KR20100016082A - Color filter, liquid crystal display device and hardening composition to be used in the production of the same - Google Patents

Abstract

The present invention is formed of a curable composition for forming colored pixels, wherein the color purity in the C light source is 65% or more with respect to the area 100 of the three primary color chromaticity points of the NTSC system, and the curable composition for forming the light shielding portion. And a light filter having an optical density (OD value) of 4.5 or more, a width of 5 to 15 µm, and a color filter contrast ratio of 5000 or more.

Description

COLOR FILTER, LIQUID CRYSTAL DISPLAY DEVICE AND HARDENING COMPOSITION TO BE USED IN THE PRODUCTION OF THE SAME}

The present invention relates to a color filter used for a liquid crystal display device (LCD), a solid state image pickup device (CCD, CMOS, etc.), a liquid crystal display device having the same, and a curable composition suitable for forming colored pixels or light blocking portions of a color filter.

The color filter is an essential component of a liquid crystal display or a solid state image pickup device.

In the use of color filters for liquid crystal displays (LCDs), substrate sizes have been expanded for large-scale TV production, and in order to improve productivity when large-sized substrates are used, the yield in application to a slit method or the like is high, and exposure is performed at low energy. In addition, a wide development latitude is required. In addition, in the liquid crystal display for TV use, higher image quality is demanded compared with the conventional notebook and monitor use. That is, the contrast and the color purity are improved.

In order to improve contrast, a finer one is required as the particle size of a colorant (organic pigment, etc.) to be used for the curable composition used for the production of a color filter. (See Patent Document 1, for example.) Therefore, the amount of dispersant added for pigment dispersion tends to increase. Moreover, in order to improve color purity, higher content is calculated | required as content rate of the coloring agent (organic pigment) in solid content of a curable composition. Therefore, there exists a tendency for the content rate of the photoinitiator, photopolymerizable monomer, and alkali-soluble resin component for giving alkali solubility to solid content in curable composition to fall.

For this reason, various novel dispersants have been proposed for the purpose of improving pigment dispersibility, for example, an amine polymer dispersant for living anionic polymerization (see, for example, Patent Document 2) and a cationic graft polymer (for example, (See Patent Document 3).

Moreover, although the technique which prescribes chromaticity of RGB which comprises a pixel as a high color purity is proposed in order to implement | achieve high color purity (for example, refer patent document 4, 5), the color purity of each coloring pattern improves, but is practical. It does not realize sufficient contrast and wide latitude in the development process.

On the other hand, proposals have been made to improve the light blocking property of the black matrix for the purpose of realizing the optimum contrast, and the OD value is set to 4 or more for the purpose of reducing the reflection of external light by increasing the shielding effect and improving the display contrast. Although black matrix formation technology is proposed (for example, refer patent document 6), it is a present state that development of the shielding layer with a larger shielding effect is calculated | required.

Patent Document 1: Japanese Patent Laid-Open No. 2005-316439

Patent Document 2: Japanese Patent Application Laid-Open No. 2005-283950

Patent Document 3: Japanese Patent Laid-Open No. 2006-52410

Patent Document 4: Japanese Patent Application Laid-Open No. 2001-228322

Patent Document 5: Japanese Patent Application Laid-Open No. 2002-107525

Patent Document 6: Japanese Patent Application Laid-Open No. 2005-281386

SUMMARY OF THE INVENTION The present invention has been made to improve all the above-mentioned drawbacks of the prior art, and an object of the present invention is to provide a color filter having a high color purity of a colored pixel and a high color concentration of a light shielding portion, and to achieve high contrast and a liquid crystal comprising the color filter. It is to provide a display device.

Still another object of the present invention is to provide a curable composition for forming a pixel capable of forming a colored pixel having a high color purity useful for forming the color filter of the present invention, and a curable composition for forming a light shielding portion capable of forming a light shield having a high color concentration. It is to offer.

MEANS TO SOLVE THE PROBLEM As a result of earnestly research, the inventors found out that the color filter excellent in contrast was obtained by providing the colored pixel produced using the specific dispersing agent, and the light shielding part formed using the specific light-shielding agent, and completed this invention.

The structure of this invention is as showing below.

It is formed with the curable composition for <1> colored pixel formation, The curable composition for colored pixels and light-shielding part formation whose color purity in C light source is 65% or more with respect to the area 100 of the three primary color chromaticity point of NTSC system in CIE color system. And a light filter having an optical density (OD value) of 4.5 or more, a light shielding portion having a width of 5 to 15 µm, and a color filter contrast ratio of 5000 or more.

The film thickness of the <2> above-mentioned colored pixel part is 1.5-2.5 micrometers, The color filter as described in <1> description.

<3> The color filter according to <1>, wherein the optical density of the light shielding portion is 4.8 or more and the film thickness is in the range of 0.3 to 1.0 µm.

<4> The color filter according to <1>, wherein the curable composition for forming colored pixels contains a polymerization initiator represented by the following General Formula (D-A).

In said general formula (DA), R <^1> , R <^2> respectively independently represents a hydrogen atom, an alkyl group, an aryl group, or the substituent represented by the following general formula (DA-1) or general formula (DA-2). R ³ and R ⁴ each independently represent 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 represent 0, 1 or 2.

R <^5> , R <^6> , R <^7> in the said general formula (DA-1) and general formula (DA-2) respectively independently represents an alkyl group or an aryl group.

<5> A coloring agent, the compound represented by the following general formula (1), the polymer containing the copolymerization unit derived from the monomer represented by the following general formula (I), and the structural unit represented by the following general formula (a) A polymer dispersant, a polymerizable compound, a polymerization initiator and a solvent selected from the group consisting of polymers having an acid value of 20 to 300 mg / g and having a weight average molecular weight in the range of 3,000 to 100,000, The curable composition for forming a color filter colored pixel which can form colored pixels whose color purity in the C light source is 65% or more with respect to the area 100 of the three primary color chromaticity points of the NTSC system.

In general formula (1), A ¹ is an organic pigment 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, a hydrocarbon group having 4 or more carbon atoms, alkoxy The monovalent organic group containing at least 1 sort (s) of site | parts chosen from a silyl group, an epoxy group, an isocyanate group, and a hydroxyl group is shown. n pieces A ¹ may be the same or different.

R <^1> represents a (m + n) valent organic coupling group, where m represents 1-8, n represents 2-9, and 3 <(m + n) <10. In addition, R ² represents a single bond or a divalent organic linking group. P ¹ represents a polymer skeleton.

R ⁰¹ in General Formula (I) represents a hydrogen atom or a substituted or unsubstituted alkyl group. R ⁰² represents an alkylene group. W represents -CO-, -C (= 0) O-, -CONH-, -OC (= 0)-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 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 0 or 1 each independently.

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

<6> Curable composition for color filter coloring pixel formation of <5> description characterized by the said polymerization initiator containing the compound represented by the following general formula (D-A).

R ¹ and R ² in the general formula (DA) each independently represent a hydrogen atom, an alkyl group, an aryl group, or a substituent represented by the following general formula (DA-1) or general formula (DA-2). R ³ and R ⁴ each independently represent 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 represent 0, 1 or 2.

R <^5> , R <^6> , R <^7> in the said general formula (DA-1) and general formula (DA-2) respectively independently represents an alkyl group or an aryl group.

<7> Curable composition for forming a color filter light-shielding portion that contains 40 to 80 mass% of carbon black in terms of solid content as a polymerizable compound, a polymerization initiator, and a light-shielding agent, and can form a light-shielding portion having an optical density (OD value) of 4.5 or more. .

<8> Curable for forming the color filter light shielding part which can contain 50-90 mass% of metal microparticles in conversion of solid content as a polymeric compound, a polymerization initiator, and a light shielding agent, and can form a light shielding part whose optical density (OD value) is 4.5 or more. Composition.

<9> Formed by the composition for colored pixel formation as described in <5> or <6>, and the composition for light-shielding part formation as described in <7> or <8>, In either <1>-<4> characterized by the above-mentioned. The color filter described.

<10> The liquid crystal display device provided with the color filter in any one of <1>-<4> and <9>.

<11> The liquid crystal display device described in <10> provided with a RGB-LED light source.

According to the function of the polymer dispersant, the pigment dispersion stability is good even if the pigment particles are miniaturized in order to achieve high contrast, which can be stored for a long time, and colored pixels of high color purity are formed with high contrast. Moreover, since the light shielding part with a large shielding effect can be formed in a thin layer by the function of the curable composition used for a light shielding part, it has aptitude to slit application | coating and a high performance colored pixel part without a foreign material, application | coating spot | dye, and an application line is formed. Therefore, it is possible to provide a color filter having a large light blocking effect of the light shielding layer, high contrast without light leakage, and good color reproducibility, thereby providing a display device with high visibility and good visibility.

In addition, since the colored pixel region has high light transmittance even with high color purity, the display device can be easily provided in an environment where power consumption may be small.

Moreover, since the curable composition which forms a colored pixel and a light shielding part can be hardened | cured with high sensitivity, a throughput is large, a yield is favorable, and productivity is high, and a cheap color filter can be provided.

In addition, in a preferred embodiment of the present invention, by using the display device using the RGB-LED light source as well as the color filter of the present invention, high color reproducibility can be further improved, and high color purity and high contrast color filter technology can be more effectively exhibited. .

(Effects of the Invention)

According to the present invention, it is possible to provide a color filter having a high color purity of a colored pixel and a color concentration of a light shielding portion, which realizes high contrast, and a liquid crystal display device having the color filter.

Moreover, according to this invention, the curable composition for pixel formation which can form the colored pixel with high color purity useful for formation of the said color filter of this invention, and the curable composition for light shielding part formation which can form the light shielding part with high shielding effect are provided. Can provide.

EMBODIMENT OF THE INVENTION Hereinafter, the curable composition for colored pixel formation and the curable composition for light shielding part formation useful for formation of the color filter, a display apparatus, and a color filter of this invention are demonstrated in detail.

[Color filter]

The color filter of the present invention is formed by the curable composition for forming colored pixels in a CIE color system, and the colored pixels and the light shielding portion 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 are obtained. It is formed of the curable composition for optical use, has an optical density (OD value) of 4.5 or more, has a light shielding portion of 5 to 15 µm in width, and the contrast ratio of each monochromatic layer is 5000 or more.

Here, the color purity of the colored pixel means that the chromaticity (in this case, RGB color filter) is represented with respect to the area 100 of the three primary color chromaticity points of the NTSC system in the CIE color system, and is JIS-Z. Based on -8701, it can measure using a commercially available side colorimeter. In the present invention, the color purity measured by the C light source of the backlight of the colored pixel needs to be 65% or more, and more preferably 70% or more. Such color purity can be achieved by, for example, a method of using a colorant having a high absorbance at a predetermined wavelength, a method of increasing the colorant content per unit area, and the like. Moreover, it can be said that use of the coloring agent with large absorbance in an unnecessary wavelength is not preferable from a viewpoint of color purity improvement.

It is preferable that the colored pixel in the color filter of this invention contains a coloring agent in high concentration, and consists of a coloring pattern with high color development and a thin film thickness, It is preferable that the film thickness of a colored pixel is 2.5 micrometers or less, More preferably, It is preferable that it is 2.0 micrometers or less. The thinner the thinner the better, as long as it can achieve the desired color purity as the pixel, but considering the film formability, developability, and uniformity of the pixel, the film thickness is preferably 1.0 μm or more, more preferably 1.4 μm or more. Do.

The colored pixel which can implement such color purity and contrast is formed by the curable composition for colored pixel formation demonstrated in detail below.

Curable Composition for Colored Pixel Formation

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 by light, and includes (A-1) a colorant, (B) a polymer dispersant, and (C) a polymerizable compound. , (D) photoinitiator and (E) solvent are contained, and other components may be included as desired.

<(A-1) Colorant>

Here, although the pigment used as a coloring agent may be an inorganic pigment or an organic pigment, considering that it is preferable that it is high transmittance | permeability, use of a thing with a small particle size is preferable as much as possible, It is preferable that average particle size is 10-100 nm, Furthermore, Preferably it is the range of 10-50 nm. In the curable composition of this invention, since the specific (B) polymer dispersing agent mentioned later is used, even if the size of a coloring agent is small, since pigment dispersibility and dispersion stability are favorable, the coloring pixel excellent in color purity can be formed even if it is thin. .

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

In addition, 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;

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. can be mentioned.

Although it does not specifically limit in this invention, The following pigment is more preferable.

Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185,

Pigment Orange 36, 71,

Pigment Red 122, 150, 171, 175, 177, 209, 224, 242, 254, 255, 264,

C.I. Pigment Violet 19, 23, 37,

Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66,

C.I. Pigment green 7, 36, 37;

These organic pigments may be used alone or in various combinations to increase color purity. The specific example of a combination is 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 bis azo yellow pigment, an isoindolin yellow pigment, and a quinophthalone yellow pigment Or a mixture of perylene-based red pigments can be used. For example, CI pigment red 177 is listed as an anthraquinone pigment, CI pigment red 155 and CI pigment red 224 are listed as a perylene pigment, and CI pigment red 254 is a diketopyrrolopyrrole pigment. It is enumerated and mixing with CI pigment yellow 139 is preferable at the point of color reproducibility. In addition, the mass ratio of the red pigment and the yellow pigment is preferably 100: 5 to 100: 50 from the viewpoint of obtaining sufficient color purity and suppressing the deviation from the NTSC target color. Especially as said mass ratio, the range of 100: 10-100: 30 is optimal. 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 alone or a mixture of this and a bis azo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment or an isoindolin yellow pigment can be used. For example, CI Pigment Green 7, 36, 37 and CI Pigment Yellow 83, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 180 or CI Pigment Yellow Mixing with 185 is preferred. The mass ratio of the green pigment and the yellow pigment is preferably 100: 5 to 100: 150 from the viewpoint of obtaining sufficient color purity and suppressing the deviation from the NTSC target color. As mass ratio, the range of 100: 30-100: 120 is especially preferable.

As a blue pigment, a phthalocyanine type pigment can be used individually or the mixture of this and a dioxazine type purple pigment can be used. For example, a mixture of C.I. Pigment Blue 15: 6 and C.I.Pigment Violet 23 is preferred. As for mass ratio of a blue pigment and a purple pigment, 100: 0-100: 50 are preferable, More preferably, it is 100: 5-100: 30.

As content of the (A-1) coloring agent (pigment) in the curable composition for coloring pixel formation of this invention, 25-75 mass% is preferable with respect to the total solid (mass) of the said composition, and 32-70 mass% More preferred. (A-1) If content of a coloring agent (pigment) is in the said range, it is effective also in ensuring the color characteristic excellent in color concentration sufficiently.

<(B) Polymer Dispersant>

The polymer dispersing agent (B) in the present invention needs to have an acid value of 20 to 300 mg / g and a weight average molecular weight in the range of 3,000 to 100,000. Such a specific polymer dispersing agent may only be called "(B) dispersion resin" below.

(B) dispersion resin in this invention functions as a dispersing agent of the light-shielding agent (pigment for black matrix formation) in the dispersing agent of the pigment listed as said (A-1) coloring agent, or the curable composition for light-shielding part formation mentioned later. It is a compound which can be.

(B) Since dispersion resin needs to have specific acid value as mentioned above, it is preferable that it is a high molecular compound which has 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 copolymers [for example, , A copolymer of a polyether / polyurethane copolymer, a polymer of a polyether / vinyl monomer, or the like (random copolymer, block copolymer, or graft copolymer may be used). At least 1 sort (s) is preferable, At least 1 sort (s) chosen from the group which consists of a polymer or copolymer of a vinyl monomer, an ester type polymer, an ether type polymer, a urethane type polymer, and these modified | denatured products or a copolymer is more preferable, Particular preference is given to polymers or copolymers.

Moreover, as a method of introducing an acidic group into the above-mentioned polymer skeleton, the method of copolymerizing the monomer containing an acidic group when superposing | polymerizing the said polymer skeleton, and also introduce | transducing the said polymer skeleton by superposition | polymerization after superposition | polymerization is mentioned, for example. The method is listed.

As a monomer containing an acidic group, for example, (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-methylpropanesulfonic acid, And monomers obtained by reacting an alcoholic hydroxyl group-containing monomer such as mono (meth) acryloylethyl ester or 2-hydroxyethyl methacrylate with cyclic acid anhydrides such as maleic anhydride and phthalic anhydride.

Among these, as an example of a preferable monomer, the monomer etc. which are obtained by making alcoholic hydroxyl group containing monomers, such as (meth) acrylic acid and 2-hydroxyethyl methacrylate, cyclic acid anhydrides, such as maleic anhydride and a phthalic anhydride, etc. are mentioned, etc. are mentioned. Examples of the cyclic acid anhydride used herein include itaconic anhydride, maleic anhydride, phthalic anhydride, succinic anhydride, glutaric anhydride, trimellitic anhydride, and the like, but phthalic anhydride and succinic anhydride are particularly preferable.

In addition, the high molecular compound which has an acidic group may be what copolymerizes a vinyl monomer component further.

Although it does not restrict | limit especially as said vinyl monomer, For example, (meth) acrylic acid ester, crotonic acid ester, vinyl ester, maleic acid diester, fumaric acid diester, itaconic acid diester, (meth) Acrylamides, vinyl ethers, esters of vinyl alcohol, styrenes, (meth) acrylonitrile and the like are preferable.

As such a vinyl monomer, the following compounds are mentioned, for example.

Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, T-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, t-octyl (meth) acrylate, (Meth) acrylate dodecyl, (meth) acrylate octadecyl, (meth) acrylate acetoxyethyl, (meth) acrylate phenyl, (meth) acrylate 2-hydroxyethyl, (meth) acrylate 2-methoxyethyl, (meth) 2-ethoxyethyl), 2- (2-methoxyethoxy) ethyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, (meth) acrylic acid di Ethylene glycol monomethyl ether, (meth) acrylic acid diethylene glycol monoethyl ether, (meth Triethylene glycol monomethyl ether (acrylate), triethylene glycol monoethyl ether (meth) acrylate, polyethylene glycol monomethyl ether (meth) acrylate, polyethylene glycol monoethyl ether (meth) acrylate, β-phenoxy (meth) acrylate Ethoxyethyl, nonylphenoxypolyethylene glycol (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, trifluoroethyl (meth) acrylate, fluorofluoro (meth) acrylate Pentyl, perfluorooctylethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tribromophenyl (meth) acrylate, tribromophenyloxyethyl (meth) acrylate, and the like.

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

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

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

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

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

As (meth) acrylamide, (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, Nn-butylacryl (meth) amide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth Ta) acrylamide, N, N-diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) acryloyl morpholine, diacetone acrylamide, and the like. Listed.

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 and bromostyrene And chloromethylstyrene, hydroxystyrene protected with a group deprotectable by an acidic substance (for example, t-Boc, etc.), methyl vinylbenzoate, α-methylstyrene, and the like.

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

In addition to the above compounds, (meth) acrylonitrile, a heterocyclic group substituted with a vinyl group (for example, vinylpyridine, vinylpyrrolidone, vinylcarbazole, etc.), N-vinylformamide, N-vinylacetamide, N -Vinylimidazole, vinyl caprolactone, etc. can also be used.

Moreover, the vinyl monomer which has functional groups, such as a urethane group, a urea group, a sulfonamide group, a phenol group, and an imide group, can also be used, for example. As a monomer which has such a urethane group or a urea group, it is possible to synthesize | combine suitably using addition reaction of an isocyanate group, a hydroxyl group, or an amino group, for example. Specifically, addition reaction of an isocyanate group-containing monomer and a compound containing one hydroxyl group or a compound containing one primary or secondary amino group, or addition of a hydroxyl group-containing monomer or a primary or secondary amino group-containing monomer and a monoisocyanate It can synthesize | combine suitably by reaction or the like.

In addition, you may consider and use a polymeric oligomer as shown below as a vinyl monomer.

The polymerizable oligomer (hereinafter, sometimes referred to as "macro monomer") is an oligomer having a terminal having an ethylenically unsaturated double bond at its terminal. In this invention, it is preferable to have the group which has the said ethylenically unsaturated double bond only in one of the both ends of the said oligomer among the said polymerizable oligomers.

As molecular weight of the said polymerizable oligomer, it is preferable that the number average molecular weight (Mn) of polystyrene conversion is 1000-20000, and it is more preferable that it is 2000-15000. When the said number average molecular weight is less than 1000, the steric repulsion effect as a dispersing agent may not be enough, and when it exceeds 20000, time may be needed for adsorption to a coloring agent (pigment) by a steric effect.

As said oligomer, the homopolymer or copolymer formed from the at least 1 sort (s) of monomer chosen from alkyl (meth) acrylate, styrene, acrylonitrile, vinyl acetate, butadiene generally is mentioned, for example, Alkyl ( Preference is given to homopolymers or copolymers of meta) acrylates, polystyrenes and the like. In this invention, these oligomers may be substituted by the substituent and there is no restriction | limiting in particular as said substituent, For example, a hydroxyl group, a halogen atom, etc. are mentioned.

Said vinyl monomer may be superposed | polymerized only by 1 type, and may be copolymerized in combination of 2 or more types, and these radical polymers are obtained by superposing | polymerizing the corresponding vinyl monomer in a well-known method according to a conventional method, respectively.

For example, these vinyl monomers and a chain transfer agent are melt | dissolved in a suitable solvent, and a radical polymerization initiator is added to this, and it is obtained using the method (solution polymerization method) which superposes | polymerizes in solution at about 50 degreeC-220 degreeC. .

As an example of a suitable solvent used by the solution polymerization method, it can select arbitrarily according to the solubility of the monomer to be used and the copolymer to produce | generate. 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. You may use these solvent in mixture of 2 or more type.

Moreover, as a radical polymerization initiator, azo compounds, such as 2,2'- azobis (isobutyronitrile) (AIBN), 2,2'- azobis- (2,4'- dimethylvaleronitrile), and benzoyl peroxide Peroxides, and persulfates, such as potassium persulfate and ammonium persulfate, etc. can be used.

As described above, the dispersion resin (B) in the present invention needs to have an acid value in the range of 20 to 300 mg / g, preferably in the range of 30 to 250 mg / g, and more preferably 30 to 200 mg. range of / g.

If the acid value of (B) dispersion resin is this range, it is excellent in the dispersibility and dispersion stability of (A) pigment (pigment), and also excellent in alkali developability.

Moreover, the weight average molecular weight of (B) dispersion resin needs to be the range of 3,000-100,000, Preferably it is the range of 3,000-70,000, More preferably, it is the range of 5,000-50,000.

If the weight average molecular weight of (B) dispersion resin is this range, it is preferable from a viewpoint of shortening of the dispersion time of the pigment used as a coloring agent (A-1) and the (A-2) light-shielding agent mentioned later, and stability with time of a dispersion. .

Moreover, as (B) dispersion resin in this invention, the high molecular compound which has 2-100 polymer pigment adsorption groups in a polymer terminal, or the high molecular compound which has a nitrogen-containing heterocycle and also has the monomer which has an ethylenically unsaturated group as a copolymerization unit Is preferably.

Hereinafter, these two high molecular compounds are demonstrated concretely.

(B) As the polymer compound having 2 to 100 pigment-adsorbent groups as the dispersing resin at the polymer terminal, the polymer compound has a specific acid value and weight average molecular weight as described above, and has 2 to 100 pigment-adsorbent groups at the polymer terminal, Although it does not restrict | limit especially, the following are preferable.

That is, the polymer compound which has 4-70 pigment | dye adsorption groups in a polymer terminal is preferable, and the polymer compound which has 5-50 pigment | dye adsorption groups in a polymer terminal is preferable. As the pigment adsorber, an organic pigment structure, a heterocyclic structure, an acidic group, a basic group and the like are preferable. Among these, it is preferable that it is a high molecular compound represented by General formula (1) mentioned later.

(B) A polymer compound having a nitrogen-containing heterocycle as a dispersion resin and containing a monomer having an ethylenically unsaturated group as a copolymerization unit has a specific acid value and a weight average molecular weight as described above, and a nitrogen-containing heterocycle Although it does not restrict | limit especially if it is a high molecular compound which has a monomer which has a monomer which has an ethylenically unsaturated group as a copolymerization unit, It is preferable to have the following nitrogen containing heterocycle.

Preferred nitrogen-containing heterocycles include pyrrole, pyrroline, pyrrolidine, pyrazole, pyrazoline, pyrazolidine, imidazole, triazole, pyridine, piperidine, morpholine, pyridazine, pyrimidine, piperazine, tri Azine, isoindolin, isoindolinone, benzimidazolone, benzothiazole, succinimide, phthalimide, naphthalimide, hydantoin and carbazole.

Especially, it is preferable that it is a polymer containing the copolymerization 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, the copolymer unit derived from the high molecular compound represented by (B-1) general formula (1) preferable as (B) dispersion resin in this invention, and the monomer represented by (B-2) general formula (I) The polymer containing and the polymer containing the structural unit represented by (B-3) general formula (a) are demonstrated.

[(B-1) Polymer compound represented by General Formula (1): (B-1) Specific Dispersion Resin]

First, the high molecular compound represented by following General formula (1) (Hereinafter, it calls suitably "(B-1) specific dispersion resin.") Is demonstrated.

In general formula (1), A ¹ is an organic pigment 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, a hydrocarbon group having 4 or more carbon atoms, alkoxy The monovalent organic group containing at least 1 sort (s) of site | parts chosen from a silyl group, an epoxy group, an isocyanate group, and a hydroxyl group is shown. n pieces A ¹ may be the same or different.

That is, A ¹ is a structure having an adsorption capacity for an organic pigment structure, a pigment such as a heterocyclic structure, an acid group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, and having 4 carbon atoms. The monovalent organic group containing at least 1 sort (s) of functional group which has the adsorption capacity with respect to a pigment, such as more than a hydrocarbon group, an alkoxy silyl group, an epoxy group, an isocyanate group, and a hydroxyl group, is shown.

In addition, the site | part (the said structure and functional group) which has the adsorption | suction ability with respect to this pigment is demonstrated generally as a "adsorption site | part" generically.

The adsorption sites are good if it contains at least one member in one of A ^1, may contain two or more kinds.

In the present invention, the "monovalent organic group containing at least one adsorption site" includes the adsorption site described above, 1 to 200 carbon atoms, 0 to 20 nitrogen atoms, 0 to 100 oxygen atoms, and 1 to 1 carbon atoms. It is a monovalent organic group which combines the organic coupling group which consists of 400 hydrogen atoms and 0-40 sulfur atoms. In addition, when the adsorption site itself can constitute a monovalent organic group, the adsorption site may be the monovalent organic group represented by A ¹ .

First, it will be described below adsorption sites constituting the A ^1.

Examples of the "organic pigment structure" include phthalocyanine, insoluble azo, azolake, anthraquinone, quinacridone, dioxazine, diketopyrrolopyrrole, anthrapyridine, ananthrene, and indanthrone. , Flavanetron, perinone, perylene-based, thioindigo-based pigment structures are listed as preferred examples, and phthalocyanine-based, azolake-based, anthraquinone-based, dioxazine-based, diketopyrrolopyrrole-based pigment structures are more preferred. In particular, a dye structure of phthalocyanine, anthraquinone and diketopyrrolopyrrole is particularly preferable.

Moreover, as said "heterocyclic structure", for example, thiophene, furan, xanthene, pyrrole, pyroline, pyrrolidine, dioxolane, pyrazole, pyrazoline, pyrazolidine, imidazole, oxazole, thia Sol, oxadiazole, triazole, thiadiazole, pyran, pyridine, piperidine, dioxane, morpholine, pyridazine, pyrimidine, piperazine, triazine, trithiane, isoindolin, isoindolinone Benzimidazolone, benzothiazole, succinimide, phthalimide, naphthalimide, hydantoin, indole, quinoline, carbazole, acridine, acridon, anthraquinone are listed as preferred examples, Pyrroline, pyrrolidine, pyrazole, pyrazoline, pyrazolidine, imidazole, triazole, pyridine, piperidine, morpholine, pyridazine, pyrimidine, piperazine, triazine, isoindolin, isoin Dolanone, benzimidazolone, benzothiazole, succinimide, phthalimide, naphthalimide, hydantoin, carba More preferred are sol, acridine, acridon and anthraquinone.

The "organic pigment structure" or "heterocyclic structure" may further have a substituent, and as said substituent, for example, C6-C20 alkyl groups, such as a methyl group and an ethyl group, a phenyl group, a naphthyl group, etc. C1-C20 alkoxy groups, such as C1-C6 acyloxy, methoxy, and ethoxy groups, such as 16 aryl groups, a hydroxyl group, an amino group, a carboxyl group, a sulfonamide group, an N-sulfonylamide group, an acetoxy group, etc. And carbonate ester groups such as alkoxycarbonyl groups having 2 to 7 carbon atoms, cyano group and t-butyl carbonate, such as halogen atoms such as chlorine and bromine, methoxycarbonyl group, ethoxycarbonyl group and cyclohexyloxycarbonyl group. Here, these substituents may be couple | bonded with the organic pigment | dye structure or heterocycle through the coupling group which the following structural unit or the said structural unit combines.

As said "acidic group", a carboxylic acid group, a sulfonic acid group, a monosulfate ester group, a phosphoric acid group, a monophosphate ester group, a boric acid group is mentioned as a preferable example, for example, a carboxylic acid group, a sulfonic acid group, a monosulfonic acid ester group, a phosphoric acid group , Monophosphate ester group is more preferable, and a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group are especially preferable.

Further, as the "group having a basic nitrogen atom", for example, an amino group (-NH _2), substituted imino group ^{(-NHR 8, -NR 9 R 10} , where, R ^8, R ^9, and R ¹⁰ are each Independently an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, an aralkyl group having 7 or more carbon atoms), a guanidyl group represented by the following formula (a1), and an amidinyl group represented by the following formula (a2): And the like are listed as preferred examples.

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

In formula (a2), R <^13> and R <^14> respectively independently represents a C1-C20 alkyl group, a C6 or more aryl group, and a C7 or more aralkyl group.

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 represent an alkyl group having 1 to 10 carbon atoms, a phenyl group, and a benzyl group .), Guanidyl group represented by said formula (a1) (In formula (a1), R <^11> and R <^12> represents a C1-C10 alkyl group, a phenyl group, and a benzyl group each independently.), The said formula (a2) More preferred are an amidinyl group (wherein R ¹³ and R ¹⁴ in the formula (a2) each independently represents an alkyl group having 1 to 10 carbon atoms, a phenyl group, or a benzyl group).

In particular, the amino group (-NH ₂ ), substituted imino group (-NHR ⁸ , -NR ⁹ R ¹⁰ , wherein R ⁸ , R ⁹ , and R ¹⁰ each independently represent an alkyl group having 1 to 5 carbon atoms, a phenyl group, and a benzyl group. The guanidyl group represented by said formula (a1) (In formula (a1), R <^11> and R <^12> represents a C1-C5 alkyl group, a phenyl group, and a benzyl group each independently.), The said formula (a2) The amidinyl group (R <^13> and R <^14> in a formula (a2) respectively independently represent a C1-C5 alkyl group, a phenyl group, and a benzyl group.) Etc. are used preferably.

As said "urea group", for example, -NR ¹⁵ CONR ¹⁶ R ¹⁷ (wherein R ¹⁵ , R ¹⁶ , and R ¹⁷ are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, Aralkyl groups having 7 or more carbon atoms are listed as preferred examples, and -NR ¹⁵ CONHR ¹⁷ (wherein R ¹⁵ and R ¹⁷ are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms and an aryl group having 6 or more carbon atoms). And aralkyl groups having 7 or more carbon atoms. More preferably, -NHCONHR ¹⁷ (wherein R ¹⁷ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms). .) Is particularly preferred.

As said "urethane group", for example, -NHCOOR ¹⁸ , -NR ¹⁹ COOR ²⁰ , -OCONHR ²¹ , -OCONR ²² R ²³ (here, R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² and R ²³ Each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, an aralkyl group having 7 or more carbon atoms, and the like. Examples thereof include -NHCOOR ¹⁸ , -OCONHR ²¹ (wherein R ¹⁸ , R ²¹ each independently represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, an aralkyl group having 7 or more carbon atoms, and the like. More preferably, -NHCOOR ¹⁸ or -OCONHR ²¹ (wherein R ¹⁸ and R ²¹ And each independently represent an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 or more carbon atoms, an aralkyl group having 7 or more carbon atoms), and the like.

As said "group which has coordinating oxygen atom", an acetylacetonato group, a crown ether, etc. are mentioned, for example.

Examples of the "hydrocarbon group having 4 or more carbon atoms" include alkyl groups having 4 or more carbon atoms, aryl groups having 6 or more carbon atoms, aralkyl groups having 7 or more carbon atoms, and the like, and examples thereof include alkyl groups having 4 to 20 carbon atoms and aryl having 6 to 20 carbon atoms. Group, a C7-20 aralkyl group, etc. are more preferable, a C4-15 alkyl group (for example, an octyl group, a dodecyl group, etc.), a C6-C15 aryl group (for example, a phenyl group, a naphthyl group) And aralkyl groups having 7 to 15 carbon atoms (e.g., benzyl groups).

As said "alkoxy silyl group", a trimethoxy silyl group, a triethoxy silyl group, etc. are mentioned, for example.

As the organic linking group bonded to the adsorption site, a single bond or 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to 20 atoms The organic coupling group which consists of a sulfur atom is preferable, and this organic coupling group may be unsubstituted, or may have a substituent further.

As a specific example of this organic coupling group, group which the following structural unit or the said structural unit combines is comprised.

When the organic linking group has a substituent, the substituent includes, for example, an alkyl group having 1 to 20 carbon atoms, such as a methyl group and an ethyl group, an aryl group having 6 to 16 carbon atoms, such as a phenyl group and a naphthyl group, a hydroxyl group, an amino group, a carboxyl group, and a sulfonamide. C1-C6 acyloxy groups, such as group, N-sulfonylamide group, and acetoxy group, C1-C6 alkoxy groups, such as a methoxy group and an ethoxy group, halogen atoms, such as chlorine and a bromine, methoxycarbonyl group, Carbonic acid ester groups, such as a C2-C7 alkoxycarbonyl group, a cyano group, t-butyl carbonate, such as an ethoxy carbonyl group and a cyclohexyloxycarbonyl group, etc. are mentioned.

The Among as the A ^1, an organic dye structure, a heterocyclic structure, an acidic group, a basic nitrogen group having atom, a urea group, and the carbon number of the monovalent organic group containing at least one type of the site selected from at least four hydrocarbon group It is preferable.

As to the A ¹ it is more preferably a monovalent organic group is represented by formula (4).

In Formula (4), B ¹ represents the adsorption site (ie, an organic pigment structure, a heterocyclic structure, an acid group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, and 4 carbon atoms). Or more hydrocarbon groups, alkoxysilyl groups, epoxy groups, isocyanate groups, and hydroxyl groups), and R ²⁴ represents a single bond or an (a + 1) valence organic linking group. a represents the integer of 1-10, and a B <^1> may be same or different.

As the adsorption sites represented by the B ¹ is open to the same as the adsorption sites constituting the A ¹ in the general formula (1) described above, the same preferable examples.

Especially, the site | part selected from an organic pigment | dye structure, a heterocyclic structure, an acidic group, the group which has a basic nitrogen atom, a urea group, and a C4 or more hydrocarbon group is preferable.

R <^24> represents a single bond or (a + 1) valent organic coupling group, and a represents 1-10. Preferably a is 1-7, More preferably, a is 1-5, Especially preferably, a is 1-3.

The (a + 1) valent organic linking group is composed of 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to 20 sulfur atoms. A group is contained and may be unsubstituted or may have a substituent further.

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

R ^{24 is a} single bond or composed of 1 to 50 carbon atoms, 0 to 8 nitrogen atoms, 0 to 25 oxygen atoms, 1 to 100 hydrogen atoms, and 0 to 10 sulfur atoms (a Preferred organic linkage groups are a single bond or 1 to 30 carbon atoms, 0 to 6 nitrogen atoms, 0 to 15 oxygen atoms, 1 to 50 hydrogen atoms, and 0 to 7 carbon atoms. (A + 1) valent organic linkage group which consists of two sulfur atoms is more preferable, and is a single bond or 1-10 carbon atoms, 0-5 nitrogen atoms, 0-10 oxygen atoms, 1-30 Particularly preferred is an organic linking group having a hydrogen atom and a (a + 1) valence of 0 to 5 sulfur atoms.

When the (a + 1) valent organic linking group has a substituent, the substituent includes, for example, an alkyl group having 1 to 20 carbon atoms, such as a methyl group and an ethyl group, an aryl group having 6 to 16 carbon atoms, such as a phenyl group and a naphthyl group, and a hydroxyl group. And alkoxy groups having 1 to 6 carbon atoms, such as amino, carboxyl, sulfonamide, N-sulfonylamide and acetoxy groups, and alkoxy groups having 1 to 6 carbon atoms such as methoxy and ethoxy groups, such as chlorine and bromine. Carbonate ester groups, such as a C2-C7 alkoxycarbonyl group, a cyano group, t-butyl carbonate, etc., such as a halogen atom, a methoxycarbonyl group, an ethoxycarbonyl group, and a cyclohexyloxycarbonyl group, are mentioned.

In General Formula (1), R ² represents a single bond or a divalent organic linking group. n R ² may be the same or different.

The divalent organic linking group includes a group consisting of 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to 20 sulfur atoms, Even if unsubstituted, it may have a substituent further.

Specific examples of the divalent organic linking group include the following structural units or groups in which the structural units are combined.

R ^{2 is a} single bond or a ^divalent compound consisting of 1 to 50 carbon atoms, 0 to 8 nitrogen atoms, 0 to 25 oxygen atoms, 1 to 100 hydrogen atoms, and 0 to 10 sulfur atoms. Organic linkages are preferred and consist of a single bond or from 1 to 30 carbon atoms, 0 to 6 nitrogen atoms, 0 to 15 oxygen atoms, 1 to 50 hydrogen atoms, and 0 to 7 sulfur atoms Divalent organic linking groups are more preferable, and are a single bond or 1-10 carbon atoms, 0-5 nitrogen atoms, 0-10 oxygen atoms, 1-30 hydrogen atoms, and 0-5 Particularly preferred is a divalent organic linking group consisting of sulfur atoms.

In the above, when the divalent organic linking group has a substituent, the substituent includes, for example, an alkyl group having 1 to 20 carbon atoms, such as a methyl group and an ethyl group, an aryl group having 6 to 16 carbon atoms, such as a phenyl group and a naphthyl group, a hydroxyl group, and an amino group. And alkoxy groups having 1 to 6 carbon atoms such as carboxyl group, sulfonamide group, N-sulfonyl amide group, acetoxy group, and alkoxy group having 1 to 6 carbon atoms such as methoxy group and ethoxy group, chlorine and bromine Carbonate ester groups, such as a C2-C7 alkoxycarbonyl group, a cyano group, t-butyl carbonate, etc., such as a halogen atom, a methoxycarbonyl group, an ethoxycarbonyl group, and a cyclohexyloxycarbonyl group, are mentioned.

R <^1> in the said General formula (1) represents a (m + n) valent organic coupling group. m + n satisfies 3-10.

Examples of the (m + n) valent organic linking group represented by R ¹ include 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 The group which consists of -20 sulfur atoms is contained, and even if it is unsubstituted, it may have a substituent further.

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

The (m + n) valent organic linking group is composed of 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 40 oxygen atoms, 1 to 120 hydrogen atoms, and 0 to 10 sulfur atoms. A group is preferable, and group which consists of 1-50 carbon atoms, 0-10 nitrogen atoms, 0-30 oxygen atoms, 1-100 hydrogen atoms, and 0-7 sulfur atoms is more preferable. And a group consisting of 1 to 40 carbon atoms, 0 to 8 nitrogen atoms, 0 to 20 oxygen atoms, 1 to 80 hydrogen atoms, and 0 to 5 sulfur atoms.

In the above, when the (m + n) valent organic linking group has a substituent, the substituent may be, for example, an alkyl group having 1 to 20 carbon atoms such as a methyl group or an ethyl group, or an aryl group having 6 to 16 carbon atoms such as a phenyl group or a naphthyl group. C1-C6 alkoxy groups, such as a C1-C6 acyloxy group, such as a hydroxyl group, an amino group, a carboxyl group, a sulfonamide group, an N-sulfonylamide group, an acetoxy group, a methoxy group, an ethoxy group, chlorine And carbonate ester groups such as a C2-7 alkoxycarbonyl group, a cyano group, t-butyl carbonate, such as a halogen atom such as bromine, a methoxycarbonyl group, an ethoxycarbonyl group, and a cyclohexyloxycarbonyl group.

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

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

M in the said General formula (1) represents 1-8. As m, 1-5 are preferable, 1-4 are more preferable, and 1-3 are especially preferable.

In addition, 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 General Formula (1), P ¹ represents a polymer skeleton and can be selected from known polymers according to the purpose and the like. m P ¹ may be the same or different.

Among the polymers, polymers or copolymers of vinyl monomers, ester-based polymers, ether-based polymers, urethane-based polymers, amide-based polymers, epoxy-based polymers, silicone-based polymers, and modified substances or copolymers thereof may be used. For example, a copolymer of a polyether / polyurethane copolymer, a polymer of a polyether / vinyl monomer, or the like (random copolymer, block copolymer, graft copolymer may be used), or the like. At least 1 sort (s) is preferable, At least 1 sort (s) chosen from the group which consists of a polymer or copolymer of a vinyl monomer, an ester type polymer, an ether type polymer, a urethane type polymer, and these modified | denatured products or a copolymer is more preferable, and a polymer of a vinyl monomer Or copolymers are particularly preferred.

In addition, the polymer is preferably soluble in an organic solvent. When the affinity with an organic solvent is low, when used as a pigment dispersant, for example, affinity with a dispersion medium may become weak and it may become impossible to ensure the adsorption layer sufficient for dispersion stabilization.

Although it does not restrict | limit especially as said vinyl monomer, For example, (meth) acrylic acid ester, crotonic acid ester, vinyl ester, maleic acid diester, fumaric acid diester, itaconic acid diester, (meth) Acrylamides, styrenes, vinyl ethers, vinyl ketones, olefins, maleimides, (meth) acrylonitrile and vinyl monomers having an acidic group are preferable.

Hereinafter, the preferable example of these vinyl monomers is demonstrated.

Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, 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, 2-ethylhexyl (meth) acrylate, (meth) T-octyl acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxy (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) 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) 2- (2-methoxyethoxy) ethyl acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, ( 2-chloroethyl methacrylate, glycidyl (meth) acrylate, -3,4-epoxycyclohexylmethyl (meth) acrylic acid, vinyl (meth) acrylate, 2-phenylvinyl (meth) acrylate, (meth) -1-propenyl acrylate, allyl (meth) acrylate, 2-allyl oxyethyl (meth) acrylate, propargyl (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 Ether, (meth) acrylic acid (beta) -phenoxy ethoxyethyl, (meth) acrylic-acid nonylphenoxy polyethylene glycol, (meth) acrylic-acid dicyclopentenyl, (meth) acrylic-acid dicyclopentenyloxyethyl, (meth) a Trifluoroethyl acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tribromophenyl (meth) acrylate, tribromophenyl (meth) acrylate Oxyethyl, (meth) acrylic acid-γ-butyrolactone, and the like.

Examples of crotonic acid esters include butyl crotonate, hexyl crotonate, and the like.

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

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

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

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

As (meth) acrylamide, (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, Nn-butylacryl (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) acryloyl morpholine, diacetone acrylamide, N-methylol acrylamide, N-hydroxyethyl acrylamide, vinyl (meth) acrylamide, N, N- diallyl (meth) acrylamide, N -Allyl (meth) 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 and bromostyrene And chloromethylstyrene, hydroxystyrene protected with a group deprotectable by an acidic substance (for example, t-Boc, etc.), methyl vinylbenzoate, α-methylstyrene, and the like.

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 ethers and the like.

Examples of vinyl ketones include methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.

Examples of the olefins include ethylene, propylene, isobutylene, butadiene, isoprene and the like.

Examples of maleimide include maleimide, butyl maleimide, cyclohexyl maleimide, phenyl maleimide and the like.

(Meth) acrylonitrile, a heterocyclic group substituted with a vinyl group (for example, vinylpyridine, N-vinylpyrrolidone, vinylcarbazole, etc.), N-vinylformamide, N-vinylacetamide, N-vinyl Imidazole, vinyl caprolactone, etc. can also be used.

In addition to the above compounds, vinyl monomers having functional groups such as urethane groups, urea groups, sulfonamide groups, phenol groups, and imide groups can also be used. As a monomer which has such a urethane group or a urea group, it is possible to synthesize | combine suitably using the addition reaction of an isocyanate group, a hydroxyl group, or an amino group, for example. Specifically, addition reaction of an isocyanate group-containing monomer and a compound containing one hydroxyl group or a compound containing one primary or secondary amino group, or addition of a hydroxyl group-containing monomer or a primary or secondary amino group-containing monomer and a monoisocyanate It can synthesize | combine suitably by reaction or the like.

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, vinylbenzoic acid, maleic acid, maleic acid monoalkyl esters, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, acrylic acid dimers, and the like. Furthermore, the addition reaction product of the monomer which has hydroxyl groups, such as 2-hydroxyethyl (meth) acrylate, and cyclic anhydrides, such as maleic anhydride, phthalic anhydride, and cyclohexane dicarboxylic anhydride, (omega)-carboxy- polycaprolactone mono ( Meth) acrylate etc. can also be used. Moreover, you may use anhydride containing monomers, such as maleic anhydride, itaconic anhydride, a citraconic acid anhydride, as a precursor of a carboxyl group. Moreover, in these, (meth) acrylic acid is especially preferable from a viewpoint of copolymerizability, cost, and solubility.

Examples of the vinyl monomer having a sulfonic acid group include 2-acrylamide-2-methylpropanesulfonic acid and the like, and examples of the vinyl monomer having a phosphoric acid group include monophosphate (2-acryloyloxyethyl ester) and mono (1-methyl phosphate). 2-acryloyloxyethyl ester) etc. are mentioned.

Moreover, as a vinyl monomer which has an acidic group, the vinyl monomer containing a phenolic hydroxyl group, the vinyl monomer containing a sulfonamide group, etc. can also be used.

Among the high molecular compounds represented by the general formula (1), the high molecular compounds represented by the following general formula (2) are preferable.

In the general formula (2), A ² is an organic pigment 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, a hydrocarbon having 4 or more carbon atoms. The monovalent organic group containing at least 1 sort (s) of site | parts chosen from group, an alkoxy silyl group, an epoxy group, an isocyanate group, and a hydroxyl group is shown. n pieces of A ² may be the same or different.

In addition, A <^2> is synonymous with said A <^1> in the said General formula (1), and its preferable aspect is also the same.

In the said General formula (2), R <^4> , R <^5> represents a single bond or a bivalent organic coupling group each independently. n R ⁴ may be the same or different. In addition, m pieces of R ⁵ may be the same or different.

As the divalent organic linking group represented by R ⁴ , R ⁵ , the same ones listed as the divalent organic linking group represented by R ² in General Formula (1) are used, and the preferred form thereof is also the same.

In the said General formula (2), R <^3> represents the (m + n) valent organic coupling 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 100 hydrogen atoms, and 0 The group which consists of -20 sulfur atoms is contained, and even if it is unsubstituted, it may have a substituent further.

As the (m + n) valent organic linking group represented by the above R ³ , specifically, the same as those listed as the (m + n) valent organic linking group represented by R ¹ of the general formula (1) is used, and a preferred form is also shown. same.

M shows 1-8 in the said General formula (2). As m, 1-5 are preferable, 1-4 are more preferable, and 1-3 are especially preferable.

In addition, 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.

In addition, P <^2> in General formula (2) shows a polymer skeleton, and can be selected from a well-known polymer etc. according to the objective. m P ² may be the same or different. About a preferable aspect of a polymer, it is the same as P <^1> in the said General formula (1).

It is most preferable to satisfy all of R <^3> , R <^4> , R <^5> , P <^2> , m, and n shown below among the high molecular compounds represented by the said General formula (2).

R ³ : the above specific examples (1), (2), (10), (11), (16) or (17)

R ⁴ : "1 to 10 carbon atoms, 0 to 5 nitrogen atoms, 0 to 10 oxygen atoms, 1 to 30 hydrogens constituted by a single bond or the following structural unit or a combination of the above structural units Atom, and 0-5 sulfur atoms "(which may have a substituent, for example, a C1-C20 alkyl group, such as a methyl group and an ethyl group, a phenyl group, a naphthyl group, etc.) C1-C6 acyloxy, methoxy, ethoxy group, such as a C6-C16 aryl group, a hydroxyl group, an amino group, a carboxyl group, a sulfonamide group, N-sulfonylamide group, an acetoxy group, etc. Carbonic esters, such as a C2-C7 alkoxycarbonyl group, a cyano group, t-butyl carbonate, such as a halogen atom, such as a C6-C6 alkoxy group, chlorine, and bromine, a methoxycarbonyl group, an ethoxycarbonyl group, and a cyclohexyloxycarbonyl group, etc. The like are listed.)

R ⁵ : single bond, ethylene group, propylene group, the following group (a), or the following group (b)

In addition, in the following group, 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 to 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 may be synthesized by the following method or the like.

1.A polymer incorporating a functional group selected from a carboxyl group, a hydroxyl group, an amino group, and the like with an acid halide having a plurality of the adsorption sites, an alkyl halide having a plurality of the adsorption sites, or an isocyanate having a plurality of the adsorption sites Method of reacting the polymer.

2. The method of Michael addition-reacting the polymer which introduce | transduced the carbon-carbon double bond at the terminal, and the mercaptan which has several said adsorption site | parts.

3. A method in which a polymer having a carbon-carbon double bond introduced at its end and a mercaptan having the adsorption site are reacted in the presence of a radical generator.

4. A method of reacting a polymer having a plurality of mercaptans introduced at its terminal, a compound having a carbon-carbon double bond and the adsorption site in the presence of a radical generator.

5. A method of radically polymerizing a vinyl monomer in the presence of a mercaptan compound having a plurality of said adsorption sites.

Among the above-mentioned, the synthesis method of 2, 3, 4, 5 is preferable, and, as for (B-1) specific dispersion resin in this invention, the synthesis method of 3, 4, 5 is more preferable. In particular, when (B-1) specific dispersion resin has a structure represented by General formula (2), it is most preferable to synthesize | combine by the synthesis method of 5 from the ease of synthesis.

As said synthesis | combining method of said 5, More specifically, the method of radically polymerizing a vinyl monomer in presence of a compound represented by following General formula (3) is preferable.

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

Although the compound represented by the said General formula (3) can be synthesize | combined with the following method etc., the method of following 7 is more preferable from the ease of synthesis.

6. Methods for converting a halide compound having a plurality of the above adsorption sites into a mercaptan compound (methods of hydrolysis by reacting with thiourea, methods of directly reacting with NaSH, methods of hydrolysis by reacting with CH ₃ COSNa, and the like are listed. do.)

7. Method for addition-reacting a compound having 3 to 10 mercapto groups in one molecule and a compound having the above adsorption site and having a functional group capable of reacting with a mercapto group

As a "functional group which can react with a mercapto group" in the said synthesis method 7, an acid halide, an alkyl halide, an isocyanate, a carbon-carbon double bond, etc. are mentioned preferably.

It is especially preferable that "the functional group which can react with a mercapto group" is a carbon-carbon double bond, and an addition reaction is a radical addition reaction. Moreover, as a carbon-carbon double bond, a mono- or bi-substituted vinyl group is more preferable at the point of the reactivity with a mercapto group.

The following compounds are mentioned as a specific example [specific examples (18)-(34)] of the compound which has 3-10 mercapto groups in 1 molecule.

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

A compound having the above adsorption site and having a carbon-carbon double bond (specifically, an organic pigment structure, a heterocyclic structure, an acid group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom) , A compound having at least one 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 also having a carbon-carbon double bond) is not particularly limited. Listed.

The radical addition reaction products of the above-mentioned "compounds having 3 to 10 mercapto groups in one molecule" and "compounds having said adsorption site and having carbon-carbon double bonds" are, for example, in the above "molecules." Compound having 3 to 10 mercapto groups &quot; and &quot; a compound having the above adsorption site and having a carbon-carbon double bond &quot; are dissolved in a suitable solvent, and a radical generator is added thereto, to about 50 ° C to 100 It is obtained using the method (thiol-ene reaction method) added at ° C.

Examples of suitable solvents used in the thiol-ene reaction method include "compounds having 3 to 10 mercapto groups in one molecule", "compounds having said adsorption sites and having carbon-carbon double bonds", and It can select arbitrarily according to the solubility of "the radical addition reaction product to produce | generate."

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. You may use these solvent in mixture of 2 or more type.

Moreover, 2,2'- azobis (isobutyronitrile) (AIBN), 2,2'- azobis- (2,4'- dimethylvaleronitrile), 2,2'- azobis as a radical generator Azo compounds such as dimethyl isobutyrate, peroxides such as benzoylperoxide, and persulfates such as potassium persulfate, ammonium persulfate, and the like.

Although it does not restrict | limit especially as a vinyl monomer used by the said synthesis | combination method of 5, For example, the same thing as the vinyl monomer used when obtaining the polymer skeleton represented by P <^1> of the said General formula (1) is used.

Said vinyl monomer may be superposed | polymerized only by 1 type, and may copolymerize 2 or more types together.

Moreover, it is more preferable that (B-1) specific dispersion resin copolymerizes the vinyl monomer which has 1 or more types of acidic groups, and the vinyl monomer which does not have 1 or more types of acidic groups.

[A polymer containing a copolymerization unit derived from the monomer represented by (B-2) General formula (I): (B-2) specific dispersion resin]

Next, it demonstrates about the polymer (Hereinafter, it calls suitably "(B-2) specific dispersion resin.") Containing the copolymer unit derived from the monomer represented by following General formula (I).

In 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 (= 0) O-, -CONH-, -OC (= 0)-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 is -NR ⁰³ - it represents a -O-, -S- or -N =, in connection with the N atom via an atomic group adjacent to it to form a cyclic structure. R ⁰³ represents a hydrogen atom, an alkyl group or an aryl group. m1 and n1 each independently represent 0 or 1.

Hereinafter, the monomer represented by general formula (I) used as an essential copolymerization unit of (B-2) specific dispersion resin in this invention is demonstrated in detail.

In General Formula (I), R ⁰¹ represents a hydrogen atom or a substituted or unsubstituted alkyl group.

As an alkyl group represented by R <^01> , a C1-C12 alkyl group is preferable, A C1-C8 alkyl group is more preferable, A C1-C4 alkyl group is especially preferable.

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, a halogen group and the like.

Specific examples of the preferred 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-hydroxyethyl group, 3- Hydroxypropyl group, 2-hydroxypropyl group, 2-methoxyethyl group, etc. are mentioned.

R ⁰² represents an alkylene group.

As an alkylene group represented by R <^02> , a C1-C12 alkylene group is preferable, A C1-C8 alkylene group is more preferable, A C1-C4 alkylene group is especially preferable.

When the alkylene group represented by R ⁰² can be introduced, it may have a substituent, and examples of the substituent include a hydroxy group, an alkoxy group, an aryloxy group, an acyloxy group, and the like.

Specific examples of the preferred alkylene group represented by R ⁰² include methylene group, ethylene group, propylene group, trimethylene group, tetramethylene group and the like.

W represents -CO-, -C (= 0) O-, -CONH-, -OC (= 0)-or a phenylene group, and it is preferable that it is -C (= 0) O- or -CONH-.

Y is -NR ⁰³ - it represents a -O-, -S- or -N =, in connection with the N atom via an atomic group adjacent to it to form a cyclic structure.

R <^03> represents a hydrogen atom, an alkyl group, or an aryl group, and it is preferable that it is a hydrogen atom or a methyl group.

As Y, it is especially preferable that it is -S-, -NH-, or -N =.

As a cyclic structure which Y connects with N atom through the atom group adjacent to this, monocyclic structures, such as an imidazole ring, a pyrimidine ring, a triazole ring, a tetrazole ring, a thiazole ring, an oxazole ring, and a benzimidazole ring, benz Condensed ring structures, such as a thiazole ring, a benzoxazole ring, a purine ring, a quinazoline ring, a perimidine ring, are mentioned, It is preferable that it is a condensed ring structure from affinity with a pigment. Moreover, a benzimidazole ring, a benzthiazole ring, and a benzoxazole ring are especially preferable among condensed ring structures.

X is -O-, -S-, -C (= O) O-, -CONH-, -C (= O) S-, -NHCONH-, -NHC (= O) O-, -NHC (= O ) S-, -OC (= O)-, -OCONH- or -NHCO-.

As X, -O-, -S-, -CONH-, -NHCONH-, and -NHC (= O) S- are especially preferable.

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

Although the specific example (monomer M-1-monomer M-18) of the monomer represented by general formula (I) is enumerated below, this invention is not limited to these.

(B-2) specific dispersion resin in this invention is a superposition | polymerization which has an ethylenically unsaturated bond at the terminal with the copolymerization unit derived from the monomer represented by the said General formula (I) from a viewpoint of the dispersion stability provision of a pigment. It is especially preferable that it is a graft copolymer which further contains the copolymerization unit derived from an oligomer.

The polymerizable oligomer having an ethylenically unsaturated bond at such terminal is also called a macromonomer because it is a compound having a predetermined molecular weight. In the following description, the "polymerizable oligomer which has an ethylenically unsaturated bond at the terminal" in this invention may be called "polymerizable oligomer" or "macro monomer" suitably.

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

Moreover, it is preferable that the number average molecular weight (Mn) of polystyrene conversion of this macromonomer exists in the range of 1000-10000, and the range of 2000-9000 is especially preferable.

Part of the polymer chain is a homopolymer or copolymer formed of at least one monomer selected from the group consisting of alkyl (meth) acrylates, styrene and derivatives thereof, acrylonitrile, vinyl acetate and butadiene, or polyethylene oxide , Polypropylene oxide and polycaprolactone are common.

It is preferable that the said polymerizable oligomer is 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, and a plurality of the alkylene groups may represent an ester bond, an ether bond, an amide bond, or the like. It may be connected through. R ¹² is preferably an alkylene group having 1 to 4 carbon atoms or an alkylene group having 1 to 4 carbon atoms connected via 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 a C1-C6 alkyl group, a phenyl group, or a C7-C10 arylalkyl group. Y ¹¹ is preferably a phenyl group or -COOR ¹⁴ , wherein R ¹⁴ represents an alkyl group having 1 to 12 carbon atoms.

q represents the integer of 20-200.

In the present invention, preferred examples of the polymerizable oligomer (macro monomer) that can be used for the synthesis of the specific dispersion resin (B-2) include polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and poly-i. -Butyl (meth) acrylate and the polymer which the (meth) acryloyl group couple | bonded with one of the molecular terminal of polystyrene can be mentioned. Such polymerizable oligomers available on the market include single-ended methacryloylated polystyrene oligomers (Mn = 6000, trade name: AS-6, manufactured by Toagosei Co., Ltd.), single-ended methacryloylated polymethylmethacrylates. Oligomer (Mn = 6000, trade name: AA-6, manufactured by Toagosei Co., Ltd.) and single-ended methacryloylated poly-n-butylacrylate oligomer (Mn = 6000, trade name: AB-6, Toagosei Co. , Ltd.).

It is preferable that the (B-2) specific dispersion resin which concerns on this invention further contains the copolymerization unit derived from the monomer which has an acidic radical, in order to acquire specific acid value.

As a monomer which has an acidic radical, Unsaturated monocarboxylic acids, such as acrylic acid, methacrylic acid, crotonic acid, (alpha)-chloroacrylic acid, cinnamic acid; Unsaturated dicarboxylic acids or anhydrides thereof such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride and mesaconic acid; Trivalent or higher unsaturated polyvalent carboxylic acid or anhydrides thereof; Succinic acid mono (2-acryloyloxyethyl), succinic acid mono (2-methacryloyloxyethyl), phthalic acid mono (2-acryloyloxyethyl), phthalic acid mono (2-methacryloyloxyethyl) Mono [(meth) acryloyloxyalkyl] esters of divalent or higher polyhydric carboxylic acid; mono (meth) acrylates of both terminal carboxy polymers such as? -carboxy-polycaprolactone monoacrylate and? -carboxy-polycaprolactone monomethacrylate.

(B-2) specific dispersion resin which concerns on this invention may further contain the polymerizable vinyl monomer as a copolymerization component in the range which does not impair the effect.

Although it does not restrict | limit especially as a vinyl monomer which can be used here, For example, (meth) acrylic acid ester, crotonic acid ester, vinyl ester, maleic acid diester, fumaric acid diester, itaconic acid diester, (meth ) Acrylamides, vinyl ethers, esters of vinyl alcohol, styrenes, (meth) acrylonitrile and the like are preferable. As a specific example of such a vinyl monomer, the following compounds are mentioned, for example.

As a preferable aspect of the (B-2) specific dispersion resin which concerns on this invention, the copolymerization unit derived from the monomer represented by the said General formula (1) is contained in 2-50 mass%, and ethylenically unsaturated bond is added to the terminal. Copolymer containing 10-90 mass% of copolymerization units derived from the polymerizable oligomer which has, and 1-30 mass% of copolymerization units derived from the monomer which has an acidic radical, and 0-20 mass% of copolymerization units derived from a vinyl monomer. Preferred is mentioned.

Although the specific example [Example compound 1-Example compound 16] of (B-2) specific dispersion resin which can be preferably used for the composition for coloring pattern formation of this invention is listed with the weight average molecular weight, this invention is It is not limited to these.

Exemplary compound (1): monomer M-2 / methacrylic acid / terminal methacryloylated polymethyl methacrylate copolymer (10/25/65 mass%, weight average molecular weight 50000, acid value 163 mg / g)

Exemplary compound (2): the monomer M-2 / methacrylic acid / terminal methacryloylated polymethyl methacrylate copolymer (10/15/75 mass%, weight average molecular weight 35000, acid value 98 mg / g)

Exemplary compound (3): monomer M-3 / methacrylic acid / methacrylic acid 2-hydroxyethyl / terminal methacryloylated polymethyl methacrylate copolymer (5/5/10/80 mass%, weight average Molecular weight 40000, acid value 33mg / g)

Exemplary compound (4): monomer M-3 / methacrylic acid / methacrylic acid benzyl copolymer / terminal methacryloylated polymethyl methacrylate copolymer (15/10/10/65 mass%, weight average molecular weight 60000 , Acid value 65mg / g)

Exemplary compound (5): the monomer M-4 / methacrylic acid / terminal 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 / terminal methacryloylated polymethyl methacrylate copolymer (10/15/75 mass%, weight average molecular weight 20000, acid value 98 mg / g)

Exemplary compound (7): the 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 / terminal methacryloylated polybutylacrylate copolymer (15/5/80 mass%, weight average molecular weight 45000, acid value 39 mg / g)

Exemplary compound (9): monomer M-6 / acrylic acid / methacrylic acid 2-hydroxyethyl / terminal methacryloylated polymethyl methacrylate copolymer (15/10/5/70% by mass, weight average molecular weight 80000 , Acid value 78mg / 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 / terminal methacryloylated polymethyl methacrylate copolymer (10/18/72 mass%, weight average molecular weight 15000, acid value 117 mg / g)

Exemplary 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 )

Exemplary compound (13): monomer M-10 / acrylic acid / methacrylic acid 2-hydroxyethyl / terminal methacryloylated polystyrene copolymer (5/35/10/50 mass%, weight average molecular weight 20000, acid value 272 mg / g)

Exemplary compound (14): the monomer M-10 / methacrylic acid / terminal methacryloylated polymethylmethacrylate copolymer (10/12/78 mass%, weight average molecular weight 10000, acid value 78 mg / g)

Exemplary compound (15): the monomer M-10 / acrylic acid / methoxypolyethylene glycol methacrylate copolymer (15/3/82% by mass, weight average molecular weight 15000, acid value 23 mg / g)

Exemplary compound (16): the monomer M-13 / methacrylic acid / terminal methacryloylated polymethylmethacrylate 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]

Next, the polymer (hereinafter, referred to as "(B-3) specific dispersion resin" suitably ") containing the structural unit represented by the following general formula (a) is demonstrated.

In 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, trimethylene group, tetramethylene group, hexamethylene group, 2-hydroxypropylene group, methyleneoxy group, ethyleneoxy group, methyleneoxycarbonyl group, methylenethio group and the like. Among them, a methylene group, a methyleneoxy group, a methyleneoxycarbonyl group, and a methylenethio group are preferable.

Z ¹ in the general formula (a) represents a nitrogen-containing heterocyclic structure, and 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 , Quinoline ring, acridine ring, phenothiazine ring, phenoxazine ring, acridon ring, anthraquinone ring, benzimidazole structure, benztriazole structure, benzthiazole structure, cyclic amide structure, cyclic urea structure, and cyclic imide It is enumerated that it has a de structure.

Among these, the nitrogen-containing heterocyclic structure represented by Z ¹ is preferably a structure represented by the following General Formula (b) or (c).

In Formula (b), X ¹ represents a single bond, an alkylene group (for example, methylene group, ethylene group, propylene group, trimethylene group, tetramethylene group, etc.), -O-, -S-, -NR- And -C (= O)-. Here, R represents a hydrogen atom or an alkyl group, and as an alkyl group in the case where R represents an alkyl group, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, t-butyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, n-octadecyl group, etc. are mentioned.

Of these, X ¹ is a single bond, a methylene group, -O-, -C (= O) - , and is preferably, -C (= O) - is particularly preferred.

Rings A, Ring B, and Ring C in the general formulas (b) and (c) each independently represent an aromatic ring. Examples of the aromatic ring include a benzene ring, naphthalene ring, indene ring, azlene ring, fluorene ring, anthracene ring, pyridine ring, pyrazine ring, pyrimidine ring, pyrrole ring, imidazole ring, indole ring, quinoline ring, Acridine ring, phenothiazine ring, phenoxazine ring, acridon ring, anthraquinone ring, etc. are mentioned, Among these, a benzene ring, a naphthalene ring, anthracene ring, a pyridine ring, a phenoxazine ring, an acridine ring, a phenothiazine ring , Phenoxazine ring, acridon ring and anthraquinone ring are preferable, and a benzene ring, a naphthalene ring and a pyridine ring are particularly preferable.

Preferable specific examples of the structural unit represented by the general formula (a) (example structural units (M'-1) to (M'-7)) are listed below, but the present invention is not limited thereto.

It is preferable that 2-50 mass% is contained in (B-3) specific dispersion resin, and, as for the structural unit represented by the said General formula (a), it is more preferable that 4-30 mass% is included, and 5-20 mass% is included It is especially preferable.

In addition to the structural unit represented by the said General formula (a), the specific dispersion resin (B-3) in this invention is a graft copolymer which further contains as a copolymerization unit the polymerizable oligomer which has an ethylenically unsaturated double bond at the terminal. Is particularly preferred.

The polymerizable oligomer which has an ethylenically unsaturated double bond in such terminal is mentioned the same thing as the polymeric oligomer used as a copolymerization component in the specific (B-2) dispersion resin of single use, and the preferable form (In general formula (II)) The oligomer shown) and the preferable example (specific example) are also the same.

It is preferable that (B-3) specific dispersion resin in this invention contains the monomer (structural unit) which has an acidic group as a copolymerization component in order to acquire a specific acid value.

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, and anhydrous 2-hydroxyethyl (meth) acrylate. Phthalic acid adducts and the like.

(B-3) specific dispersion resin in this invention may further contain the copolymerizable vinyl monomer as a copolymerization component in the range which does not impair the effect.

As a vinyl monomer which can be used here, the thing similar to the vinyl monomer used as a copolymerization component in above-mentioned (B-2) specific dispersion resin is mentioned, The preferable example is also the same.

Moreover, as a preferable aspect of specific dispersion resin which concerns on this invention, the polymerizable oligomer which contains the structural unit represented by the said General formula (a) in 2-50 mass%, and has ethylenically unsaturated double bond in the terminal is 10-. The copolymer containing 1-30 mass% of structural units which have 90 mass% and an acidic radical, and 0-20 mass% of vinyl monomers is mentioned preferably.

Although the specific example [example compound (I)-(XV)] of (B-3) specific dispersion resin which can be used suitably for the composition for coloring pattern formation of this invention is listed together with the weight average molecular weight, The invention is not limited to these.

Exemplary Compound (I): Monomer / methacrylic acid / terminal methacryloylated polymethyl methacrylate copolymer capable of forming the exemplary structural unit (M′-1) (copolymerization ratio = 10/4/86% by mass) , Weight average molecular weight 50000, acid value 26mg / g)

Exemplary Compound (II): Monomer / methacrylic acid / terminal methacryloylated polymethylmethacrylate copolymer (10/33/57% by mass, weight average) capable of forming the exemplary structural unit (M′-1) Molecular weight 30000, acid value 214 mg / g)

Exemplary Compound (III): Monomer / methacrylic acid / methacrylic acid 2-hydroxyethyl / terminal methacryloylated polymethylmethacrylate copolymer capable of forming the exemplary structural unit (M′-1) (5) / 28/10/57 mass%, weight average molecular weight 40000, acid value 182 mg / g)

Exemplary Compound (IV): Monomer / methacrylic acid / methacrylic acid benzyl copolymer / terminal methacryloylated polymethylmethacrylate copolymer capable of forming the above exemplary structural unit (M′-1) (15/5) / 10/70 mass%, weight average molecular weight 60000, acid value 33 mg / g)

Exemplary Compound (V): Monomer / methacrylic acid / terminal methacryloylated polymethylmethacrylate copolymer (20/20/60% by mass, weight average) capable of forming the exemplary structural unit (M′-5) Molecular weight 80000, acid value 130mg / g)

Exemplary Compound (VI): Monomer / methacrylic acid / terminal methacryloylated polymethylmethacrylate copolymer (10/20/70% by mass, weight average) capable of forming the exemplary structural unit (M′-5) Molecular weight 30000, acid value 130mg / g)

Exemplary Compound (VII): Monomer / acrylic acid / terminal methacryloylated polymethylmethacrylate copolymer (25/20/55% by mass, weight average molecular weight 60000) capable of forming the above exemplary structural unit (M′-5) , Acid value 156 mg / g)

Exemplary Compound (VIII): Monomer / acrylic acid / terminal methacryloylated polybutylacrylate copolymer (15/15/70% by mass, weight average molecular weight 40000) capable of forming the exemplary structural unit (M′-5) Acid value 117 mg / g)

Exemplary Compound (IX): Monomer / acrylic acid / methacrylic acid 2-hydroxyethyl / terminal methacryloylated polymethylmethacrylate copolymer (15/5) capable of forming the above exemplary structural unit (M′-5) / 5/75 mass%, weight average molecular weight 80000, acid value 39 mg / g)

Exemplary Compound (X): Monomer / methacrylic acid / terminal methacryloylated polymethylmethacrylate copolymer (12/17/71 mass%, weight average) capable of forming the exemplary structural unit (M′-6) Molecular Weight 50000, Acid Value 110mg / g)

Exemplary Compound (XI): Monomer / methacrylic acid / terminal methacryloylated polymethylmethacrylate copolymer (10/12/78% by mass, weight average) capable of forming the exemplary structural unit (M′-6) Molecular Weight 20000, Acid Value 78mg / g)

Exemplary Compound (XII): Monomer / methacrylic acid / benzyl methacrylate / methoxypolyethyleneglycol methacrylate copolymer (10/10/50/30 mass) capable of forming the exemplary structural unit (M′-6) %, Weight average molecular weight 35000, acid value 65 mg / g)

Exemplary Compound (XIII): Monomer / acrylic acid / methacrylic acid 2-hydroxyethyl / terminal methacryloylated polystyrene copolymer capable of forming the exemplary structural unit (M′-6) (5/5/10/80) Mass%, weight average molecular weight 20000, acid value 39 mg / g)

Exemplary Compound (XIV): Monomer / methacrylic acid / methyl methacrylate / terminal methacryloylated polymethylmethacrylate copolymer (8/12/10) capable of forming the exemplary structural unit (M′-7) / 70 mass%, weight average molecular weight 70000, acid value 78 mg / g)

Exemplary Compound (XV): Monomer / acrylic acid / methoxypolyethyleneglycol methacrylate copolymer (15/20/65 mass%, weight average molecular weight 15000, acid value 156 mg) capable of forming the exemplary structural unit (M′-7) / g)

As the above-mentioned copolymer which is (B-3) specific dispersion resin in this invention, the monomer which can be a structural unit represented by the said General formula (a), the polymerizable oligomer and other monomer used together as desired, It can obtain by radical polymerization in a solvent. In this radical polymerization, the same radical polymerization initiator and chain transfer agent used when synthesize | combining (B-2) specific dispersion resin are used.

As content of the (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 the said composition, and 10-30 mass% is more preferable. When content of the (B) polymer dispersing agent is in the said range, since the dispersion time of the pigment used as a (A-1) coloring agent can be shortened and stability after dispersion is kept long, it is preferable.

[Other Dispersants]

The composition for coloring pattern formation of this invention can also use together a conventionally well-known dispersing agent (pigment dispersing agent) other than (B) dispersion resin.

Known dispersants (pigment dispersants) include polymer dispersants [eg, polyamideamines and salts thereof, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, modified poly (meth) acrylates, (meth) acrylic copolymers. And polyoxyethylene alkyl phosphate esters, polyoxyethylene alkylamines, alkanolamines, pigment derivatives, and the like.

Polymeric dispersants may be further classified into linear polymers, terminal modified polymers, graft polymers, and block polymers from the structure thereof.

The polymeric dispersant adsorbs on the surface of the pigment and acts to prevent reagglomeration. For that purpose, the terminal-modified polymer, the graft polymer, and the block polymer having an anchor portion to the pigment surface are mentioned as preferable structures. On the other hand, the pigment derivative has the effect of promoting the adsorption of the polymer dispersant by modifying the pigment surface.

As a specific example of the well-known dispersing agent (pigment dispersing agent) which can be used for this invention, "Disperbyk-107 (carboxylic acid ester), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 by BYK Chemie company (Polymer copolymer) "," EFKA4047, 4050, 4010, 4165 (polyurethane type), EFKA4330, 4340 (block copolymer), 4400, 4402 (modified polyacrylate), 5010 (polyesteramide), 6220 by EFKA company (Fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative) ”, Ajinomoto Fine-Techno Co., Ltd. `` Azisper PB821, PB822 '', Kyoeisha Chemical Co., Ltd. Production "Florene TG-710 (urethane oligomer)", "polyflow No.50E, No.300 (acrylic copolymer)", Kusumoto Chemicals, Ltd. Production "Disparon # 7004 (polyether ester), DA-703-50, DA-705, DA-725", Kao Corporation make "Imulgen 920, 930, 935, 985 (polyoxyethylene nonyl phenyl ether)" `` Acetamine 86 (stearylylamine acetate) '', `` Solpers 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine), 3000, 17000, 27000 (terminal part) produced by The Lubrizol Corporation Polymers having functional parts), 24000, 28000, 32000, 38500 (grafted polymers), Nikko Ts (polyoxyethylene sorbitan monooleate), and MYS-IEX (polyoxyethylene) manufactured by Nikko Chemicals Co., Ltd. Monostearate) "and the like.

The above-mentioned well-known dispersing agent can be used in 10-100 mass%, 1 / 10-1 / 1 (equivalent amount) with respect to (B) dispersion resin as needed.

<(C) polymeric compound>

The curable composition for coloring pixel formation of this invention contains the (C) polymeric compound.

The polymerizable compound which can be used in the present invention is an addition polymerizable compound having at least one ethylenically unsaturated double bond, and is selected from compounds having at least one, preferably two or more terminal ethylenically unsaturated bonds. Such compound groups are widely known in the industrial field, and in the present invention, these can be used without particular limitation. These have, for example, chemical forms such as monomers, prepolymers, ie dimers, trimers and oligomers, or mixtures thereof and copolymers thereof. Examples of monomers and their copolymers include unsaturated carboxylic acids (e.g. acrylic acid, Methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, and amides thereof, and preferably esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, unsaturated carboxylic acids and aliphatic polyamines. Amides of the compounds are used. Furthermore, addition reaction products of unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxyl groups, amino groups, and mercapto groups with monofunctional or polyfunctional isocyanates or epoxies, and monofunctional or polyfunctional The dehydration condensation reaction product with carboxylic acid, etc. are also used preferably. In addition, addition reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups and epoxy groups with monofunctional or polyfunctional alcohols, amines and thiols, and desorption substituents such as halogen groups and tosyloxy groups Substituted reactants of unsaturated carboxylic acid esters or amides with monofunctional or polyfunctional alcohols, amines and thiols are also preferable. As another example, it is also possible to use a compound group substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the above unsaturated carboxylic acid.

As an example of the monomer of the ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid, it is an acrylic ester, Ethylene glycol diacrylate, a triethylene glycol diacrylate, 1, 3- butanediol diacrylate, tetramethylene glycol diacrylate, and propylene Glycol diacrylate, neopentyl glycol diacrylate, trimethylol propane triacrylate, trimethylol propane tri (acryloyloxypropyl) ether, trimethylol ethane triacrylate, hexanediol diacrylate, 1,4-cyclo Hexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, Sor And the like toll tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligonucleotide hairpins, isocyanuric acid EO modified triacrylate.

As methacrylic acid ester, tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylol propane trimethacrylate, trimethylol ethane trimethacrylate, ethylene glycol dimethacryl Latex, 1,3-butanediol dimethacrylate, hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipenta Erythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacryloxy-2-hydroxypropoxy) phenyl] dimethylmethane, bis- [p- (methacryloxy Ethoxy) phenyl] dimethylmethane and the like.

As itaconic acid ester, ethylene glycol diitaconate, propylene glycol diitaconate, 1, 3- butanediol diitaconate, 1, 4- butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate, sorbitol tetraitaco Nate and the like. Examples of the crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, sorbitol tetracrotonate, and the like. Examples of isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate. Examples of the maleic acid ester include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, sorbitol tetramalate and the like.

As examples of other esters, for example, aliphatic alcohol esters described in Japanese Patent Publication No. 51-47334, Japanese Patent Publication No. 57-196231, Japanese Patent Publication No. 59-5240, Japanese Patent Publication No. 59-5241, and Japanese Patent The thing which has an aromatic skeleton of Unexamined-Japanese-Patent 2-226149, the thing containing the amino group of Unexamined-Japanese-Patent No. 1-165613, etc. can also be used preferably. In addition, the above-mentioned ester monomer can be used also as a mixture.

Moreover, as an example of the monomer of the amide of an aliphatic polyhydric amine compound and an unsaturated carboxylic acid, methylenebis- acrylamide, methylenebis-methacrylamide, 1, 6- hexamethylenebis- acrylamide, 1, 6- hexamethylene bis- Methacrylamide, diethylenetriamine trisacrylamide, xylylenebisacrylamide, xylylenebismethacrylamide and the like. As an example of another preferable amide monomer, what has a cyclohexylene structure of Unexamined-Japanese-Patent No. 54-21726 is mentioned.

Moreover, the urethane type addition polymerizable compound manufactured using addition reaction of an isocyanate and a hydroxyl group is also preferable, As such a specific example, 2 or more isocyanate groups per molecule are described, for example in Unexamined-Japanese-Patent No. 48-41708. The vinyl urethane compound etc. which contain 2 or more polymerizable vinyl groups in 1 molecule which added the vinyl monomer containing the hydroxyl group represented by following General formula (V) to the polyisocyanate compound which have is mentioned.

CH ₂ = C (R ⁴ ) COOCH ₂ CH (R ⁵ ) OH (V)

(Wherein R ⁴ and R ⁵ represent H or CH ₃ ).

Furthermore, urethane acrylates and Japanese Patent Publications No. 58-49860 and Japanese Patent Publications as described in Japanese Patent Application Laid-open No. 51-37193, Japanese Patent Application Laid-Open No. 2-32293, and Japanese Patent Application Laid-open No. Hei 2-16765. Also preferred are urethane compounds having an ethylene oxide skeleton described in Japanese Patent Application Laid-Open No. 56-17654, Japanese Patent Publication No. 62-39417, and Japanese Patent Publication No. 62-39418. Furthermore, by using addition polymerizable compounds having an amino structure or sulfide structure in the molecules described in Japanese Patent Application Laid-Open No. 63-277653, Japanese Patent Application Laid-Open No. 63-260909, and Japanese Patent Application Laid-open No. Hei 1-105238. The photopolymerizable composition which is very excellent in speed can be obtained.

Other examples include polyester acrylates, epoxy resins, and (meth) as described in Japanese Patent Application Laid-Open No. 48-64183, Japanese Patent Publication No. 49-43191, and Japanese Patent Publication No. 52-30490; Polyfunctional acrylates and methacrylates, such as epoxy acrylate which made acrylic acid react, are mentioned. Moreover, the specific unsaturated compound of Unexamined-Japanese-Patent No. 46-43946, Unexamined-Japanese-Patent No. 1-40337, Unexamined-Japanese-Patent No. 1-40336, the vinyl phosphonic acid type-compound of Unexamined-Japanese-Patent No. 2-25493, etc. are also mentioned. Can be mentioned. In either case, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Moreover, the thing introduce | transduced as a photocurable monomer and oligomer can also be used by Japanese adhesion association vol.20, No. 7, page 300-308 (1984).

About these polymeric compounds, the detail of usage methods, such as the structure, single use, combined use, and addition amount, can be arbitrarily set according to the performance design of a final sensing material. For example, it selects from the following viewpoints.

In terms of sensitivity, a structure having a high content of unsaturated groups per molecule is preferable, and in most cases, bifunctional or more is preferable. In order to increase the strength of the burned part, that is, the cured film, a trifunctional or more functional thing is preferable, and another functional water and another polymerizable group (e.g., acrylic acid ester, methacrylic acid ester, styrene compound, vinyl ether compound) By using together, the method of adjusting both sensitivity and intensity 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 to use a compound containing three or more, and to use a compound containing four or more. Most preferred. Moreover, it is preferable to contain an EO modified body from a 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 strength.

In addition, the selection and use of the addition polymerization compound are also important factors in terms of compatibility and dispersibility with other components (eg, binder polymers, initiators, colorants (pigments, dyes, etc.)) in the polymerizable layer. Compatibility may be improved by the use of a purity compound and 2 or more types of combined use A specific structure can also be selected in order to improve adhesiveness, such as a board | substrate and an overcoat layer mentioned later.

From the above viewpoints, bisphenol A diacrylate, bisphenol A diacrylate EO modified substance, trimethylol propane triacrylate, trimethylol propane tri (acryloyloxypropyl) ether, trimethylol ethane triacrylate, and tetraethylene glycol di Acrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol Tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, pentaerythritol tetraacrylate EO modification, dipentaerythritol hexaacrylate EO modification, etc. are preferable. The commercially available products include urethane oligomers UAS-10, UAB-140 (manufactured by Nippon Paper Chemicals Co., Ltd.), DPHA (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, and UA-306I. , AH-600, T-600, and AI-600 (manufactured by Kyoeisha Chemicals Co., Ltd.) are preferred.

Among these, bisphenol A diacrylate EO modified product, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, Pentaerythritol tetraacrylate EO modifier, dipentaerythritol hexaacrylate EO modifier, etc. are commercially available products such as DPHA (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600 and AI-600 (made by Kyoeisha Chemicals Co., Ltd.) are more preferable.

(C) It is preferable that content of a polymeric compound is 5-50 mass% in the total solid of the curable composition for colored pixel formation of this invention, It is more preferable that it is 7-40 mass%, It is 10-35 mass% More preferred.

<(D) Photoinitiator>

The curable composition for coloring pixel formation of this invention contains the (D) photoinitiator.

The photoinitiator in this invention is a compound which decomposes | disassembles with light and starts and accelerates superposition | polymerization of the said (C) polymeric compound, It is preferable to have absorption in the area | region of wavelength 300-500 nm. In addition, a photoinitiator can be used individually or in combination of 2 or more types.

Examples of the photopolymerization initiator include organic halogenated compounds, oxadiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxide compounds, azo compounds, coumarin compounds, azide compounds, and metallocene compounds. And hexaarylbiimidazole 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 Patent No. 3,905,815, Japanese Patent Publication No. 46-4605, Japanese Patent Publication No. 48-36281, Japan Japanese Patent Laid-Open No. 55-32070, Japanese Patent Laid-Open No. 60-239736, Japanese Patent Laid-Open No. 61-169835, Japanese Patent Laid-Open No. 61-169837, Japanese Patent Laid-Open No. 62-58241, Japanese Patent Laid-Open No. 62- 212401, Japanese Patent Laid-Open No. 63-70243, Japanese Patent Laid-Open No. 63-298339, MPHutt "Journal of Heterocyclic Chemistry" 1 (No3), (1970), and the like. The oxazole compound in which the methyl group was substituted, and the s-triazine compound are mentioned.

Hereinafter, the s-triazine compound which is a preferable polymerization initiator in this invention is demonstrated in detail.

As the s-triazine compound, more preferably an s-triazine derivative in which at least one mono, di, or tri halogen-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 (trichloromethyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4, 6-bis (trichloromethyl) -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 (tree Roromethyl) -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-nathoxynaphthyl) -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 and the like.

As a photoinitiator of a halomethyl-s-triazine type compound, 4- (p-aminophenyl) -2,6-di as represented by the following general formula (DA) of Unexamined-Japanese-Patent No. 11-323057 also is mentioned. -Halomethyl-s-triazine compound, vinyl-halomethyl-s-triazine compound as represented by the following general formula (DB) described in Japanese Patent Publication No. 59-1281, and Japanese Patent Publication No. 53- 2- (naphtho-1-yl) -4,6-bis-halomethyl-s-triazine compound represented by the following general formula (DC) described in 133428 is listed as a preferable thing.

R ¹ and R ² in the general formula (DA) each independently represent a hydrogen atom, an alkyl group, an aryl group, or a substituent represented by the following general formula (DA-1) or general formula (DA-2). R ³ and R ⁴ each independently represent 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 represent 0, 1 or 2.

In said general formula (DA-1) and general formula (DA-2), R <^5> , R <^6> , R <^7> respectively independently represents an alkyl group or an aryl group.

In the general formulas (DA) to (DA-2), the alkyl group and the aryl group represented by R ¹ to R ⁷ may further have a substituent, and examples of the substituent that can be introduced include aryl groups such as phenyl groups and halogen atoms And an alkoxy group, a carboalkoxy group, a carboaryloxy group, an acyl group, a nitro group, a dialkylamino group, or a sulfonyl derivative.

In general formula (DA), you may form the ring structure which consists of a nonmetallic atom with the nitrogen atom which R <^1> and R <^2> couple | bond with it, and what is shown below is mentioned as a ring structure formed in that case.

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) amino Phenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-methyl-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl)- s-triazine, 4- (pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (pN-ethoxycarbonylmethylaminophenyl) -2,6- Di (trichloromethyl) -s-triazine, 4- [pN, N-di (phenyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (pN-chloroethyl Carbonylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- [pN- (p-methoxyphenyl) carbonylaminophenyl] 2,6-di (trichloromethyl)- s-triazine, 4- [mN, N-di (ethoxycarbonylmethyl) Minophenyl] -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 (trichloromethyl) -s-triazine, 4- [o-fluoro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-bromo-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-chloro-pN, N-di ( Chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-fluoro-pN, N-di (chloroethyl) aminophenyl] -2,6-di ( Trichloromethyl) -s-triazine, 4- (m-bromo-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m- Chloro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-fluoro-pN- Oxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloro Rhomethyl) -s-triazine, 4- (o-chloro-pN-ethoxycarbonylmethylaminophenyl) -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-pN -Chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl)- s-triazine, 4- (o-chloro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-fluoro-pN-chloroethyl aminophenyl ) -2,6-di (trichloromethyl ) -s-triazine and the like.

In General Formula (DB), Q ³ represents Br or Cl, and P represents -CQ ³ , -NH ₂ , -NHR, -N (R) ₂ or -OR (where R represents a phenyl group or an alkyl group). W also represents an aromatic ring which may have a substituent, a substituent represented by the following general formula (DB-1), or in general formula (DB-1), Z is -O- or -S-, and R is A phenyl group or an alkyl group is represented. n is an integer of 0-2.

Specific examples of the compound represented by the general formula (DB) include 2,4-bis (trichloromethyl) -6-p-methoxystyryl-s-triazine and 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 Listed.

In General Formula (DC), X and Y respectively independently represent -Br or -Cl, and m and n are integers of 0-3. R 'is a substituent represented by the general formula (DC-1), wherein R ¹ represents a hydrogen atom or -OR ^c , where R ^c represents an alkyl group, a cycloalkyl group, an alkenyl 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 (DC) include 2- (naphtho-1-yl) -4,6-bis-trichloromethyl-s-triazine and 2- (4-methoxy-naphtho- 1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-ethoxy-naphtho-1-yl) -4,6-bis-trichloromethyl-s-triazine , 2- (4-butoxy-naphtho-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2-methoxyethyl) -naphtho-1- Il] -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2-ethoxyethyl) -naphtho-1-yl] -4,6-bis-trichloromethyl-s -Triazine, 2- [4- (2-butoxyethyl) -naphtho-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- (2-methoxy-naphtho -1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-methoxy-5-methyl-naphtho-2-yl) -4,6-bis-trichloromethyl -s-triazine, 2- (6-methoxy-naphtho-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (5-methoxy-naphtho-1- Il) -4,6-bis-trichloromethyl-s-triazine , 2- (4,7-dimethoxy-naphtho-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-ethoxy-naphtho-2-yl)- 4,6-bis-trichloromethyl-s-triazine, 2- (4,5-dimethoxy-naphtho-1-yl) -4,6-bis-trichloromethyl-s-triazine and the like do.

Examples of the oxadiazole compounds include 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (cyanostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (naphtho-1-yl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (4-styryl) styryl-1,3,4- Oxadiazole and the like.

Moreover, the compound represented by general formula (D-D) shown below is mentioned as a preferable example of another triazine type initiator.

R <^1> represents a hydrogen atom, a hydroxyl group, a C1-C3 alkyl group, or a C1-C3 alkoxy group in general formula (DD), and m is an integer of 1-3. Here, when m is 2 or 3, two or more R <^1> may mutually be same or different.

As a specific example of a compound represented by general formula (DD), for example, 1, 3-bistrichloromethyl-5-benzooxolatriazine, 1,3-bistrichloromethyl-5- (5-methylbenzo jade Solan) triazine, 1,3-bistrichloromethyl-5- (6-methoxybenzooxolane) triazine and the like.

As the carbonyl compound, benzos such as benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, and 2-carboxybenzophenone Phenone derivatives, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexylphenylketone, α-hydroxy-2-methylphenylpropane, 1-hydroxy- 1-methylethyl- (p-isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl-1- (4 '-(methylthio) phenyl) -2-mor Polyno-1-propaneone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2,4,6-trimethylbenzoyl-diphenyl-phosphineoxide, 1 Acetophenone derivatives such as 1,1-trichloromethyl- (p-butylphenyl) ketone, 2-benzyl-2-dimethylamino-4-morpholinobutyrophenone, thioxanthone, 2-ethyl thioxanthone, 2-isopropyl thioxanthone, 2-chloro thioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl Thioxanthone, and the like can be mentioned 2,4-diisopropyl thioxanthone, etc. of thioxanthone derivatives, p- dimethylaminobenzoic acid ethyl, p--diethylamino-benzoic acid ethyl ester derivatives such as the acid.

Benzyl dimethyl ketal, benzyl- (beta)-methoxyethyl ethyl acetal, etc. are mentioned as a ketal compound.

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 -Butyl peroxy) cyclohexane, 2,2-bis (tert-butylperoxy) butane, tert-butylhydroperoxide, cumene hydroperoxide, diisopropylbenzenehydroperoxide, 2,5-dimethylhexane-2 , 5-dihydroperoxide, 1,1,3,3-tetramethylbutylhydroperoxide, tert-butylcumylperoxide, dicumylperoxide, 2,5-dimethyl-2,5-di (tert-butyl Peroxy) hexane, 2,5-oxanoyl peroxide, succinic peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, diisopropylperoxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-2- Ethoxyethylperoxydicarbonate, dimethoxyisopropylperoxycarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, tert-butylperoxyacetate , tert-butylperoxy pivalate, tert-butylperoxy neodecanoate, tert-butylperoxyoctanoate, tert-butylperoxylaurate, tert-carbonate, 3,3 ', 4,4'- Tetra- (t-butylperoxycarbonyl) benzophenone, 3,3 ', 4,4'-tetra- (t-hexylperoxycarbonyl) benzophenone, 3,3', 4,4'-tetra- (p-isopropylcumylperoxycarbonyl) benzophenone, carbonyldi (t-butylperoxy dihydrogen phthalate), carbonyldi (t-hexylperoxy dihydrogen phthalate), and the like.

As an azo compound, the azo compound etc. of Unexamined-Japanese-Patent No. 8-108621 are mentioned, for example.

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

Examples of the azide compound include the organic azide compounds described in US Patent No. 2848328, US Patent No. 2852379, and US Patent No. 2940853, and 2,6-bis (4-azidebenzylidene) -4-ethylcyclohexa Rice (BAC-E) and the like.

As a metallocene compound, Unexamined-Japanese-Patent No. 59-152396, Unexamined-Japanese-Patent No. 61-151197, Unexamined-Japanese-Patent No. 63-41484, Unexamined-Japanese-Patent No. 2-249, Unexamined-Japanese-Patent No. 2 Various titanocene compounds disclosed in JP-A-4705 and JP-A-5-83588, for example, di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti-bis- 2,6-difluoropheni-1-yl, di-cyclopentadienyl-Ti-bis-2,4-di-fluorophenni-1-yl, di-cyclopentadienyl-Ti-bis-2 , 4,6-trifluoropheni-1-yl, di-cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluoropheni-1-yl, di-cyclopentadienyl-Ti -Bis-2,3,4,5,6-pentafluoropheni-1-yl, di-methylcyclopentadienyl-Ti-bis-2,6-difluoropheni-1-yl, di-methyl Cyclopentadienyl-Ti-bis-2,4,6-trifluoropheni-1-yl, di-methylcyclopentadienyl-Ti-bis-2, 3,5,6-tetra Fluoropheni-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluoropheni-1-yl, Japanese Patent Laid-Open No. 1-304453, Japan The iron-alein complexes of Unexamined-Japanese-Patent No. 1-52109 are mentioned.

As a hexaaryl biimidazole compound, the various compounds described in each specification, such as Unexamined-Japanese-Patent No. 6-29285, US Patent 3,479,185, 4,311,783, 4,622,286, 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) biimidazole, 2,2'-bis (o, o'-dichlorophenyl) -4,4', 5,5'-tetra Phenylbiimidazole, 2,2'-bis (o-nitrophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-methylphenyl) -4,4' , 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-trifluorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, etc. are mentioned.

As the organic borate compound, for example, Japanese Patent Laid-Open No. 62-143044, Japanese Patent Laid-Open No. 62-150242, Japanese Patent Laid-Open No. 9-188685, Japanese Patent Laid-Open No. 9-188686, and Japanese Patent Laid-Open No. 9- 188710, Japanese Patent Laid-Open No. 2000-131837, Japanese Patent 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 , An organic boron sulfonium complex or organic boron described in Japanese Patent Application Laid-Open No. 6-157623, Japanese Patent Application Laid-Open No. 6-175564, Japanese Patent Application Laid-Open No. 6-175561, etc. Iodine sulfonium complex, organoboron iodonium complex described in JP-A-6-175554, JP-A-6-175553, organoboron phosphonium complex described in JP-A-9-188710, Japan Japanese Patent Laid-Open No. 6-348011, Japanese Patent Laid-Open No. 7-128785 , And Japanese Patent Publication No. Hei 7-140589 discloses, in Japanese Patent Publication No. Hei 7-306527 discloses, in Japanese Patent Publication No. 7-292014 discloses the like of the organic boron transition metal coordination complexes are exemplified as specific examples.

As a disulfone compound, the compound etc. which are described in Unexamined-Japanese-Patent No. 61-166544, the specification of Unexamined-Japanese-Patent No. 2001-132318, etc. are mentioned.

As an oxime ester compound, it is J.C.S. Perkin II (1979) 1653-1660), J.C.S. Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, Japanese Patent Laid-Open No. 2000-66385, Japanese Patent Laid-Open No. 2000-80068, Japanese Patent Laid-Open No. 2004-534797 The compound of the publication, etc. are mentioned. Specific examples thereof include Chiba Specialty Chemicals K.K. Production monovalent OXE-01, OXE-02, etc. are preferable.

As an onium salt compound, for example, the diazonium salt described in SISchlesinger, Photogr. Sci. Eng., 18, 387 (1974), TSBal et al, Polymer, 21, 423 (1980), US Pat. No. 4,069,055 , Ammonium salts described in Japanese Patent Application Laid-Open No. 4-365049 and the like, phosphonium salts described in the US Patent Nos. 4,069,055 and 4,069,056, European Patents 104,143, US Patents 339,049, and 410,201, respectively The iodonium salt etc. which were described in each of Unexamined-Japanese-Patent No. 2-150848 and Unexamined-Japanese-Patent No. 2-296514 are mentioned.

The iodonium salt which can be preferably used in the present invention is a diaryl iodonium salt, and from the viewpoint of stability, it is preferable that two or more of the iodonium salts are substituted with an electron-supply group such as an alkyl group, an alkoxy group or an aryloxy group. Moreover, as a form of another preferable sulfonium salt, the iodonium salt etc. which one substituent of a triarylsulfonium salt has a coumarin and anthraquinone structure, and has absorption in 300 nm or more are preferable.

The sulfonium salts that can be preferably used in the present invention include European Patent Nos. 370,693, 390,214, 233,567, 297,443, 297,442, 4,933,377, 161,811, 410,201, 339,049 4,760,013, 4,734,444, 2,833,827, German Patent Nos. 2,904,626, 3,604,580, 3,604,581, and the sulfonium salts described in the specifications, and are preferably substituted with electron withdrawing groups from the sensitivity point of stability. It is preferable that it is done. As an electron withdrawing group, a thing with a Hammett value larger than zero is preferable. Preferred electron withdrawing groups include halogen atoms, carboxylic acids and the like.

Moreover, as another preferable sulfonium salt, the sulfonium salt in which one substituent of a triarylsulfonium salt has a coumarin and anthraquinone structure, and has absorption in 300 nm or more is mentioned. As another preferable sulfonium salt, the sulfonium salt which has absorption in 300 nm or more in which a triaryl sulfonium salt has an allyloxy group and an arylthio group as a substituent is mentioned.

Moreover, as an onium salt compound, the selenoids described in JVCrivello et al, Macromolecules, 10 (6), 1307 (1977), JVCrivello et al, J. Polymer Sci., Polymer Chem. Ed., 17, 1047 (1979). Onium salts, such as an nium salt, an arsonium salt as described in CSWen et al, Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988), etc. are mentioned.

As the acylphosphine (oxide) compound, Chiba Specialty Chemicals K.K. Production of monocure 819, Tarocure 4265, Tarocure TPO, and the like.

As (D) photoinitiator used for this invention, from a viewpoint of exposure sensitivity, a trihalomethyl triazine type compound, the benzyl dimethyl ketal compound, the (alpha)-hydroxy ketone compound, the (alpha)-amino ketone compound, the acyl phosphine type compound, and a phosphine jade Seed compound, metallocene compound, oxime compound, triarylimidazole dimer, onium compound, benzothiazole compound, benzophenone compound, acetophenone compound and derivatives thereof, cyclopentadiene-benzene-iron complex And a salt, a halomethyloxadiazole compound, or a compound selected from the group consisting of a 3-aryl substituted coumarin compound is preferable.

More preferably, trihalomethyl triazine compound, α-amino ketone compound, acyl phosphine compound, phosphine oxide compound, oxime compound, triarylimidazole dimer, onium compound, benzophenone compound, aceto It is a phenone type compound, At least 1 sort (s) of compound chosen from the group which consists of a trihalomethyl triazine compound, the (alpha)-amino ketone compound, an oxime type compound, a triaryl imidazole dimer, and a benzophenone type compound is the most preferable.

It is preferable that content of the (D) photoinitiator contained in the curable composition of this invention is 0.1-50 mass% with respect to the total solid of a curable composition, More preferably, it is 0.5-30 mass%, Especially preferably, it is 1-20. Mass%. In this range, good sensitivity and pattern formability are obtained.

<(E) solvent>

Generally the curable composition for colored pixel formation of this invention can be prepared using a solvent.

Examples of the solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, and lactic acid Methyl, ethyl lactate, methyl oxyacetic acid, ethyl oxyacetic acid, butyl oxyacetate, methoxyacetic acid methyl, methoxyacetic acid ethyl, methoxyacetic acid butyl, ethoxyacetic acid methyl, ethoxyacetic acid ethyl, and 3-oxypropionate methyl, 3 3-oxypropionic acid alkyl esters such as ethyl oxypropionate (for example, 3-methoxypropionate methyl, 3-methoxypropionate ethyl, 3-ethoxypropionate methyl, 3-ethoxypropionate, etc.), 2- 2-oxypropionate alkyl esters such as methyl oxypropionate, ethyl 2-oxypropionate and propyl 2-oxypropionate Leu (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate) , Ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, and the like), and methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetic acid, acet Ethyl acetate, 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 mono Butyl 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, deep Propylene glycol monomethyl ether acetate, dipropylene glycol n- propyl ether acetate, dipropylene glycol n- butyl ether acetate, tripropylene glycol n- butyl ether, tripropylene glycol methyl ether acetate and the like;

Ketones such as acetone, methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and the like;

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.

Of these, 3-ethoxypropionate methyl, 3-ethoxypropionate ethyl, 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 preferable.

You may use a solvent in combination of 2 or more type other than using independently.

[Curable Compositions for Shading the Shading Part and Shading Part]

Next, the light shielding part (black matrix) in the color filter of this invention is demonstrated.

The light shielding portion preferably has an optical density (OD value) of 4.5 or more and 8.0 or less, and more preferably 4.8 or more, and more preferably 5.0 to 7.0. If the optical density is less than 4.5, the display quality of the display device such as contrast decreases. In addition, the optical density here means the optical density (OD value) measured by the method of Example description.

In addition, it is preferable that a light shielding part is 5-15 micrometers in width from a viewpoint of ensuring the brightness by high aperture ratio. The thickness of a light shielding part is 0.2-1.5 micrometers, More preferably, it is 0.3-1.0 micrometer, More preferably, it is the range of 0.3-0.8 micrometer. Within this thickness range, irregularities of the substrate on which the light shielding portion is provided, that is, the step difference between the formation region and the non-forming region of the light shielding portion are appropriately maintained, and high accuracy is achieved even when a colored pixel of BRG is formed thereon after the light shielding portion is formed. Pixel can be formed.

Curable Composition For Shading Part Formation

The light shielding part in the color filter of this invention contains (A-2) light-shielding agent, (B) polymer dispersing agent, (C) polymeric compound, (D) polymerization initiator, and (E) solvent, and it is carbon black as a light-shielding agent It is formed with the curable composition for color filter light-shielding part formation which contains 40-80 mass% or 50-90 mass% of metal type microparticles | fine-particles in conversion of solid content.

<(A-2) Shading Agent>

Here, as the light-shielding agent (A-2), carbon black, titanium black, metal fine particles, metal oxides, sulfide fine particles and the like are preferably listed.

These are used individually or in combination of multiple types as needed. For example, carbon black alone, metal microparticles | fine-particles, a combination of both, or the form which uses another coloring pigment and titanium carbon further together are mentioned.

As a material for light shielding, at least 2 or more types of pigments which shield the visible light region have been used in combination as a black colorant in the past. As these pigments, the pigments of Unexamined-Japanese-Patent No. 2005-17716 [0038]-[0040], and the Unexamined-Japanese-Patent No. 2005-17521-[0080]-[0088] are mentioned, The light-shielding layer using these pigments is mentioned. The formation of is disclosed in Japanese Patent Laid-Open No. 7-271020 and the like. However, when the pigment was used for the light shielding layer, sufficient shielding was not obtained.

In order to increase the light shielding effect, in Japanese Patent Application Laid-Open No. 2000-147240, Japanese Patent Application Laid-Open 2000-143985, Japanese Patent Application Laid-Open 2005-338328, Japanese Patent Application Laid-Open 2006-154849 and the like, carbon black, titanium black, graphite, and the like are preferred as light-shielding materials. Has been developed. In the present invention, carbon black is preferred 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. As carbon black, carbon black # 2400, # 2350, # 2300, # 2200, # 1000, # 980, # 970, # 960, # 950, # 900, # 850, MCF88, # made by Mitsubishi Chemicals 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 N339, 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; Carbon Black Color Black FW200, Color Black FW2, Color Black FW1, Color Black FW18, Color Black S170, Color Black S160, Special Black 6, Special Black 5, Special Black 4, Special Black 4A, Printex U, Printex V, Printex 140U, Printex 140V; Carbon black REGAL 400, REGAL 400R, REGAL XC72, VULCAN XC72R, MOGUL L, MONARCH 1400, MONARCH 1000, black PEARLS1400 manufactured by Cabot; Asahi Carbon Co., Ltd. Carbon black SUNBLACK 900, copper 910, copper 930, copper 960, copper 970 etc. of the production are mentioned. It is also preferable to coat these with a high molecular compound in order to increase the electrical resistance. The preferred size of single particles 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 or a mixture thereof is preferable. As a commercial item, Mitsubishi Material Corporation make (brand name) 12S and 13M are mentioned. As for the average particle diameter of titanium black, 10-100 nm is preferable.

As an example of graphite, by using graphite having a long diameter of 1 µm or less as the light shielding material for color filters, the contour shape of the light shielding pattern becomes uniform and the sharpness is good. 20 nm or more and 500 nm or less are more preferable. Moreover, it is preferable that the existence ratio of the particle | grains which have a particle diameter of 100 nm or less is 70% or more.

The above-mentioned titanium black is also metal fine particles, but as a result of obtaining higher light shielding properties, particles having metals or metals such as silver or the like (hereinafter referred to as JP 2005-17322, JP 2005-179632, JP 2005-263920, etc.) And "metal-based fine particles" may be developed.

Examples of preferred metals constituting these metallic fine particles include copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium, iron, calcium, ruthenium, osmium, manganese, molybdenum, tungsten, niobium, tantalum, bismuth , Antimony, and at least one selected from these alloys. More preferred metals are at least one selected from copper, silver, gold, platinum, palladium, tin, calcium, and alloys thereof, and particularly preferred metals are selected from copper, silver, gold, platinum, tin and alloys thereof It is at least 1 type, and a compound with other elements other than a metal is also preferable. Examples of the compound of the metal and other elements include oxides of metals, sulfides, sulfates, carbonates, and the like, and as the metal compound particles, these particles are preferable. Especially, the particle | grains of a sulfide are preferable from the ease of color tone and microparticle formation. Moreover, you may use together with a metal, its alloy, and a metal compound, and 2 or more types may be sufficient as it. Among them, silver or alloys thereof and sulfides thereof are particularly preferred because of their high shielding effect. As an example of an alloy, silver tin alloy is listed as a preferable example.

Moreover, the composite particle which the metal and the metal compound couple | bonded and became one particle is also preferable, For example, the thing from which a composition differs in the inside and the surface of particle | grain, the thing of two types of particle | grains, etc. are mentioned. As a specific example, composite fine particles of silver and silver sulfide, composite fine particles of silver and copper oxide (II), and the like are preferable.

The metal-based fine particles may be core shell composite particles (core shell particles). The core shell type composite particles (core shell particles) are those obtained by coating the surface of a core material with a shell material, and specific examples thereof include core shells described in paragraphs [0024] to [0027] of JP 2006-18210A. Particulates are listed.

Since these metallic fine particles have high black concentration, can exhibit excellent light shielding performance in a small amount or thin film, and have high thermal stability, heat treatment at high temperature (for example, 200 degrees or more) without damaging black concentration It is possible to ensure a high degree of light shielding stably. For example, a high light shielding property is required and it is generally preferable for a light shielding film (so-called black matrix) or the like for a color filter subjected to a baking treatment.

In addition to the commercially available metal fine particles in the present invention, the metal-based fine particles can be prepared by chemical reduction of metal ions, electroless plating, evaporation of metals, or the like. For example, the rod-shaped silver fine particles are spherical silver fine particles as seed particles, and then silver salt is further added, and a relatively reducing power such as ascorbic acid is used in the presence of a surfactant such as cetyltrimethylammonium bromide, thereby reducing silver. Bars or wires are obtained. This is described in Advanced Materials 2002, 14, 80-82. The same substrate is also found in Materials Chemistry and Physics 2004, 84, 197-204, Advanced Functional Materials 2004, 14, 183-189.

In the present invention, the number average particle diameter of the metallic fine particles is preferably 5 to 100 nm, more preferably 5 to 80 nm, and particularly preferably 5 to 50 nm. If the number average particle diameter of the particles is 100 nm or less, the surface smoothness is good, and there is an advantage that the fish eye due to the coarse particles is also reduced.

As content of the metal microparticles | fine-particles in the curable composition for light shielding part formation of this invention, considering preventing metal microparticles | fine-particles etc. at the time of post-baking, such as at the time of preparation of a color filter, for example, considers the light-shielding effect If it is lower, it is preferable to adjust so that it may be about 50-90 mass% with respect to the total solid of the curable composition for light shielding part formation formed, Preferably it is 50-85 mass%.

In addition, it is preferable to perform content of metal type microparticles | fine-particles in consideration of the fluctuation | variation of the optical density by an average particle diameter. In addition, depending on the metallic fine particles to be used, the above-described pigment, carbon and the like may be used in combination for color correction.

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

<(B) Dispersant>

It is preferable that the metallic microparticles | fine-particles in this invention exist in stable dispersion state, for example, it is more preferable that it is a colloidal state. In the case of the colloidal state, for example, it is preferable that the metal-based fine particles are substantially dispersed in the fine particle state. Here, substantially dispersed means a state in which primary particles are dispersed independently without agglomeration or soft aggregation.

As an additive which may be mix | blended with the dispersing agent and composition at the time of disperse | distributing metal type microparticles | fine-particles, the dispersing agent and additive of Paragraph No. [0027]-[0031] of Unexamined-Japanese-Patent No. 2005-17322 are mentioned as a preferable thing also in this invention.

The dispersing agent used here is a specific dispersing resin listed as said curable composition for colored pixel formation, ie, the polymeric dispersing agent which has an acid value of 20-300 mg / g, and a weight average molecular weight is in the range of 3,000-100,000, More specifically, The dispersion resin enumerated as specific resin dispersion resin (B-1)-dispersion resin (B-3) is used preferably, and the preferable aspect in curable composition for light shielding part formation is also the same as that mentioned above.

Examples of the dispersant for the metal-based fine particles include hydrophilic moieties such as a carboxyl group, an OH group, a sulfonic acid group, a phosphoric acid group, an amino group, a carbonyl group, a thiol group, and a polyoxyalkylene moiety, and a phenyl group (including a naphthalene ring), an alicyclic ring, an alkyl group, and substituted groups thereof. Although the compound etc. which carry lipophilic part etc. are common as a dispersing agent, For example, the compound illustrated below can be used as a commercial item. 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 (more than EFKA ADDITIVES company),

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 (by BYK company),

Disparlon 7301, 325, 374, 234, 1220, 2100, 2200, KS260, KS273N, 1210, 2150, KS860, KS873N, 7004, 1813, 1860, 1401, 1200, 550, EDAPLAN470, 472, 480, 482, K-SPERSE131 , 152, 152MS (more than Kusumoto Chemicals, Ltd.),

Solspers 3000, 5000, 9000, 12000, 13240, 13940, 17000, 22000, 24000, 26000, 28000, etc. (manufactured by AVECIA),

Caribbean B, Copper L-400, Eleminol MBN-1, Sanspur PS-2, Copper PS-8, Ionet S-20 (manufactured by Sanyo Chemical Industries, Ltd.),

Disperse Ade 6, Disperse Ade 8, Disperse Ade 15, Disperse Ade 9100 (manufactured by San Nopco Limited) and the like can be used.

These specific dispersion resins may be used independently and may use 2 or more types together.

The addition amount of a dispersing agent is 3-30 mass parts with respect to a pigment (light-shielding agent), Preferably it is 5-20 mass parts.

If necessary, in addition to the specific dispersion resin according to the present invention, a polymer dispersant may be used. By using a polymeric dispersant, dispersion stability and preservation property improve. About the dispersion resin which can be used as a dispersing agent, it is described, for example in "the dictionary of pigments" (Itosei Shiro edition, Asakura Co., Ltd., 2000).

<(C-2) polymeric compound>

As a polymeric compound in the curable composition for light shielding part formation, although the polymeric compound used in the said curable composition for colored pixel formation is also listed as a preferable thing, what is shown below is especially preferable.

As a polymeric compound in the curable composition for light-shielding part formation of this invention, it is preferable that it is a monomer or oligomer which has two or more ethylenically unsaturated double bonds and add-polymerizes by light irradiation. As such a monomer and an oligomer, the compound which has at least 1 addition-polymerizable ethylenically unsaturated group in a molecule, and whose boiling point is 100 degreeC or more at normal pressure is mentioned. Examples thereof 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, trimethylol ethane triacrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropanediacrylate, neopentyl glycol di (meth) Acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, hexanediol di (meth) acrylate, Trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin tri (meth) acrylate; And polyfunctional acrylates and polyfunctional methacrylates such as those obtained by adding ethylene oxide or propylene oxide to polyfunctional alcohols such as trimethylolpropane and glycerin and then (meth) acrylated.

Acidic polyfunctional photocurable compounds are also preferred compounds. As the acidic polyfunctional photocurable compound, (1) a monomer or oligomer having three or more photocurable functional groups together with a hydroxyl group is introduced into a dibasic anhydride to introduce a carboxyl group, and (2) three or more photocurable groups together with a hydroxyl group. A carboxyl group is introduced by adding a glycidyl group or a compound having an isocyanate group and a COOH group to a monomer or oligomer having a functional group, or (3) an aromatic compound having three or more photocurable functional groups is modified with concentrated sulfuric acid or fuming sulfuric acid. The thing which introduce | transduced a sulfonic acid group etc. can be used by this. 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, it is preferable to represent with the following general formula (i) and general formula (ii). In General Formulas (i) and (ii), when T or G is an oxyalkylene group, the terminal on the carbon atom side is bonded to R, X and W.

In the general formula (i) R represents an acryloyloxy group in a (meth) acrylate, X represents a group -COOH, -OPO ₃ H _2. 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 three or more W of six W is R. G is synonymous with T in General 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), Toagosei Co., Ltd., for example. TO-756 which is a carboxyl group-containing trifunctional acrylate of a product, TO-1382 which is a carboxyl group-containing 5-functional acrylate, etc. are mentioned.

Urethane acrylates described in JP-A-48-41708, JP-A-50-6034, and JP-A-51-37193; Polyester acrylates described in JP-A-48-64183, JP-A-49-43191 and JP-A-52-30490; Polyfunctional acrylates and methacrylates, such as epoxy acrylates which are reaction products of an epoxy resin and (meth) acrylic acid, are mentioned. Among them, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, the carboxyl group-containing 5-functional acrylate and the like This is preferred. In addition, "polymerizable compound B" described in Unexamined-Japanese-Patent No. 11-133600 is also mentioned as a preferable thing.

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, It is more preferable that it is 7-40 mass%, 10 More preferably, it is -35 mass%.

The (D) polymerization initiator, the (E) solvent, etc. which are used for the curable composition for light shielding part formation are the same as that in the curable composition for colored pixel formation mentioned above, and its preferable content is also the same.

Moreover, in addition to the said essential component, various well-known additives can be used for the curable composition for colored pixel formation and the curable composition for light shielding part formation of this invention according to the objective.

Hereinafter, such an additive is explained in full detail.

<Alkali Soluble Resin>

In each said curable composition of this invention, alkali-soluble resin can be used as a binder polymer for the purpose of a film characteristic improvement, etc.

As alkali-soluble resin used by this invention, it is a linear organic high molecular polymer, group which promotes at least 1 alkali solubility in a molecule | numerator (preferably an acryl-type copolymer, the molecule which has a styrene-type copolymer as main chain) (for example, a carboxyl group) , Phosphoric acid group, sulfonic acid group, hydroxyl group, etc.) can be suitably selected from alkali-soluble resin.

More preferred as the alkali-soluble resin are polymers having a carboxylic acid in the side chain, for example, Japanese Patent Application Laid-Open No. 59-44615, Japanese Patent Publication No. 54-34327, Japanese Patent Publication No. 58-12577, and Japanese Patent. Methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid, as described in Japanese Patent Application Laid-Open Nos. 54-25957, JP-A-59-53836 and JP-A-59-71048. Examples thereof include copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, and acrylic copolymers such as acidic cellulose derivatives having a carboxylic acid in the side chain and an acid anhydride added to a polymer having a hydroxyl group.

As acid value, 20-200 mgKOH / g, Preferably it is 30-180 mgKOH / g, More preferably, the thing of the range of 50-150 mgKOH / g is preferable.

About the specific structural unit of alkali-soluble resin, the copolymer of (meth) acrylic acid and another monomer copolymerizable with this is especially preferable. As another monomer copolymerizable with the said (meth) acrylic acid, an alkyl (meth) acrylate, an aryl (meth) acrylate, a vinyl compound, etc. are mentioned. Here, the hydrogen atom of an alkyl group and an aryl group may be substituted by the substituent.

The alkyl (meth) acrylate and aryl (meth) acrylates Examples of ^{_{CH 2 = C (R 1)}} (COOR 3) [ wherein, R ¹ is a hydrogen atom or a C1-5 alkyl group, R ² is C 6 It represents -10 aromatic hydrocarbon rings, and R <^3> represents a C1-C8 alkyl group or a C6-C12 aralkyl group.] Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, and 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), hydroxyglycol Cydyl methacrylate, tet And the like dihydro furfuryl methacrylate.

Moreover, the resin which has a polyalkylene oxide chain in a molecular side chain is also preferable. As said polyalkylene oxide chain, a polyethylene oxide chain, a polypropylene oxide chain, a polytetramethylene glycol chain, or these combination can also be used, 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. Examples of the acrylic copolymer having a polyalkylene oxide chain in these side chains include polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and poly (ethylene glycol-propylene glycol) mono (meth). Acrylate etc. and the compound which alkyl-blocked these terminal OH groups, for example, methoxy polyethyleneglycol mono (meth) acrylate, ethoxy polypropylene glycol mono (meth) acrylate, methoxy poly (ethylene glycol propylene glycol) It is an acryl-type copolymer which uses mono (meth) acrylate etc. as a copolymerization component.

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, R ² represents an aromatic hydrocarbon ring having 6 to 10 carbon atoms, and R ³ represents 1 to 8 carbon atoms Alkyl group or aralkyl group having 6 to 12 carbon atoms.] Specifically, styrene, α-methylstyrene, vinyltoluene, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, polystyrene macromonomer, polymethylmethacrylate A macromonomer etc. are mentioned.

The other monomer copolymerizable can be used individually by 1 type or in combination of 2 or more types. Among these, in particular, a multipart copolymer composed of a benzyl (meth) acrylate / (meth) acrylic acid copolymer and benzyl (meth) acrylate / (meth) acrylic acid / other monomers is preferable.

As described above, the acrylic resin has an acid value in the range of 20 to 200 mgKOH / g. When the acid value is more than 200, the acrylic resin has an excessive solubility in alkali, resulting in a narrow development development range (developing latitude). On the other hand, if it is too small (less than 20), the solubility in alkali is small and the development takes too long, which is not preferable.

In addition, the mass average molecular weight Mw (polystyrene conversion value measured by GPC method) of acrylic resin is 2,000-100,000 in order to realize the viscosity range which is easy to use in the process of apply | coating a color resist, and to ensure film strength. It is preferable, More preferably, it is 3,000-50,000.

Moreover, in order to improve the crosslinking efficiency of the curable composition in this invention, you may use together resin which has a polymeric group in alkali-soluble resin alone or with alkali-soluble resin which does not have a polymeric group, and an aryl group and a (meth) acryl group Polymers containing an aryloxyalkyl group and the like in the side chain are useful. Alkali-soluble resin which has a polymerizable double bond can develop in alkaline developing solution, and is equipped with photocurability and thermosetting. Although the example of the polymer containing these polymerizable groups is shown below, if the molecule contains an unsaturated bond between alkali-soluble groups, such as a COOH group and an OH group, and a carbon carbon, it will not be limited to the following.

(1) urethane-modified by reacting an isocyanate group and an OH group in advance, leaving one unreacted isocyanate group, and also reacting a compound containing at least one (meth) acryloyl group with an acrylic resin containing a carboxyl group. Polymerizable double bond-containing acrylic resin,

(2) an unsaturated group-containing acrylic resin obtained by reaction of an acrylic resin containing a carboxyl group with a compound having an epoxy group and a polymerizable double bond together in a molecule,

(3) acid pendant 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.

Among the above, resin of (1) and (2) is especially preferable.

Specific examples include copolymers of monomers such as, for example, methacrylic acid and an acrylic or vinyl compound copolymerizable with, for example, 2-hydroxyethyl acrylate having a OH group and a COOH group, with respect to the OH group. Compounds obtained by reacting a reactive epoxy ring with a compound having a carbon-to-carbon unsaturated bond group (for example, a compound such as glycidyl acrylate) can be used. In reaction with an OH group, the compound which has an acid anhydride, an isocyanate group, and an acryloyl group can also be used besides an epoxy ring.

Further, a saturated or unsaturated polybasic acid anhydride is reacted with 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. The reactant obtained by making it available can also be used.

As a compound which has an alkali solubilizer and a carbon-to-carbon unsaturated group together, such as a COOH group, For example, Diamond NR series (made by Mitsubishi Rayon Co., Ltd.); Photomer 6173 (COOH group-containing polyurethane acrylic oligomer, manufactured by Diamond Shamrock Co. Ltd.); Bis coat R-264, KS resist 106 (all manufactured by Osaka Organic Chemical Indusry Ltd.); Cychrom P Series, Fraxel CF200 Series (all manufactured by Daicel Chemical Industries, Ltd.); Ebecryl 3800 (manufactured by Daicel UCB Co., Ltd.) and the like.

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.

It is more preferable to add the following epoxy resin in addition to the said alkali-soluble resin at the time of preparation of a resist. As an epoxy resin, it is a compound which has 2 or more epoxy rings in a molecule | numerator, such as bisphenol-A, cresol novolak-type, a biphenyl type, and an alicyclic epoxy compound.

For example, as bisphenol A, Efototo YD-115, YD-118T, YD-127, YD-128, YD-134, YD-8125, YD-7011R, ZX-1059, YDF-8170, YDF-170 (Above, manufactured by Tohto Kasei Co., Ltd.), Denacol EX-1101, EX-1102, EX-1103 (above produced by Nagase Chemicals Ltd.), Fraxel GL-61, GL-62, G101, G102 ( The above-mentioned Daicel Chemical Industries, Ltd. make) etc. are mentioned, In addition, bisphenol F type and bisphenol S type epoxy resin similar to these are mentioned as usable.

In addition, epoxy acrylates such as Ebecryl 3700, 3701, 600 (produced by Daicel UCB Co., Ltd.) can also be used. As the cresol novolak type, Efototo YDPN-638, YDPN-701, YDPN-702, YDPN-703, YDPN-704, etc. (above manufactured by Tohto Kasei Co., Ltd.), Denacol EM-125, etc. (above Nagase Chemicals Ltd.) and 3,5,3 ', 5'-tetramethyl-4,4'-diglycidyl biphenyl, such as biphenyl type, include ceoxide 2021, 2081, 2083, 2085 and epoxide as alicyclic epoxy compounds. Lead GT-301, GT-302, GT-401, GT-403, EHPE-3150 (above produced by Daicel Chemical Industries, Ltd.), Santoto ST-3000, ST-4000, ST-5080, ST-5100, etc. ( Tohto Kasei Co., Ltd.), Epiclon 430, 673, 695, 850S, 4032 (above Dainippon Ink Corporation), etc. are mentioned. 1,1,2,2-tetrakis (p-glycidyloxyphenyl) ethane, tris (p-glycidyloxyphenyl) methane, triglycidyltris (hydroxyethyl) isocyanurate, o Diglycidyl esters of phthalic acid, diglycidyl esters of terephthalic acid, and glycidyl esters in which the dimer acid is modified in the skeleton of an amine epoxy resin, efototo YH-434, YH-434L, or a bisphenol A epoxy resin. Etc. can also be used.

Among these, "molecular weight / number of epoxy rings" is preferably 100 or more, 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 too large, and if too large, the curability is insufficient, the reliability is deteriorated, or the flatness is deteriorated.

Specific preferred compounds include Efototo YD-115, 118T, 127, YDF-170, YDPN-638, YDPN-701, Fraxel GL-61, GL-6,2,3,5,3 ', 5'-tetramethyl -4,4 'diglycidyl biphenyl, ceoxide 2021, 2081, eporide GT-302, GT-403, EHPE-3150, etc. are mentioned.

In addition, when the pigment concentration is increased to create high color purity, the thixotropy of the coating liquid is generally increased, and thus, the film thickness non-uniformity after coating is likely to occur, and in particular, in the slit coat method, the liquid is leveled to dry to give uniform thickness. It is important to form a coating film. For this reason, it is preferable to contain an appropriate surfactant in the said colored photosensitive resin composition.

As said surfactant, surfactant disclosed by Unexamined-Japanese-Patent No. 2003-337424 and Unexamined-Japanese-Patent No. 11-133600 is mentioned as a preferable thing.

As surfactant for improving applicability | paintability, a nonionic surfactant, a fluorine-type surfactant, a silicone type surfactant, etc. are added.

As nonionic surfactant, polyoxyethylene glycol, polyoxypropylene glycol, polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene alkyl ester, polyoxypropylene alkyl ether, for example. And nonionic surfactants such as polyoxypropylene alkylaryl ethers, polyoxypropylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters are preferable.

Specifically, Polyoxyalkylene glycol, such as polyoxyethylene glycol and polyoxypropylene glycol; Polyoxyalkylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxypropylene stearyl ether and polyoxyethylene oleyl ether; Polyoxyethylene aryl ethers such as polyoxyethylene octylphenyl ether, polyoxyethylene polythiylated ether, polyoxyethylene tribenzylphenyl ether, polyoxyethylene-propylene polytyrylated ether and polyoxyethylene nonylphenyl ether; And nonionic surfactants such as polyoxyalkylenedialkyl esters such as polyoxyethylenedilaurate and polyoxyethylene distearate, sorbitan fatty acid esters and polyoxyalkylene sorbitan fatty acid esters.

Specific examples of these include, for example, the Adeka Pluronic series, the Adecanol series, the Tetronic series (above ADEKA Corporation), the Emulgen series, the Leodol series (manufactured by Kao Corporation), the Eleminol series, Noni Pole series, Octapol series, Dodekapol series, Newpole series (more than Sanyo Chemical Industries, Ltd.), pionein series (more than, TAKEMOTO OIL & FAT Co., Ltd.), Nissan nonion series (more than NOF Corporation Production). Those commercially available can be used suitably. Preferable HLB value is 8-20, More preferably, it is 10-17.

As the fluorine-based surfactant, a compound having a fluoroalkyl or a fluoroalkylene group in at least one of terminal, main chain and side chain can be preferably used.

As a specific commercial item, Megapack F142D, copper F172, copper F173, copper F176, copper F177, copper F183, copper 780, copper 781, copper R30, copper R08 (made by Dainippon Ink Corporation), fluoride FC-135, copper FC-170C, copper FC-430, copper FC-431 (manufactured by Sumitomo 3M Co., Ltd.), Supron S-112, copper S-113, copper S-131, copper S-141, copper S-145, East S-382, East SC-101, East SC-102, East SC-103, East SC-104, East SC-105, East SC-106 (manufactured by Asahi Glass Co., Ltd.), F-Top EF351, Copper 352, 801, 802 (manufactured by JEMCO Corporation.), And the like.

As silicone type surfactant, Toray silicon DC3PA, copper DC7PA, copper SH11PA, copper SH21PA, copper SH28PA, copper SH29PA, copper SH30PA, copper SH-190, copper SH-193, copper SZ-6032, copper SF-8428, copper DC-57, Copper DC-190 (above, manufactured by Daw Corning Toray Silicone Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452 (above, GE Toshiba Silicone Co., Ltd.) etc. are mentioned.

These surfactant is used with respect to 100 weight part of resist liquids, Preferably it is 5 weight part or less, More preferably, it is used 2 weight part or less. When the amount of the surfactant exceeds 5 parts by weight, surface roughness in coating drying tends to occur, and smoothness tends to deteriorate.

In addition, when promoting alkali solubility of an uncured part and further aiming at developability of a photocurable composition, addition of organic carboxylic acid, Preferably low molecular weight organic carboxylic acid with a molecular weight of 1000 or less can be performed. Specific examples include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, capric acid, diethyl acetic acid, enanthic acid and caprylic acid; Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, sublinic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methyl succinic acid, tetramethylsuccinic acid Aliphatic dicarboxylic acids such as citraconic acid; Aliphatic tricarboxylic acids such as tricarbaric acid, aconitic acid and camphoronic acid; Aromatic monocarboxylic acids such as benzoic acid, toluic acid, cuminic acid, hemelic acid and mesitylene acid; Aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, melanoic acid and pyromellitic acid; Phenylacetic acid, phenoxyacetic acid, methoxyphenoxyacetic acid, hydroatroic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atroic acid, cinnamic acid, methyl cinnamic acid, cinnamic acid benzyl, cinnamildeacetic acid, coumalic acid And other carboxylic acids such as umbelic acid.

<Alkoxysilane Compound>

It is preferable to use together an alkoxysilane compound and a silane coupling agent together in each curable composition of this invention from a viewpoint of adhesive improvement with a board | 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, phenyl, mercapto, which exhibit affinity by interacting or forming a bond with an organic resin, It is preferable that it is an epoxy silane, and it is more preferable that it is (meth) acryloylpropyl trimethoxysilane especially.

As addition amount at the time of using a silane coupling agent, it is preferable that it is the range of 0.2-5.0 mass% in the total solid of the curable composition of this invention, and 0.5-3.0 mass% is more preferable.

Notary sensitizer

It is also preferable that each curable composition of this invention contains a sensitizer as desired. In the present invention, the sensitizer has an action of further improving the sensitivity of the sensitizing dye and the initiator to the actinic radiation or suppressing the inhibition of polymerization of the polymerizable compound by oxygen.

Examples of such a sensitizer include amines such as MR Sander et al., Journal of Polymer Society, Vol. 10, page 3173 (1972), Japanese Patent Publication No. 44-20189, Japanese Patent Publication No. 51-82102, Japan Japanese Patent Laid-Open No. 52-134692, Japanese Patent Laid-Open No. 59-138205, Japanese Patent Laid-Open No. 60-84305, Japanese Patent Laid-Open No. 62-18537, Japanese Patent Laid-Open No. 64-33104, Research The compound of Disclosure 33825, etc. are mentioned, Specifically, triethanolamine, p-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, p-methylthiodimethylaniline, etc. are mentioned.

As other examples of the sensitizer, thiols and sulfides, for example, thiol compounds disclosed in Japanese Patent Application Laid-Open No. 53-702, Japanese Patent Application Laid-Open No. 55-500806, Japanese Patent Application Laid-Open No. 5-142772, and Japanese Patent The bisulphide compounds of Unexamined-Japanese-Patent No. 56-75643, etc. are mentioned, Specifically, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, 2-mercapto-4 ( 3H) -quinazolin, β-mercaptonaphthalene, and the like.

Other examples of the co-sensitizer include amino acid compounds (e.g., N-phenylglycine), organometallic compounds (e.g., tributyltin acetate, etc.) described in JP-A-48-42965, JP-A-55-34414 Hydrogen donors described in Japanese Patent Application Laid-Open, sulfur compounds described in Japanese Patent Application Laid-Open No. 6-308727 (for example, trithiane and the like), and the like are listed.

As for content of these co-sensitizers, the range of 0.1-30 mass% is preferable with respect to the mass of the total solid of a curable composition from a viewpoint of the improvement of the hardening rate by the balance of a polymerization growth rate and a chain transfer, and is 1-25 mass% The range of is more preferable, and the range of 0.5-20 mass% is further more preferable.

<Polymerization inhibitor>

In the present invention, it is preferable to add a small amount of thermal polymerization inhibitor in order to prevent unnecessary thermal polymerization of the compound having a polymerizable ethylenically unsaturated double bond during the preparation or storage of the curable composition.

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-butyl phenol), N-nitrosophenylhydroxyamine cerium salt, etc. are mentioned.

As for the addition amount of a thermal polymerization inhibitor, about 0.01 mass%-about 5 mass% are preferable with respect to the mass of the whole composition. Moreover, in order to prevent the polymerization inhibition by oxygen, you may add higher fatty acid derivatives, such as behenic acid and behenic acid amide, as needed, and may make it localize on the surface of the photosensitive layer in the drying process after application | 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>

In addition, in this invention, in order to improve the physical property of a cured film, you may add well-known additives, such as an inorganic filler, a plasticizer, and a sensing agent which can improve the ink developability of the photosensitive layer surface.

Examples of the plasticizer include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerin and the like, When it does, 10 mass% or less can be added with respect to the total mass of a compound and an binder which have an ethylenically unsaturated double bond.

The curable composition of the present invention is cured with high sensitivity, and storage stability is also good. Moreover, high adhesiveness to hard material surfaces, such as a board | substrate to which a curable composition is applied, is shown. Therefore, the curable composition of this invention can be used suitably in the field | areas of the image forming material, ink, coating material, adhesive agent, and coating agent which used three-dimensional optical shaping | molding, holography, and a color filter.

[Color filter and its manufacturing method]

Next, the color filter of this invention and its manufacturing method are demonstrated.

The color filter of this invention has a coloring pattern (color pixel) which uses the curable composition for colored pixel formation of this invention, and the light shielding part (black matrix) formed using the curable composition for light shielding part formation on a support body, It is characterized by the above-mentioned. do.

Hereinafter, the color filter of this invention is explained in full detail through the manufacturing method.

The process of apply | coating each said curable composition of this invention on a support body, and forming a curable composition layer (henceforth abbreviated as "curable composition layer formation process suitably"), and the process of exposing the said curable composition layer through a mask. (Hereinafter, abbreviated as "exposure process" suitably.) And the process of developing the said curable composition layer after exposure, and forming a coloring pattern (henceforth abbreviated as "development process" suitably.). Each of these processes is the same as when forming a color pixel or when forming a light shielding part. Generally, first, a light shielding portion is formed, and then colored pixels of each color of RGB are formed.

Hereinafter, 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 onto a support to form a curable composition layer.

Examples of the support that can be used in the present step include alkali-free glass, soda glass, pyrex (registered glass), quartz glass, and the like that have a transparent conductive film attached thereto, or are used in solid-state imaging devices. Photoelectric conversion element substrates, such as a silicon substrate, are mentioned. Plastic substrates are also possible. These substrates first form a light shielding portion on a grid or the like so as to isolate each pixel, and a colored pixel is formed in a portion where the grid is empty.

Moreover, on these support bodies, you may form an undercoat layer as needed for the improvement of close_contact | adherence with the upper layer, the prevention of the diffusion of a substance, or the planarization of a board | substrate surface.

As a coating method of the curable composition of this invention on a support body, various coating methods, such as a slit coating, an inkjet method, a spin coating, casting coating, a roll coating, and a screen printing method, can be applied.

Moreover, as a method of forming a curable composition film | membrane on a support body, the method of transferring the coating film formed by apply | coating by the said method on the support body in advance and forming on a board | substrate other than the said application method can also be applied.

Regarding the transfer method, paragraphs [0023], [0036] to [0051] of JP-A-2006-23696 and paragraphs [0096] to [0108] of JP-A-2006-47592 are prepared. The method can also be preferably used in the present invention.

Although the coating film thickness of a curable composition is prepared timely by the design value of the light shielding part to form and the thickness of a colored pixel, 0.1-10 micrometers is preferable generally, and in this invention, a colored layer is 1.5-2.5 micrometers, light-shielding As for a part, it is more preferable that it is the range of 0.3-1.0 micrometer.

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

Exposure process

In an exposure process, the curable composition layer formed in the said curable composition layer formation process is exposed through the mask which has a predetermined mask pattern.

The exposure in this step is performed by exposing a pattern of the coating film through a predetermined mask pattern, curing only the irradiated coating film portion, developing with a developing solution, and forming pixels of each color (three or four colors). It can be performed by forming a patterned film. As radiation which can be used at the time of exposure, especially ultraviolet rays, such as g line | wire, h line | wire, i line | wire, are used preferably. Dose 5~1500mJ / cm ² are preferred, 10~1000mJ / cm ^2, and more preferably, 10~500mJ / cm ² is most preferred.

When the color filter of this invention is for liquid crystal display elements, 5-200 mJ / cm <^2> is preferable in the said range, 10-150 mJ / cm <^2> is more preferable, 10-100 mJ / cm <^2> is the most preferable. The exposure machine can be a proximity exposure machine, a mirror projection system, or a stepper system.

Moreover, when the color filter of this invention is for a solid-state image sensor, 30-1500mJ / cm <^2> is preferable in the said range, 50-1000mJ / cm <^2> is more preferable, 80-500mJ / cm <^2> is the most preferable. In this case, an i-line stepper exposure machine is preferable.

Development Process

Subsequently, by performing an alkali developing process, the tailings irradiation part is eluted in aqueous alkali solution by the said exposure, and only the part which photocured remains. As a developing solution, an organic alkali developing solution which does not cause damage to a circuit of an underlayer etc. in the case of a solid-state image sensor is preferable. In the case of a color filter for a liquid crystal display device, an inorganic alkali developer is used. As image development temperature, it is 20 degreeC-30 degreeC normally, and developing time is 20 to 90 second.

As an alkali chemicals used for a developing solution, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium silicate, sodium metasilicate, ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, Organic alkaline compounds such as tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene, and these alkalizing agents The alkaline aqueous solution diluted with pure water so that it may be 0.001-10 mass%, Preferably it is 0.01-1 mass% is used suitably as a developing solution. In addition, when the developing solution which consists of such alkaline aqueous solution is used, it is generally wash | cleaned (rinse) with pure water after image development.

Subsequently, the excess developer is washed off and dried, followed by heat treatment (post baking). Thus, a cured film can be manufactured by repeating the said process for every color sequentially.

As a result, a color filter is obtained.

Post-baking is the heat processing after image development to make hardening perfect, and the thermosetting process of 100 degreeC-240 degreeC is normally performed. When a board | substrate is a glass substrate or a silicon substrate, 200 degreeC-240 degreeC is preferable also in the said temperature range.

This post-baking process can be performed continuously or batchwise using heating means, such as a hotplate, a convection oven (hot air circulation type dryer), and a high frequency heater, so that the coating film after image development may be said conditions.

Moreover, the manufacturing method of this invention includes the hardening process of hardening the light shielding part and colored pixel which were formed by heating and / or exposure as needed after performing the above-mentioned curable composition layer formation process, exposure process, and image development process. You may do it.

The curable composition layer forming step, the exposure step, and the developing step (also a curing step if necessary) described above are performed. First, after forming the light shielding portion, these steps are repeated by the desired number of colors to form the colored pixels. Thereby, the color filter provided with the light shielding part and the coloring pixel which consists of a desired color 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, a CRT display device, and the like. For the definition of the display device and the description of each display device, see, for example, "Electronic display device (Akio Sasaki by Kogyo Chosakai Publishing, Inc. 1990)", "Display device (by Ibuki Sugiaki, Sangyo-Tosho Publishing Co. Ltd.). , Ltd., issued in 1989).

Among the display devices of the present invention, liquid crystal display devices are particularly preferable. The liquid crystal display device is described, for example, in "next-generation liquid crystal display technology (Tatsuo Uchida editing, Kogyo Chosakai Publishing, Inc. 1994)." There is no restriction | limiting in particular in the liquid crystal display device which can apply this invention, For example, it can apply to the liquid crystal display device of various systems described in said "next-generation liquid crystal display technology."

Among these, the present invention is particularly effective for a color TFT type liquid crystal display device. The liquid crystal display device of the color TFT system is described, for example, in "Color TFT liquid crystal display (Kyoritsu Shuppan Co., Ltd. issued in 1996)". In addition, the present invention can be applied to liquid crystal display devices having an enlarged viewing angle such as lateral electric field driving methods such as IPS and pixel division methods such as MVA, STN, TN, VA, IPS, OCS, FFS, and R-OCB. . These methods are described, for example, on page 43 of EL, PDP, LCD Display Technology and the Latest Trends in the Market (Published by Toray Research Center Research, 2001). In addition to the color filter, the liquid crystal display is composed of various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, a viewing angle guarantee film, and the like. The substrate having the light shielding film of the present invention can be applied to a liquid crystal display device composed of these known members.

For the absence of these materials, for example, the "94 market of liquid crystal display peripheral materials and chemicals (Token Taro, CMC Publishing Co., Ltd. 1994 issuance)", "the current state and future of the liquid crystal related market in 2003" Prospect (the lower volume) (Omoteryo Yoshi, Fuji Kimer Research Institute, 2003).

Backlights are described in SID meeting Digest 1380 (2005) (A.Konno et.al), pages 18-24 (Shima Yasuhiro), pages 25-30 (Yagi Takaaki), etc. The color filter of the present invention can realize high contrast when it is combined with the three-wavelength tube of a conventionally known cold cathode tube, but the luminance is high and the color purity is high by using a red, green, and blue LED light source (RGB-LED) as a backlight. A good liquid crystal display device having high color reproducibility can be provided.

The black matrix of high optical density formed using the composition like this invention has the effect (shadow effect) which light-shields a backlight, makes the transmitted light of each colored pixel part sharp, and visually recognizes it as a fixed color. When the OD value of the light shielding portion is low, the black image does not become black at the time of black display, and the visual image is blurred.

On the other hand, when the depolarization of the colored pixel portion (hereinafter referred to as the pixel portion) is low, the backlight is not shielded by scattering in the pixel, and stray light is generated, and the light is transmitted through the so-called "light leakage" and "color leakage". A phenomenon occurs. (= Low contrast) At this time, the entire screen is colored even when black display is performed. For example, when the contrast of the red pixel portion is low, it appears reddish, and when the contrast of the blue pixel portion is low, it appears bluish and poor in color reproducibility. For this reason, the improvement of the contrast of a pixel part was anticipated and requested | required.

In the present invention, as described above, the use of the curable composition containing a specific polymer dispersant enables high dispersion of the pigment fine particles used in the colored pixel portion, thereby achieving contrast improvement in the pixel portion. When both the contrast improvement and the high OD value in the light shielding portion are compatible, the expression of a sufficient effect can be achieved even when viewed as an entire display device as the present invention for the first time, thereby realizing a higher contrast as the display device.

That is, by setting the light shielding portion to a high OD value, it is possible to suppress the transmission of the backlight to the light shielding portion and to block the stray light incident on the light shielding portion from the colored pixel portion, and to realize color reproduction by the synergistic effect of the pixel portion and the light shielding portion. This was very good and a fixed display device was obtained.

In addition, as a display device, more natural color reproduction is required. For this reason, although it is expected to improve about 70% of NTSC ratio equivalent to CRT which is an index of color reproducibility, color reproducibility can be improved significantly by using the color filter and RGB-LED of this invention for a backlight.

On the other hand, the performance required for the liquid crystal display device is an improvement in the response speed of the image. In order to improve the response speed, the alignment speed of the liquid crystal has been improved. On the other hand, in terms of the structure of the cell, the thickness reduction of the liquid crystal layer is also necessary in terms of cost down. Another technique required for reducing the thickness of the liquid crystal layer is to reduce the orientation disturbance of the liquid crystal at the boundary portion 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 of the boundary portion, the visibility of the pixel portion and the light shielding portion is also improved. Since the colored layer of this invention has moderate alkali solubility and hydrophobicity, the superposition | polymerization part of each colored pixel tends to become flat. In particular, when the thickness of the light shielding portion is small, this effect is remarkable, and when combined with the light shielding portion of the present invention, flatness due to the linearity of the pattern of the light shielding portion and the overlapping of each colored portion on the BM becomes good. If the flatness is good, there is no need to thin the liquid crystal layer or to provide a flattening layer before laying the transparent electrode ITO, and it can contribute to the rationalization of the process and the cost down and mass production. It is the realization of the thin light shielding layer which is another characteristic of this invention, and when combined with this, the high contrast performance of the coloring part which is a big element of this invention can be exhibited without regret.

(Example)

Hereinafter, although an Example demonstrates this invention further more concretely, it is not limited to a following example. In addition, "%" and "part" are mass references | standards unless there is particular notice.

Example 1

<1. Preparation of Shading Curable Composition>

1-1. Preparation of dispersion (dispersion liquid K-1) of particles having a silver tin alloy portion

To 1,000 ml of pure water, acetic acid was added to 23.1 g of acetic acid (I), 65.1 g of tin (II) acetate, 54 g of gluconic acid, 45 g of sodium pyrophosphate, 2 g of polyethylene glycol (molecular weight: 3,000) and PVP- 5 g of polyvinylpyrrolidone polymer) was dissolved to obtain a solution 1. Separately, 46.1 g of hydroxy acetone was dissolved in 500 ml of pure water, and Solution 2 was obtained.

The solution 2 was added to this over 2 minutes, stirring vigorously, maintaining solution 1 obtained above at 25 degreeC, and stirring was continued for 6 hours gently. The liquid mixture changed to black, and metal particles (hereinafter, referred to as "silver tin alloy portion-containing particles") having silver tin alloy portions were obtained. Next, this mixed solution was centrifuged to precipitate the silver tin alloy portion-containing particles. The centrifugation was subdivided into a liquid amount of 150 ml, and was carried out for 30 minutes at a rotational speed of 2,000 r.p.m. using a tabletop centrifuge H-103n (manufactured by Ipros Corporation). The supernatant liquid was discarded to make the total liquid amount to 150 ml, 1350 ml of pure water was added thereto, and stirred for 15 minutes to disperse the silver-tin alloy portion-containing particles again. The redispersion was centrifuged in the same manner as described above to precipitate the silver tin alloy portion-containing particles. This operation (addition of pure water and centrifugation) was repeated twice to wash the silver tin alloy portion-containing particles.

The silver tin alloy part containing particle | grains obtained above were made into a dispersion liquid, centrifugation was further performed with respect to this dispersion liquid, and the silver tin alloy part containing particle was precipitated again. Centrifugation was performed on the same conditions as the above. After centrifugation, the supernatant was discarded in the same manner as described above to make the total liquid amount to 150 ml, 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 further disperse the silver-tin alloy portion-containing particles.

In the same manner as above, centrifugation was carried out, and the silver-tin alloy part-containing particles were precipitated, and then the supernatant was discarded in the same manner as above to make 150 ml of liquid, and 150 ml of pure water and 1200 ml of normal propyl alcohol were added thereto for 15 minutes. It stirred and disperse | distributed the silver tin alloy part containing particle again. And again, centrifugation was performed. The conditions for centrifugation at this time were the same as above except that the time was extended to 90 minutes. Thereafter, the supernatant was discarded to make the total liquid amount 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: 130 g of diameter 0.65 mm zirconia beads, manufactured by Eiger Japan Co., Ltd.), and the silver tin alloy portion-containing particles (silver tin particle concentration of 25 masses). %, The dispersion liquid (dispersion liquid K-1) of PVP-K30 residual amount 1.0 mass%) was prepared.

Silver-tin alloy part containing particle | grains obtained above were made into Hitachi Ltd. The composite was composed of AgSn alloy (2θ = 39.5 °) and Sn metal (2θ = 30.5 °) as analyzed using HD-2300 manufactured by Eran (Energy Dispersive X-ray Analyzer) manufactured by Noran. It was confirmed by line scattering. Here, the number in parentheses is the scattering angle of each (III) plane. In addition, the number average particle diameter of the silver tin alloy part containing particle | grains in this dispersion liquid K-1 was about 40 nm.

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

1-2. Preparation of dispersion (dispersion liquid K-2) of particles having silver sulfide fine particles

25.2 g of acetic acid was dissolved in 100 ml of diethylaminoethanol (solution 3). 25.8 g of ammonium sulfide was dissolved in 100 ml of ethanol separately (solution 4). Solution 4 was added to this, stirring solution 3 kept at 25 degreeC vigorously. Then, stirring was continued gently for 15 minutes. The mixed solution turned black, producing silver sulfide. After stopping for 8 hours, silver sulfide was precipitated and the supernatant was discarded. Subsequently, 100 ml of methyl ethyl ketone was added thereto, stirred for 15 minutes, and then stopped for 8 hours to precipitate silver sulfide to discard the supernatant. This operation was repeated again. Methyl ethyl ketone was added to the silver sulfide slurry obtained in this way, and the total amount was 50 ml. This silver sulfide dispersion was put into a 100 ml glass bottle with 40 g of 0.3 mm diameter zirconia beads and dispersed in a paint shaker for 6 hours. The glass beads were removed after dispersion to obtain a silver sulfide fine particle dispersion K-2. The amount of liquid obtained was 47 mL and the amount of silver sulfide was 17.2 g. When the microparticles | fine-particles were observed with the transmission electron microscope, the average particle diameter was about 20 nm.

1-3. Preparation of Carbon Black Dispersion (K-3)

Carbon black dispersion liquid K-3 was prepared by the following prescription.

Carbon black (manufactured by Degussa, color black FW2); Part 26.7

Dispersant (manufactured by Kusumoto Chemicals, Ltd., Disparon DA7500 acid number 26 amine number 40). Part 3.3

Benzyl methacrylate / methacrylic acid (= 72/28 molar ratio) copolymer,

  Mw10000, 50 wt% solution of propylene glycol monomethyl ether acetate. Part 10

Propylene glycol monomethyl ether acetate... 60 copies

The composition was stirred for 1 hour using a homogenizer at 3000 rpm. The obtained mixed solution was microdispersed for 8 hours using the bead disperser (brand name: dispermat, the GETZMANN company make) using 0.3 mm zirconia beads, and the dispersion was obtained.

1-4. Preparation of light-shielding curable composition

The curable composition was prepared by the prescription of following Table 1 using the obtained light-shielding dispersion liquid. The numbers in the table represent the mass ratios.

The detail of each compound used in the table is as showing below.

Compound C-1: a compound having a = 1, b = 13, c = 30, d = 12, e = 44 in the 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, (Mw 10000, 50 wt% solution of propylene glycol monomethyl ether acetate)

UV curable resin C-3: trade name Cymer P ACA-250 Daicel Chemical Industries, Ltd. making

[Acrylic copolymer having alicyclic, COOH group, acryloyl group in the side chain, propylene glycol monomethyl ether acetate solution (solid content: 50% by mass)]

Polymerizable compound C-4: dipentaerythritol pentahexahexaacrylate

(Product name DPHA Nippon Kayaku Co., Ltd. production)

Polymerizable Compound C-5: trade name TO-1382 Toagosei Co., Ltd. making

The monomer which has a 5-functional acryloyl group which substituted a part of terminal OH group of dipentaerythritol pentaacrylate with COOH group is a main component.

Initiator C-6: trade name "Ilgacure 379" by Chiba Specialty Chemicals K.K. making

Initiator C-7: trade name "OXE-02" Chiba Specialty Chemicals K.K. making

Surfactant C-8: Product name "Megapack R30" produced by Dainippon Ink Corporation

Solvent: MEK = methylethyl ketone

        PGMEA = propylene glycol monomethyl ether acetate

        EEP = 3-Ethoxyethyl Propionate

<2-1. Formation of Black Matrix (BM) by Application>

The obtained shading curable compositions CK-2 to CK-4 were used on a glass substrate (0.7 mm thickness of Corining Incorporated) using a slit coating apparatus having a slit head having a slit interval of 100 µm and a coating effective width of 500 mm. Evaluation was performed. The space | interval between a slit and a glass substrate, and discharge amount were adjusted so that the film thickness after post-baking might be 0.5 micrometer-1.5 micrometers, and it apply | coated at the application | coating speed | rate 100 mm / sec.

Subsequently, after heating (prebaking) at 100 degreeC for 120 second using a hotplate, 100mJ was made into 100 micrometers by using a HITACHI exposure machine LE5565 (full wavelength) and making a proximity gap 300 micrometers with the mask of 10 micrometers of line widths. It was exposed at / cm ² (roughness: 20 mW / cm ² ).

Then, it developed with 1.0% developer (25 degreeC) of potassium hydroxide type developing solution CDK-1 (made by Fuji Film Electronics Materials Co., Ltd.), and wash | cleaned with pure water. Subsequently, it post-baked for 30 minutes in the 220 degreeC clean oven, and formed the grid | lattice-shaped black-matrix board | substrate whose line width of a light shielding layer is about 13 micrometers so that opening of a colored pixel formation area might be 90 micrometer x 200 micrometers.

<2-2. Formation of Black Matrix (BM) by Transfer>

2-2-1. Fabrication of Photosensitive Transfer Material

The following coating liquid for thermoplastic resin layers was apply | coated and dried using the slit-shaped nozzle on the 75-micrometer-thick polyethylene terephthalate film support body (PET support body), and the thermoplastic resin layer was formed.

[Prescription of Coating Liquid for Thermoplastic Resin Layer]

Methanol; Part 11.1

Propylene glycol monomethyl ether acetate... Part 6.36

Methyl ethyl ketone. Part 52.4

Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (copolymerization ratio [molar ratio] = 55 / 11.7 / 4.5 / 28.8, weight average molecular weight = 90,000, Tg ≒ 70 ° C) … Part 5.83

Styrene / acrylic acid copolymer Part 13.6

(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 .; a compound in which bisphenol A is dehydrated and condensed with 2 equivalents of pentaethylene glycol monomethacrylate) … Part 9.1

Surfactant C-8... 0.54part

Next, the coating liquid for intermediate | middle layers of the following prescription was further apply | coated on this thermoplastic resin layer, it was made to dry, and the intermediate | middle layer was laminated | stacked. Subsequently, light-shielding curable composition CK-1 was apply | coated on the intermediate | middle layer, it dried, and further laminated | stacked the black photosensitive composition layer. A photosensitive composition layer is formed on the PET support as described above so that the thermoplastic resin layer having a dry layer thickness of 14.6 μm, the intermediate layer having a dry layer thickness of 1.6 μm, and the optical density (OD) is 4.5, and is protected on the surface of the photosensitive composition layer. The film (polypropylene film of 12 micrometers in thickness) was crimped | bonded, and the photosensitive transfer material comprised in the laminated structure of the support body / thermoplastic resin layer / middle layer / photosensitive composition layer was produced. Hereinafter, this is used as the photosensitive transfer material for BM.

[Prescription of Intermediate Layer Coating Liquid]

Polyvinyl alcohol (PVA-105, manufactured by Kuraray Co., Ltd.) Part 3.0

Carboxymethyl cellulose (TC-5E, manufactured by Shin-Etsu Chemical Co., Ltd.). 0.15part

Surfactant 2 (Supron S-131, Seimi Chemical Co., Ltd.) 0.01 part

·Distilled water … 524 copies

Methanol; Part 429

2-2-2. Formation of Black Matrix (BM)

The glass substrate (0.7 mm thickness made by Corining Incorporated) was washed with a rotary brush having a nylon wool while blowing the glass cleaner liquid heated to 25 ° C. for 20 seconds by a shower, and after washing with pure water, the silane coupling liquid (N- 0.3 mass% aqueous solution of (beta) (amino ethyl) (gamma) -aminopropyl trimethoxysilane; brand name: KBM603 by Shin-Etsu Chemical Co., Ltd.) was blown with a shower for 20 second, and the pure water shower was wash | cleaned. Then, this board | substrate was heated at 100 degreeC for 2 minutes with the board | substrate preheating apparatus, and it sent to the laminator.

The protective film is peeled off from the photosensitive transfer material for BM obtained above to the glass substrate after a silane coupling process, and it overlaps so that the surface of the photosensitive composition layer exposed after removal may contact the surface of the said glass substrate, and the laminator type LamicII [ Hitachi Plant Technologies, Ltd. Production] was laminated under the conditions of a rubber roller temperature of 130 ° C., a linear pressure of 100 N / cm, and a conveyance speed of 2.2 m / min.

Subsequently, the PET support was peeled off at the interface with the thermoplastic resin layer, and the support was removed. After peeling off the supporting member, the substrate surface and the mask (a quartz exposure mask having an image pattern) were vertically placed using a proximity exposure machine (manufactured by Hitachi High-Tech Engineering Corporation) equipped with an ultra-high pressure mercury lamp. The distance between the photosensitive composition layers was set to 200 micrometers, and pattern exposure was performed by exposure amount 30mJ / cm <^2> .

Next, the triethanolamine-based developer (containing 30% by mass of triethanolamine, trade name: T-PD2, manufactured by FujiFilm Corporation) was diluted with pure water 12 times (mixing 1 part by mass of T-PD2 with 11 parts by mass of pure water). Using one liquid (30 degreeC) for 50 second, it shower-developed by the flat nozzle at the pressure of 0.04 Mpa, and removed the thermoplastic resin layer and the intermediate | middle layer. Subsequently, air was blown onto the substrate to remove the liquid, and then pure water was blown by a shower for 10 seconds to perform pure shower cleaning, and air was blown to reduce the liquid level on the substrate.

Next, containing Na carbonate developer (0.38 mol / L sodium hydrogen carbonate, 0.47 mol / L sodium carbonate, 5 mass% sodium dibutylnaphthalenesulfonate, anionic surfactant, antifoamer, and stabilizer; brand name: T-CD1, FujiFilm Corporation) was shower-developed at a pressure of 0.15 MPa with a cone nozzle for 30 seconds using a solution diluted five times with pure water (29 ° C) to develop and remove the photosensitive composition layer, thereby obtaining a pattern image.

Subsequently, with a cone-shaped nozzle for 20 seconds using a liquid (33 ° C) diluted 10-fold with a pure water (containing a phosphate, silicate, nonionic surfactant, antifoaming agent, and stabilizer; trade name: T-SD1, manufactured by FujiFilm Corporation). Blowing was performed by shower at a pressure of 0.02 MPa, and the residue was removed by rubbing the pattern image with a rotary brush having nylon wool to obtain a black matrix.

Subsequently, a post-exposure was performed on the substrate on which the black matrix was formed at an exposure amount of 500 mJ / cm ² from both sides with ultra-high pressure mercury or the like, followed by heat treatment (baking) at 220 ° C. for 15 minutes to form a light shielding layer having a line width of 14 μm. A black matrix substrate was produced.

The light-shielding property was measured by the optical density (OD value) in visual mode using the transmission density meter X-RITE 310T. The thickness of the substrate after the post-baking ULVAC, Inc. It measured with the produced stylus type film thickness measuring instrument DECTAC-3.

Hereinafter, the glass substrate in which the black matrix was formed by application | coating and / or transfer was called "BM board | substrate," and the obtained BM board | substrate was put together 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 on 3000 rpm conditions. The obtained mixed solution was microdispersed for 4 hours using the bead disperser (brand name: dispermat, the GETZMANN company make) using 0.3 mm zirconia beads, and dispersion liquid R-1 was obtained.

(RED R-1 dispersion)

Pigment Red 254 (average particle diameter 20 nm in SEM observation). Part 11

Pigment Red 177 (average particle diameter 18 nm in SEM observation). Part 4

Dispersion resin A-1. Part 5

[Monomer M-4 / methacrylic acid / terminal methacryloylated polymethyl methacrylate copolymer (10/15/75 mass%, weight average molecular weight 20000, acid value 98 mg / g) The said dispersion resin: Exemplary compound (6) ]

Dispersant (brand name: Disperbyk-161, manufactured by BYK-Chemie K.K.). Part Three

30% solution of propylene glycol monomethyl ether acetate

Alkali-soluble resin: benzyl methacrylate / methacrylic acid copolymer Part 4

Propylene glycol monomethyl ether acetate solution (solid content: 50 mass%) of = 75/25 [mass ratio] copolymer, weight average molecular weight Mw: 5000)

Solvent B: propylene glycol monomethyl ether acetate... Part 73

(RED CR-1 Coating Liquid)

Dispersion of RED R-1. 100 copies

Epoxy resin: (trade name: EHPE3150 produced by Daicel Chemical Industries, Ltd.). Part Two

Polymerizable compound: dipentaerythritol pentahexahexa ... Part 8

Polymerization initiator: 4- (o-bromo-p-N, N-di (ethoxycarbonylmethyl) amino-phenyl) -2,6-di (trichloromethyl) -s-triazine... chapter 1

Polymerization initiator: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1... chapter 1

Polymerization initiator: diethyl thioxanthone... 0.5 part

Polymerization inhibitor: p-methoxyphenol... 0.001 copies

Fluorine-based surfactant (trade name: manufactured by Megafac R30 Dainippon Ink Corporation). 0.01 part

Nonionic surfactant (trade name: manufactured by Tetronic R150 ADEKA)... 0.2 part

Solvent: Propylene glycol n-butyl ether acetate Part 30

Solvent: Propylene glycol monomethyl ether acetate 100 copies

The said composition was mixed and stirred, and the CR-1 coating liquid of curable coloring composition was obtained.

3-2. Preparation of Green Curable Composition

The R-1 composition of Example 1 was changed to the following G-1 dispersion composition to obtain a dispersion.

(GREEN G-1 dispersion)

Pigment Green 36 (average particle diameter 19 nm in SEM observation). Part 11

Pigment Yellow 150 (average particle diameter 22 nm in SEM observation). Part 7

Dispersion resin A-2. Part 5

EXAMPLES Monomer / methacrylic acid / terminal methacryloylated polymethyl methacrylate copolymer (12/17/71 mass%, weight average molecular weight 50000, acid value 110 mg / which can form structural unit (M'-6) g) said dispersion resin: exemplary compound (X)];

Dispersant (brand name: Disperbyk-161, BYK-Chemie K.K. 30% solution). Part Three

Alkali-soluble resin: benzyl methacrylate / methacrylic acid copolymer 4 parts = 85/15 [mass ratio] copolymer, the weight average molecular weight Mw: 5000) propylene glycol monomethyl ether acetate solution (solid content: 50 mass%)

Solvent: Propylene glycol monomethyl ether acetate 70 copies

(GREEN CG-1 coating liquid)

· GREEN G-1 dispersion... 100 copies

Epoxy resin: (trade name EHPE3150, manufactured by Daicel Chemical Industries, Ltd.). Part Two

Polymerizable compound: dipentaerythritol pentahexahexa ... Part 6

Polymerizable compound: tetra (ethoxyacrylate) of pentaerythritol; Part Two

Polymerization initiator: 1,3-bistrihalomethyl-5-benzooxolatritriamine... Part Two

Polymerization initiator: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1... chapter 1

Polymerization initiator: diethyl thioxanthone... 0.5 part

Polymerization inhibitor: p-methoxyphenol... 0.001 copies

Fluorine-based surfactant (trade name: manufactured by Megafac R08 Dainippon Ink Corporation). 0.02part

Nonionic surfactant (trade name: Emulgen A-60, manufactured by Kao Corporation)... 0.5 part

Solvent: Propylene glycol monomethyl ether acetate 120 copies

Solvent: Propylene glycol n-propyl ether acetate Part 30

The said composition was mixed and stirred, and the coating liquid of curable coloring composition CG-1 was obtained.

3-3. Preparation of Green Curable Composition

Said 3-2. In the preparation of the green curable composition, the polymerization initiator used for (GREEN CG-1 coating liquid): 1,3-bistrihalomethyl-5-benzooxolatritriamine is polymerized initiator: 4- (o-bromo- The present invention was prepared in the same manner as in the CG-1 coating solution except that pN, N-di (ethoxycarbonylmethyl) amino-phenyl) -2,6-di (trichloromethyl) -s-triazine was changed. The curable composition for coloring pixel formation (GREEN CG-2 coating liquid) which concerns on this was obtained.

3-4. Preparation of Blue Curable Compositions

The R-1 composition of Example 1 was changed to the following BLUE B-1 dispersion composition to obtain a dispersion.

(BLUE B-1 dispersion)

Pigment Blue 15: 6 (average particle diameter 15 nm in SEM observation). Part 14

Pigment Violet 23 (average particle diameter 23 nm in SEM observation). chapter 1

Dispersion resin A-3. Part 5

[Dispersion resin which belongs to specific dispersion resin (B-1) obtained by the following synthesis example]

Dispersant (trade name: Disperbyk-161, BYK-Chemie K.K. 30% solution). Part Three

Alkali-soluble resin: benzyl methacrylate / methacrylic acid copolymer Part 4

= 80/20 [mass ratio] copolymer, the weight average molecular weight Mw: 5000) propylene glycol monomethyl ether acetate solution (solid content: 50 mass%)

Solvent: Propylene glycol monomethyl ether acetate Part 73

Synthesis Example Synthesis of Dispersant A-3

(1.Synthesis of Chain Transfer Agent A3)

Dipentaerythritol hexakis (3-mercaptopropionate) [DPMP; Sakai Chemical Industry Co., Ltd. Preparation] 4.55 parts of compound (m-6) which has 7.83 parts and the following adsorption site, and has a carbon-carbon double bond was melt | dissolved in 28.90 parts of propylene glycol monomethyl ether, and it heated at 70 degreeC under nitrogen stream. 2,2'-azobis (2,4-dimethylvaleronitrile) [V-65, Wako Pure Chemical Industries, Ltd. Production] 0.04 parts were added and heated for 3 hours. Furthermore, 0.04 part of V-65 was added and it was made to react at 70 degreeC under nitrogen stream for 3 hours. 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 Dispersion Resin)

The mixed solution of 4.99 parts of 30% solution of the chain transfer agent A3 obtained as mentioned above, 19.0 parts of methyl methacrylate, 1.0 part of methacrylic acid, and 4.66 parts of propylene glycol monomethyl ether was heated at 90 degreeC under nitrogen stream. While stirring the mixed solution, 2,2'-azobisisobutyric acid dimethyl [V-601, Wako Pure Chemical Industries, Ltd. Preparation] The mixed solution of 0.139 parts, 5.36 parts of propylene glycol monomethyl ether, and 9.40 parts of propylene glycol monomethyl ether acetate was dripped over 2.5 hours. After completion | finish of dripping, after making it react at 90 degreeC for 2.5 hours, the mixed solution of 0.046 parts of dimethyl 2,2'- azobisisobutyric acid and 4.00 parts of propylene glycol monomethyl ether acetate was thrown in, and it was made to react for 2 hours. 1.52 parts of propylene glycol monomethyl ether and 21.7 parts of propylene glycol monomethyl ether acetate were added to the reaction solution, followed by cooling to room temperature (B-1) solution of specific dispersion resin (A-3: weight average molecular weight 24000 in terms of polystyrene) (specific 30 mass% of dispersion resin, 21 mass% of propylene glycol monomethyl ether, and 49 mass% of propylene glycol monomethyl ether acetate) were obtained.

The acid value of this (B-1) specific dispersion resin A-3 was 48 mg / g. The structure of specific dispersion resin A-3 is shown below.

(BLUE CB-1 coating liquid)

BLUE B-1 dispersion. 100 copies

Alkali-soluble resin: benzyl methacrylate / methacrylic acid copolymer Part 6

= 80/20 [mass ratio] copolymer, the weight average molecular weight Mw: 5000) propylene glycol monomethyl ether acetate solution (solid content: 50 mass%)

Epoxy resin: (brand name Celoxide 2080 Daicel Chemical Industries, Ltd.). Part Two

UV curable resin: (trade name Cymer P ACA-250 produced by Daicel Chemical Industries, Ltd.) Part 4

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 pentahexahexa ... Part 12

Polymerization initiator: 1- (9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl) -1- (o-acetyl oxime) ethanone Part Three

Polymerization inhibitor: p-methoxyphenol... 0.001 copies

Fluorine-based surfactant (trade name: manufactured by Megafac R08 Dainippon Ink Corporation). 0.02part

Nonionic surfactant (trade name: manufactured by Emulgen A-60 Kao Corporation); 1.0 part

Solvent: 3-ethoxypropionate ethyl Part 20

Solvent: Propylene glycol monomethyl ether acetate 150 copies

The said composition was mixed and stirred, and the coating liquid of curable coloring composition CB-1 was obtained.

3-5. Preparation of Blue Curable Compositions

3-4. The polymerization initiator used for (BLUE CB-1 coating liquid) in the preparation of a blue curable composition: 1- (9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl) -1- ( o-acetyloxime) ethanone polymerization initiator: 4- (o-bromo-pN, N-di (ethoxycarbonylmethyl) amino-phenyl) -2,6-di (trichloromethyl) -s-tri Except having changed into azine, it prepared similarly to CB-1 coating liquid and obtained the curable composition for colored pixel formation (BLUE CB-2 coating liquid) which concerns on this invention.

[Comparative Example]

<1. Preparation of Red Curable Composition>

In RED R-1, the part of dispersion resin A-1 was changed to alkali-soluble resin, ie, the dispersion liquid was created with the following RED composition R-2.

(RED R-2 Dispersion)

Pigment Red 254 (average particle diameter 20 nm in SEM observation). Part 11

Pigment Red 177 (average particle diameter 18 nm in SEM observation). Part 4

Dispersant (brand name: Disperbyk-161, BYK-Chemie K.K. 30% solution). Part Three

Alkali-soluble resin: benzyl methacrylate / methacrylic acid copolymer Propylene glycol monomethyl ether acetate solution (solid content: 50 mass%) of 14 parts = 75/25 [mass ratio] copolymer and a weight average molecular weight Mw: 5000)

Propylene glycol monomethyl ether acetate... Part 68

Instead of R-1 in CR-1 composition, the comparative curable composition for coloring pixel formation (RED CR-3) was prepared using R-2.

<2. Preparation of Green Curable Composition>

The part of dispersion resin A-2 was changed to alkali-soluble resin in GREEN G-1, ie, the dispersion liquid was created with the following composition G-2.

(GREEN G-2 dispersion)

Pigment Green 36 (average particle diameter 19 nm in SEM observation). Part 11

Pigment Yellow 150 (average particle diameter 22 nm in SEM observation). Part 7

Dispersant (trade name: Disperbyk-161, BYK-Chemie K.K. 30% solution). Part Three

Alkali-soluble resin: benzyl methacrylate / methacrylic acid copolymer Part 14

Propylene glycol monomethyl ether acetate solution (solid content: 50 mass%) of = 85/15 [mass ratio] copolymer and a weight average molecular weight Mw: 5000)

Propylene glycol monomethyl ether acetate... Part 68

In the CG-1 composition, a curable composition for forming colored pixels for comparison (GREEN CG-3) was prepared using G-2 instead of G-1.

<3. Preparation of Blue Curable Composition>

The part of dispersion resin A-3 was changed to alkali-soluble resin in BLUE B-1, ie, the dispersion liquid was created with the following composition B-2.

(BLUE B-2 dispersion)

Pigment Blue 15: 6 (average particle diameter 15 nm in SEM observation). Part 14

Pigment Violet 23 (average particle diameter 23 nm in SEM observation). chapter 1

Dispersant (trade name: Disperbyk-161, BYK-Chemie K.K. 30% solution). Part Three

Alkali-soluble resin: benzyl methacrylate / methacrylic acid copolymer Part 14

= 80/20 [mass ratio] copolymer, the weight average molecular weight Mw: 5000) propylene glycol monomethyl ether acetate solution (solid content: 50 mass%)

Propylene glycol monomethyl ether acetate... Part 68

A curable composition for forming colored pixels for comparison (BLUE CB-3) was prepared by using B-2 instead of B-1 in the CB-1 composition.

<Evaluation result>

As shown below, the colored layer was formed in monochromatic color, evaluation of the said colored layer (equivalent to the colored pixel) on the board | substrate was performed, and the result was shown to Tables 3 and 4. In addition, the evaluation result of the color filter which formed the multi-colored coloring pixel was put together in Table 5.

<Formation of Colored Layer in Monochromatic>

Slit coating aptitude was evaluated using the slit coating apparatus provided with the slit head of 100 micrometers of slit spaces, and 500 mm of coating effective widths. After apply | coating on 10 glass substrates (width 550mm, length 650mm, thickness 0.7mm) by a conventional method, the said slit head was made to air hold for 5 minutes, and it forcedly dried. Dummy dispense was performed for 3 seconds after waiting, and 10 sheets of slit were applied to the glass substrate as it was intermittently. The space | interval between a slit and a glass substrate was adjusted so that the coating film thickness after postbaking might be set to 2 micrometers, and the curable composition was apply | coated at the application | coating speed | rate 100 mm / sec. After application, after prebaking at 90 ° C. for 60 seconds on a hot plate, the number of irregularities on the line of the application surface was visually counted using a sodium light source, and the following criteria were evaluated.

A: No nonuniformity in line on the coated surface

B: 1-5 nonuniformity in a line was observed

C: 6 or more spots on the line were observed

At the same time, the presence or absence of a foreign material having a size of 10 µm or more was observed with an optical microscope having an XY stage, the number of foreign materials was measured, and the number per substrate was shown.

Contrast was measured by the method mentioned later.

In Table 3, it turns out that the coloring pattern formed using the curable composition for colored pixel formation of this invention is a high contrast, without application | coating nonuniformity and mixing of a foreign material with respect to a comparative example. Moreover, it was confirmed that it was excellent in color purity and brightness | luminance, and is preferable as a pixel of a color filter. In addition, from the results in Table 4, it was confirmed that when RGB-LED is used as the backlight, improvement in color purity and luminance can be further achieved as compared with the case where three wavelength tubes are 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 by the same process as formation of a monochromatic colored layer. The space | interval between a slit and a BM board | substrate and discharge amount were adjusted so that the film thickness after postbaking might be set to 1.5 micrometers-3.0 micrometers, and it apply | coated at the application | coating speed of 100 mm / sec. Subsequently, after heating (prebaking) at 100 degreeC for 120 second using a hotplate, it exposed at 100 mJ / cm <^2> using a HITACHI exposure machine LE 5565 (full wavelength) with a proximity gap of 300 micrometers. (Roughness: 20 mW / cm ² ). Then, it developed in 1.0% developing solution (25 degreeC) of potassium hydroxide type developing solution CDK-1 (made by Fuji Film Electronics Materials Co., Ltd.), and wash | cleaned with pure water. Subsequently, it post-baked for 30 minutes in the 220 degreeC clean oven, and formed the red pixel of the heat processing completion.

Next, the green pixel part was formed, the blue pixel part was similarly formed, and the color filter of Example 1 was obtained.

EXAMPLES 2-6

Example 2 was carried out similarly to Example 1 except having changed the curable composition for light shielding part formation (BM-1) used in Example 1, and the curable composition for pixel formation of each color as shown in Table 5 below. The color filter of Example 6 was obtained. Evaluation shown below was performed about the color filter of obtained Example 1-Example 6. The results are shown in Table 5.

<Observing the shape of the coloring part>

In the color filter preparation process, the pattern of the light shielding layer and the colored layer after image development and post-baking was observed with the scanning electron microscope. In Table 5, the result after post-baking was shown unless there is particular notice. The height of the angle measured the height from the flat part of the coloring part by the SEM photograph.

<Contrast Measurement of Color Filters and Monochromatic Substrates>

As the backlight unit, a diffuser plate was installed in a three-wavelength cold cathode light source (FWL18EX-N manufactured by Toshiba Lighting & Technology Corporation), and the above-mentioned R, G, and B components were used between two polarizing plates (G1220DUN manufactured by Nitto Denko Corporation). The contrast was calculated | required by providing a monochromatic board | substrate, and dividing the Yp value of the chromaticity of the light which passes when a polarizing plate is installed in parallel nicole by the Yc value of the chromaticity of the light which passes when it installs in a cross nicole. The chromaticity meter (BM-5 by Topcon Corporation) was used for the measurement of chromaticity.

<Color Evaluation of Monochromatic Substrates>

Light source is red LED as FR1112H (Stanley Electric Co., Ltd. chip type LED), green LED as DG1112H (Stanley Electric Co., Ltd. chip type LED), blue LED as DB1112H (Stanley Electric Co., Ltd. chip type LED was used to configure a side light type backlight. Using this light source and the said three-wavelength cold cathode tourism source, chromaticity was measured with said MCPD-2000 and color reproducibility was evaluated.

<Production and visibility evaluation of liquid crystal display device>

A transparent electrode of indium tin oxide (ITO) was further formed on the black matrix by sputtering on the R, G, and B pixel arrays of the color filter substrate thus obtained. Subsequently, according to Example 1 of JP-A-2006-64921, a spacer was formed in the part corresponding to the upper part of the partition wall (black matrix) on the ITO membrane formed above. Separately, a glass substrate is prepared as an opposing substrate, and patterned for PVA mode on the transparent electrode and the opposing substrate of the color filter substrate, respectively, and a polyimide alignment film (manufactured by Nissan Chemical Industries, Ltd., Sun Everber) thereon. 70 nm after baking 7492) were installed and baked at 180 ° C for 1 hour. Thereafter, a sealant of an ultraviolet curable resin was applied to the position corresponding to the black matrix outer frame formed around the pixel group of the color filter by a dispenser method, the liquid crystal for PVA mode was dropped, and then bonded to the counter substrate. The bonded substrates were UV irradiated and then heat treated to cure the sealant. A deflection plate (NPF-SEG1224DU, manufactured by Nitto Denko Corporation) was bonded to both surfaces of the liquid crystal cell thus obtained. Subsequently, what provided the diffuser plate in the 3-wavelength cold-cathode light source (FWL18EX-N by Toshiba Lighting & Technology Corporation) was arrange | positioned on the side which becomes the back surface of the liquid crystal cell in which the said polarizing plate was installed, and was called the liquid crystal display device.

In the evaluation of the visibility, light leakage was observed by applying a voltage and observing the BM on the screen with a microscope of 100 times in the state of black display.

Shading part OD value / film thickness (μm) of BM RGB RGB film thickness (㎛) Form of colored pixels Color filter contrast Visibility Example 1 BM-2 5.0 / 0.5 CR-1 CG-1 CB-1 2.0 A Good, taper angle was 60-75 degrees with RGB. The angle was not seen even after development. 8000 A The boundary between the BM and the colored part could not be confirmed. Example 2 BM-1 4.5 / 0.7 CR-1 CG-1 CB-1 2.0 B The taper angle with RGB was 60-75 °. After development, the angle of 0.1 micrometer or less was seen in R, but it was not seen after postbaking. 7900 A The boundary between the BM and the colored part could not be confirmed. Example 3 BM-3 4.5 / 1.0 CR-1 CG-1 CB-1 2.0 B A small angle (height 0.1 μm) was seen in R, but could be used as it is. 7500 B Faint blue was recognized at the boundary of BM and B coloring. Comparative Example 1 BM-4 3.0 / 1.0 CR-3 CG-3 CB-3 2.0 C A small angle (0.3 μm in height) was seen in R. Polished and used. 7000 D Each color RGB was recognized at the boundary of the BM and RGB coloring portions. Example 4 BM-5 4.5 / 1.5 CR-1 CG-1 CB-1 2.0 C A small angle (0.5 μm in height) was seen in R. Polished and used. 7800 A The boundary between the BM and the colored part could not be recognized. Comparative Example 2 BM-2 5.0 / 0.5 CR-3 CG-3 CB-3 2.0 E Undercutting was observed after development in RG, and an angle of 1.0 mu m in height was observed even after postbaking. Although it was an unusable level, it polished and continued evaluation. 4800 D Each color RGB was recognized at the boundary of the BM and RGB coloring units. Example 5 BM-2 5.0 / 0.5 CR-1 CG-1 CB-1 2.8 C Undercuts were seen after development in RG and an angle of about 0.5 μm was observed after postbaking. Polished and used. 7600 A The boundary between the BM and the colored part could not be recognized. Example 6 BM-3 4.5 / 1.0 CR-1 CG-2 CB-2 2.0 A A small angle (height 0.1 μm) was seen in R, but could be used as it is. 7700 A The boundary between the BM and the colored part could not be recognized.

As apparent from Table 5, the color filter of the Example which formed the light shielding part and the colored pixel using the curable composition for light shielding part formation, and the curable composition for colored pixel formation of this invention is suitable for pixel shape, and is excellent in contrast, It was confirmed that an image excellent in visibility could be formed.

In addition, according to the contrast between Example 3 and Example 6, by using a triazine-based compound as the polymerization initiator, the liquid crystal display device having the same light shielding portion, the contrast and visibility of the color filter is more improved, and the contrast is high and the visibility is good. It is confirmed that it is obtained.

Claims (13)

It is formed of the curable composition for forming colored pixels, and the color purity in the C light source in the CIE color system is formed by the colored pixel and the curable composition for forming the light shielding portion having 65% or more of the area 100 of the three primary color chromaticity points of the NTSC system. And an optical density (OD value) of 4.5 or more, a light shielding portion having a width of 5 to 15 µm, and a color filter contrast ratio of 5000 or more. The method of claim 1, The film thickness of the said colored pixel part is 1.5-2.5 micrometers, The color filter characterized by the above-mentioned. The method of claim 1, The optical density of the said light shielding part is 4.8 or more, and the film thickness is 0.3-1.0 micrometer, The color filter characterized by the above-mentioned. The method of claim 1, The said curable composition for colored pixel formation contains the polymerization initiator represented by the following general formula (D-A), The color filter characterized by the above-mentioned.

[In Formula (DA), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, an aryl group, or a substituent represented by the following General Formula (DA-1) or General Formula (DA-2). R ³ and R ⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. X and Y each independently represent -Cl or -Br, and m, n represents 0, 1 or 2.

In the general formulas (DA-1) and (DA-2), R ⁵ , R ⁶ , and R ⁷ each independently represent an alkyl group or an aryl group.] As a polymer containing a coloring agent, the compound represented by following General formula (1), the copolymer unit derived from the monomer represented by following General formula (I), and the structural unit represented by following General formula (a) It is selected from the group which consists of an acid value of 20-300 mg / g, and a weight average molecular weight contains 1 or more types of polymeric dispersing agents, a polymeric compound, a polymerization initiator, and a solvent, and it is C in a CIE color system. A curable composition for forming a color filter colored pixel, wherein the color purity of the light source can form a color pixel of 65% or more with respect to the area 100 of the three primary color chromaticity points of the NTSC system.

[In Formula (1), A ¹ represents an organic pigment 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, a hydrocarbon group having 4 or more carbon atoms, The monovalent organic group containing 1 or more types of sites chosen from an alkoxy silyl group, an epoxy group, an isocyanate group, and a hydroxyl group is shown. n pieces A ¹ may be the same or different. R <^1> represents the (m + n) valent organic coupling group, where m represents 1-8, n represents 2-9, and 3 <(m + n) <10. In addition, R ² represents a single bond or a divalent organic linking group. P ¹ represents a polymer skeleton.

R ⁰¹ in General Formula (I) represents a hydrogen atom or a substituted or unsubstituted alkyl group. R ⁰² represents an alkylene group. W represents -CO-, -C (= 0) O-, -CONH-, -OC (= 0)-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 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 0 or 1 each independently.

In 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 method of claim 5, The said polymerization initiator contains the compound represented by the following general formula (D-A), The curable composition for color filter colored pixel formation characterized by the above-mentioned.

[In Formula (DA), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, an aryl group, or a substituent represented by the following General Formula (DA-1) or General Formula (DA-2). R ³ and R ⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group. X and Y each independently represent -Cl or -Br, and m, n represents 0, 1 or 2.

In the general formulas (DA-1) and (DA-2), R ⁵ , R ⁶ , and R ⁷ each independently represent an alkyl group or an aryl group.] 40-80 mass% of carbon black is converted into solid content as a polymeric compound, a polymerization initiator, and a light-shielding agent, The light-shielding part formation for color filters characterized by being able to form the light-shielding part whose optical density (OD value) is 4.5 or more. Curable composition. 50-90 mass% of metal fine particles are converted into solid content as a polymeric compound, a polymerization initiator, and a light shielding agent, and the light-shielding part for optical filter (OD value) of 4.5 or more can be formed. Curable composition. The method according to any one of claims 1 to 4, It is formed with the curable composition for colored pixel formation of Claim 5, or 6, and the curable composition for light shielding part formation of Claim 7 or 8. It is characterized by the above-mentioned. A liquid crystal display device comprising the color filter according to any one of claims 1 to 4. The liquid crystal display device provided with the color filter of Claim 9. The method of claim 10, A liquid crystal display device comprising an RGB-LED light source as a backlight. The method of claim 11, A liquid crystal display device comprising an RGB-LED light source as a backlight.