation: 23 nm)
... 1 part / dispersion resin A-3 ... 5 parts [dispersion resin belonging to the specific dispersion resin (B-1) obtained in the following synthesis example]
・ Dispersant (trade name: Disperbyk-161, 30% solution manufactured by Big Chemie)
... 3 parts, alkali-soluble resin: benzyl methacrylate / methacrylic acid copolymer ... 4 parts = 80/20 [mass ratio] copolymer, weight average molecular weight Mw: 5000) propylene glycol monomethyl ether acetate solution ( Solid content: 50% by mass)
Solvent: propylene glycol monomethyl ether acetate 73 parts

[Synthesis Example: Synthesis of Dispersant A-3]
(1. Synthesis of chain transfer agent A3)
7.83 parts of dipentaerythritol hexakis (3-mercaptopropionate) [DPMP; manufactured by Sakai Chemical Industry Co., Ltd.] and the following compound having an adsorption site and having a carbon-carbon double bond ( m-6) 4.55 parts was dissolved in 28.90 parts of propylene glycol monomethyl ether and heated to 70 ° C. under a nitrogen stream. To this, 0.04 part of 2,2′-azobis (2,4-dimethylvaleronitrile) [V-65, manufactured by Wako Pure Chemical Industries, Ltd.] was added and heated for 3 hours. Further, 0.04 part of V-65 was added and reacted at 70 ° C. for 3 hours under a nitrogen stream. By cooling to room temperature, a 30% solution of the mercaptan compound (chain transfer agent A3) according to the present invention shown below was obtained.

(2. Synthesis of dispersed resin)
A mixed solution of 4.99 parts of a 30% solution of chain transfer agent A3 obtained as described above, 19.0 parts of methyl methacrylate, 1.0 part of methacrylic acid, and 4.66 parts of propylene glycol monomethyl ether, It heated at 90 degreeC under nitrogen stream. While stirring this mixed solution, 0.139 part of dimethyl 2,2′-azobisisobutyrate [V-601, manufactured by Wako Pure Chemical Industries, Ltd.], 5.36 parts of propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate 9 40 parts of the mixed solution was added dropwise over 2.5 hours. After the completion of the dropwise addition, the mixture was reacted at 90 ° C. for 2.5 hours, and then a mixed solution of 0.046 parts of dimethyl 2,2′-azobisisobutyrate and 4.00 parts of propylene glycol monomethyl ether acetate was added, and further 2 hours. Reacted. By adding 1.52 parts of propylene glycol monomethyl ether and 21.7 parts of propylene glycol monomethyl ether acetate to the reaction liquid and cooling to room temperature, (B-1) specific dispersion resin (A-3: weight average molecular weight 24,000 in terms of polystyrene) ) Solution (specific dispersion resin 30% by mass, propylene glycol monomethyl ether 21% by mass, propylene glycol monomethyl ether acetate 49% by mass).
The acid value of this (B-1) specific dispersion resin A-3 was 48 mg / g. The structure of the specific dispersion resin A-3 is shown below.

(BLUE CB-1 coating solution)
BLUE B-1 dispersion: 100 parts Alkali-soluble resin: benzyl methacrylate / methacrylic acid copolymer: 6 parts = 80/20 [mass ratio] copolymer, weight average molecular weight Mw: 5000) Propylene glycol monomethyl ether acetate solution (solid content: 50% by mass)
・ Epoxy resin: (trade name, Celoxide 2080, manufactured by Daicel Chemical Industries Ltd.) 2 parts ・ UV curable resin: (trade name: Cyclomer P ACA-250, manufactured by Daicel Chemical Industries)
... 4 parts Acrylic copolymer with alicyclic, COOH and acryloyl groups in the side chain Propylene glycol monomethyl ether acetate solution (solid content: 50% by mass)
Polymerizable compound: dipentaerythritol pentahexaacrylate ... 12 parts Polymerization initiator: 1- (9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl) -1- (O-acetyloxime) ethanone 3 parts ・ Polymerization inhibitor: p-methoxyphenol 0.001 part ・ Fluorosurfactant (trade name: Megafac R08, manufactured by Dainippon Ink)
... 0.02 part, nonionic surfactant (trade name: Emulgen A-60, manufactured by Kao) ... 1.0 part, solvent: ethyl 3-ethoxypropionate ... 20 parts, solvent: propylene glycol Monomethyl ether acetate: 150 parts The above composition was mixed and stirred to obtain a coating solution of curable coloring composition CB-1.

3-5. Preparation of blue curable composition 3-4. In the preparation of the blue curable composition, the polymerization initiator used in (BLUE CB-1 coating solution): 1- (9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl) -1 -(O-acetyloxime) ethanone is converted into a polymerization initiator: 4- (o-bromo-pN, N-di (ethoxycarbonylmethyl) amino-phenyl) -2,6-di (trichloromethyl) -s- A curable composition for forming a colored pixel (BLUE CB-2 coating liquid) according to the present invention was obtained by preparing in the same manner as the CB-1 coating liquid except that it was changed to triazine.

[Comparative example]
<1. Preparation of red curable composition>
The dispersion resin A-1 was replaced with an alkali-soluble resin with RED R-1, that is, a dispersion was prepared with the following RED composition R-2.
(RED R-2 dispersion)
Pigment Red 254 (average particle size 20 nm in SEM observation)
・ ・ ・ 11 parts ・ Pigment Red 177 (average particle diameter 18 nm by SEM observation) ・ ・ ・ 4 parts ・ Dispersant (trade name: Disperbyk-161, 30% solution manufactured by Big Chemie)
... 3 parts, alkali-soluble resin: benzyl methacrylate / methacrylic acid copolymer ... 14 parts = 75/25 [mass ratio] copolymer, weight average molecular weight Mw: 5000) propylene glycol monomethyl ether acetate solution ( Solid content: 50% by mass)
Propylene glycol monomethyl ether acetate: 68 parts A curable composition for forming colored pixels (RED CR-3) was prepared by using R-2 instead of R-1 in a CR-1 composition.

<2. Preparation of green curable composition>
With GRREN G-1, the dispersion resin A-2 was replaced with an alkali-soluble resin, that is, a dispersion with the following composition G-2 was prepared.
(GREEN G-2 dispersion)
・ Pigment Green 36 (average particle size 19 nm in SEM observation)
... 11 parts Pigment Yellow 150 (average particle diameter of 22 nm by SEM observation)
... 7 parts Dispersant (Brand name: Disperbyk-161, 30% solution manufactured by Big Chemie)
... 3 parts, alkali-soluble resin: benzyl methacrylate / methacrylic acid copolymer ... 14 parts = 85/15 [mass ratio] copolymer, weight average molecular weight Mw: 5000) propylene glycol monomethyl ether acetate solution ( Solid content: 50% by mass)
Propylene glycol monomethyl ether acetate: 68 parts A curable composition for forming colored pixels (GREEN CG-3) was prepared by using G-2 instead of G-1 in a CG-1 composition.

<3. Preparation of blue curable composition>
In BLUE B-1, the dispersion resin A-3 was replaced with an alkali-soluble resin, that is, a dispersion was prepared with the following composition B-2.
(BLUE B-2 dispersion)
Pigment Blue 15: 6 (average particle diameter by SEM observation: 15 nm)
... 14 parts ・ Pigment Violet 23 (average particle diameter by SEM observation: 23 nm)
... 1 part Dispersant (Brand name: Disperbyk-161, 30% solution manufactured by Big Chemie)
... 3 parts, alkali-soluble resin: benzyl methacrylate / methacrylic acid copolymer ... 14 parts = 80/20 [mass ratio] copolymer, weight average molecular weight Mw: 5000) propylene glycol monomethyl ether acetate solution ( Solid content: 50% by mass)
Propylene glycol monomethyl ether acetate: 68 parts A curable composition for forming a colored pixel (BLUE CB-3) for comparison was prepared using B-2 instead of B-1 in the CB-1 composition.

<Evaluation results>
As shown below, a colored layer was formed in a single color, and the colored layer (corresponding to a colored pixel) was evaluated on the substrate. The results are shown in Tables 3 and 4. Table 5 summarizes the evaluation results of the color filter in which multicolored colored pixels are formed.
<Formation of a monochromatic colored layer>
Slit coating suitability was evaluated using a slit coating apparatus equipped with a slit head having a slit interval of 100 μm and a coating effective width of 500 mm. After coating on 10 glass substrates (width 550 mm, length 650 mm, thickness 0.7 mm) by a usual method, the slit head was kept in the air for 5 minutes and forcedly dried. After waiting, a dummy dispense was applied for 3 seconds, and 10 slits were applied to the glass substrate intermittently. The interval between the slit and the glass substrate was adjusted so that the coating thickness after post-baking was 2 μm, and the curable composition was applied at a coating speed of 100 mm / second. After the application, the sample was pre-baked on a hot plate at 90 ° C. for 60 seconds, and then the number of streaky irregularities on the coated surface was visually counted using a sodium light source and evaluated according to the following criteria.
○: No streak-like unevenness on the coated surface. Δ: One to five streaky unevennesses observed. X: Six or more streaky unevennesses observed. At the same time with an optical microscope having an XY stage. The presence / absence of foreign matters having a size of 10 μm or more was observed, the number of foreign matters was measured, and the number was shown per substrate.
The contrast was measured by the method described later.

  From Table 3, it can be seen that the colored pattern formed using the curable composition for forming a colored pixel of the present invention has a high contrast with respect to the comparative example, with no coating unevenness and no foreign matter mixed therein. Moreover, it was confirmed that it was excellent in color purity and luminance, and suitable as a pixel of a color filter. From the results in Table 4, it was confirmed that when RGB-LEDs were used as the backlight, further improvements in color purity and luminance could be achieved as compared with the case where a three-wavelength tube was used.

<Production of color filter>
The obtained colored curable composition was apply | coated to the BM formation surface side of the said BM board | substrate at the process similar to monochromatic colored layer formation. Coating was performed at a coating speed of 100 mm / second by adjusting the distance between the slit and the BM substrate and the discharge amount so that the film thickness after post-baking was 1.5 μm to 3.0 μm. Next, after heating (prebaking treatment) at 100 ° C. for 120 seconds using a hot plate, exposure was performed at 100 mJ / cm ² with a proximity gap of 300 μm using a HITACHI exposure machine LE5565 (all wavelengths). (Illuminance: 20 mW / cm ² ). Thereafter, development was performed with a 1.0% developer (25 ° C.) of potassium hydroxide developer CDK-1 (manufactured by FUJIFILM Electronics Materials Co., Ltd.) and washed with pure water. Next, post-baking was performed in a 220 ° C. clean oven for 30 minutes to form heat-treated red pixels.
Next, a green pixel portion was formed, and similarly a blue pixel portion was formed to obtain the color filter of Example 1.

[Examples 2 to 6]
The light-shielding part-forming curable composition (BM-1) used in Example 1 and the pixel-forming curable composition for each hue were changed as shown in Table 5 below, in the same manner as in Example 1. Thus, color filters of Examples 2 to 6 were obtained. The obtained color filters of Examples 1 to 6 were evaluated as follows. The results are shown in Table 5.

<Observation of morphology of colored part>
In the process of creating the color filter, the pattern of the light shielding layer and the colored layer after development and post-baking was observed with a scanning electron microscope. Table 5 shows the results after post-baking unless otherwise specified. As for the height of the corners, the height from the flat surface of the colored portion was measured with an SEM photograph.

<Contrast measurement of color filters and single color substrates>
As a backlight unit, a three-wavelength cold cathode tube light source (FWL18EX-N manufactured by Toshiba Lighting & Technology Co., Ltd.) was used, and between the two polarizing plates (G1220DUN manufactured by Nitto Denko Corporation) The Yc value of the chromaticity of light that passes when a single color substrate of R, G, and B is installed and the polarizing plate is installed in parallel Nicol is the Yc value of the chromaticity of the light that passes when installed in crossed Nicols. The contrast was obtained by dividing. A color luminance meter (BM-5 manufactured by Topcon Corporation) was used for the measurement of chromaticity.

<Chromaticity evaluation of monochromatic substrate>
The light source is FR1112H (chip type LED manufactured by Stanley Electric Co., Ltd.) as a red LED, DG1112H (chip type LED manufactured by Stanley Electric Co., Ltd.) as a green LED, and DB1112H (chip manufactured by Stanley Electric Co., Ltd.) as a blue LED. Sidelight type backlight was constructed using a type LED). Using this light source and the above-mentioned three-wavelength cold cathode tube light source, chromaticity was measured with the MCPD-2000, and color reproducibility was evaluated.

<Production and visibility evaluation of liquid crystal display device>
A transparent electrode made of ITO (Indium Tin Oxide) was further formed on the R, G, B pixels and black matrix of the color filter substrate obtained as described above by sputtering. Next, according to Example 1 of Japanese Patent Application Laid-Open No. 2006-64921, a spacer was formed in a portion corresponding to the upper part of the partition wall (black matrix) on the ITO film formed as described above. Separately, a glass substrate is prepared as a counter substrate, patterning is performed for the PVA mode on the transparent electrode and the counter substrate of the color filter substrate, respectively, and a polyimide alignment film (Nissan Chemical's Sun Ever 7492 70 nm after baking) is provided thereon. And baked at 180 ° C. for 1 hour. After that, a UV curable resin sealant is applied by a dispenser method at a position corresponding to the outer periphery of the black matrix provided around the pixel group of the color filter, and a liquid crystal for PVA mode is dropped and attached to the counter substrate. After bonding, the bonded substrate was irradiated with UV, and then heat-treated to cure the sealant. A polarizing plate (NPF-SEG1224DU manufactured by Nitto Denko) was attached to both surfaces of the liquid crystal cell thus obtained. Next, a three-wavelength cold-cathode tube light source (FWL18EX-N manufactured by Toshiba Lighting & Technology Co., Ltd.) was placed on the side of the liquid crystal cell on which the polarizing plate was provided to form a liquid crystal display device.
In the evaluation of visibility, a voltage was applied and black display was performed, and the vicinity of the BM on the screen was observed with a 100 × microscope to observe light leakage.

As is clear from Table 5, the color filter of the example in which the light-shielding portion and the colored pixel are formed using the light-shielding portion-forming curable composition and the colored pixel-forming curable composition of the present invention has an appropriate pixel shape. It was confirmed that an image having excellent contrast and excellent visibility could be formed.
Further, by comparing the Example 3 and the Example 6, by using a triazine compound as a polymerization initiator, the contrast and visibility of the color filter are further improved while having the same light shielding part, and the contrast is improved. It can be seen that a high-visibility liquid crystal display device can be obtained.

Claims (11)

  A colored pixel formed of a curable composition for forming a colored pixel and having a color purity of 65% or more with respect to the area (100) of the three primary color chromaticity points of the NTSC system in the CIE color system, A color filter formed of a curable composition for forming a light shielding part, having an optical density (OD value) of 4.5 or more, a light shielding part having a width of 5 to 15 μm, and a color filter contrast ratio of 5000 or more.   The color filter according to claim 1, wherein a film thickness of the colored pixel portion is in a range of 1.5 to 2.5 μm.   2. The color filter according to claim 1, wherein the optical density of the light-shielding part is 4.8 or more and the film thickness is in the range of 0.3 to 1.0 [mu] m. The color filter according to claim 1, wherein the curable composition for forming colored pixels contains a polymerization initiator represented by the following general formula (DA).

In the general formula (DA), R ¹ and R ² are each independently a hydrogen atom, an alkyl group, an aryl group, or the following general formula (DA-1) or general formula (DA-A- The substituent shown by 2) is represented. R ³ and R ⁴ each independently represents a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group. X and Y each independently represent —Cl or —Br, and m and n each represents 0, 1 or 2.

In general formula (D-A-1) and the general formula ^(D-A-2), R 5, R 6, R 7 each independently represent an alkyl group, or an aryl group. A colorant, a compound represented by the following general formula (1), a polymer containing a copolymer unit derived from the monomer represented by the following general formula (I), and the following general formula (a) One or more polymer dispersants selected from the group consisting of polymers containing structural units having an acid value of 20 to 300 mg / g and a weight average molecular weight in the range of 3,000 to 100,000, A colored pixel containing a polymerizable compound, a polymerization initiator and a solvent, and having a color purity of 65% or more with respect to the area (100) of the NTSC three primary color chromaticity points in the CIE color system A curable composition for forming a color filter colored pixel which can be formed.

In the general formula (1), A ¹ represents an organic dye structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, or 4 or more carbon atoms. Represents a monovalent organic group containing at least one portion selected from a hydrocarbon group, an alkoxysilyl group, an epoxy group, an isocyanate group, and a hydroxyl group. The n A ¹ may be the same or different.
R ¹ represents an (m + n) -valent organic linking group, where 3 <(m + n) <10. R ² represents a single bond or a divalent organic linking group. P ¹ represents a polymer skeleton.

In the general formula (I), R ⁰¹ represents a hydrogen atom or a substituted or unsubstituted alkyl group. R ⁰² represents an alkylene group. W represents -CO-, -C (= O) O-, -CONH-, -OC (= O)-, or a phenylene group. X is —O—, —S—, —C (═O) O—, —CONH—, —C (═O) S—, —NHCONH—, —NHC (═O) O—, —NHC (═O ) Represents one selected from S-, -OC (= O)-, -OCONH-, and -NHCO-. Y represents any one selected from NR ⁰³ , O, and S, and R ⁰³ represents a hydrogen atom, an alkyl group, or an aryl group. In the formula, N and Y are connected to each other to form a cyclic structure. m1 and n1 are each independently 0 or 1.

In the general formula (a), R ^1a represents hydrogen or a methyl group, R ^2a represents an alkylene group, and Z ¹ represents a nitrogen-containing heterocyclic structure. The said polymerization initiator contains the compound represented by the following general formula (DA), The curable composition for color filter coloring pixel formation of Claim 5 characterized by the above-mentioned.

In the general formula (DA), R ¹ and R ² are each independently a hydrogen atom, an alkyl group, an aryl group, or the following general formula (DA-1) or general formula (DA-A- The substituent shown by 2) is represented. R ³ and R ⁴ each independently represents a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group. X and Y each independently represent —Cl or —Br, and m and n each represents 0, 1 or 2.

In general formula (D-A-1) and the general formula ^(D-A-2), R 5, R 6, R 7 each independently represent an alkyl group, or an aryl group.   A color filter light-shielding part that can form a light-shielding part having an optical density (OD value) of 4.5 or more, containing 40 to 80% by mass of carbon black as a solid content as a polymerizable compound, a polymerization initiator, and a light-shielding agent Curable composition for forming.   Color filter light-shielding part which can form light-shielding part having optical density (OD value) of 4.5 or more containing metal compound as a polymerizable compound, polymerization initiator and light-shielding agent in solid content of 50 to 90% by mass Curable composition for forming.   It forms with the curable composition for colored pixel formation of Claim 5 or Claim 6, and the curable composition for light-shielding part formation of Claim 7 or Claim 8, It is characterized by the above-mentioned. The color filter according to claim 4.   A liquid crystal display device comprising the color filter according to any one of claims 1 to 4 and 9.   The liquid crystal display device according to claim 10, comprising an RGB-LED light source as a backlight.