KR101304267B1 - Colored radiation-sensitive composition, method of manufacturing color filter, color filter, and solid-state imaging sensor - Google Patents

Abstract

(Problem) Provides the colored radiation-sensitive composition which shows the outstanding film thickness uniformity, is excellent in heat resistance, and can form the coloring pattern which reduced the color shift and color nonuniformity.
(Solution) A binder containing (A) CI Pigment Orange 71, (B) a compound represented by the following General Formula (1) as a copolymerization component, (C) a polymerizable compound, and (D) a photopolymerization initiator. Colored radiation-sensitive composition.

Description

Colored radiation-sensitive composition, manufacturing method of color filter, color filter, and solid-state image sensor {COLORED RADIATION-SENSITIVE COMPOSITION, METHOD OF MANUFACTURING COLOR FILTER, COLOR FILTER, AND SOLID-STATE IMAGING SENSOR}

The present invention relates to a colored radiation-sensitive composition, a method for producing a color filter using the colored radiation-sensitive composition, a color filter, and a solid-state imaging device.

Color filters are indispensable components for liquid crystal displays or solid-state imaging sensors.

Such a color filter is composed of a coloring pattern of a plurality of colors, and at least red, green, and blue coloring regions (hereinafter, also referred to as "coloring patterns" or "coloring pixels") are formed. As this formation method, after first apply | coating the curable composition containing the coloring agent of any one of red, green, and blue in a 1st color, performing exposure, image development, and heat processing as needed, and forming the coloring pattern of the said color. In the second and third colors, the same coating, exposure, development, and heat treatment processes as necessary are repeated.

In recent years, it is required to form a fine colored pattern (for example, a colored pattern of which one side is 2.0 µm or less in a solid-state imaging device) with good reproducibility for the purpose of improving the resolution in either the liquid crystal display or the solid-state imaging device. The film thickness of a pattern is also required to be thin (for example, 1 micrometer or less in film thickness in a solid-state image sensor).

In view of such a problem, various studies have been made in the past (for example, Japanese Patent Laid-Open No. 2009-151274, Japanese Patent Laid-Open No. 2009-216952, Japanese Patent Laid-Open No. 2010-85457, and Japanese Patent Laid-Open 2006) -161035, Japanese Patent Laid-Open No. 2008-268943, and the like. However, there is a strong demand for the development of a colored radiation-sensitive composition which can exhibit more favorable film thickness uniformity and can form a colored pattern excellent in heat resistance.

This invention is made | formed in view of the said point, and makes it a subject to achieve the following objectives.

That is, it is an object of the present invention to provide a colored radiation-sensitive composition which can exhibit excellent film thickness uniformity, is excellent in heat resistance, and can form a colored pattern with reduced color shift and color unevenness. Moreover, even if it is thin, it is providing the color filter which is excellent in heat resistance, has a color pattern with little color shift and color nonuniformity, the manufacturing method of the said color filter, and the solid-state image sensor provided with the said color filter.

MEANS TO SOLVE THE PROBLEM The present inventors earnestly researched in view of the said situation, As a result, the binder which contains the compound represented by (A) coloring agent, (B) General formula (1) as a copolymerization component, (C) polymeric compound, and (D) It contains a photoinitiator, and (A) CI as a coloring agent It was found that the said subject was solved by the coloring radiation sensitive composition containing pigment orange 71, and completed this invention.

Means for solving the above problems are as follows.

<1> (A) C.I. Pigment orange 71, (B) Colored radiation-sensitive composition containing the binder represented by following General formula (1) as a copolymerization component, (C) polymeric compound, and (D) photoinitiator.

In General Formula (1), R ¹ and R ² each independently represent a hydrogen atom or an alkyl group.

<2> The colored radiation-sensitive composition according to <1>, wherein the (B) binder is a binder further containing aryl (meth) acrylate or alkyl (meth) acrylate as the polymerizable component.

<3> The colored radiation-sensitive composition according to <1>, wherein the (B) binder is a binder further containing (meth) acrylic acid as a polymerizable component.

<4> The colored radiation-sensitive composition according to <2>, wherein the (B) binder is a binder further containing (meth) acrylic acid as a polymerizable component.

<5> The colored radiation-sensitive composition in any one of <1>-<4> which further contains a red pigment.

<6> The colored radiation-sensitive composition in any one of <1>-<5> which further contains a yellow pigment.

<7> The colored radiation-sensitive composition in any one of <1>-<6> whose said (D) photoinitiator is an oxime compound.

<8> Colored cured film obtained by hardening | curing the colored radiation-sensitive composition in any one of <1>-<7>.

<9> Color filter provided with the colored cured film as described in <8>.

<10> The colored radiation-sensitive composition layer forming process which gives the colored radiation-sensitive composition in any one of <1>-<7> on a board | substrate, and forms a colored radiation-sensitive composition layer, and the said colored radiation-sensitive property The pattern formation method containing the exposure process which exposes a composition layer in a pattern form, and the coloring pattern formation process which develops the said colored radiation-sensitive composition layer after exposure, and forms a coloring pattern.

<11> The colored radiation-sensitive composition layer forming process of providing the colored radiation-sensitive composition in any one of <1>-<7> on a board | substrate, and forming a colored radiation-sensitive composition layer, and the said colored radiation-sensitive property The manufacturing method of the color filter which has an exposure process which exposes a composition layer in a pattern form, and the coloring pattern formation process which develops the said colored radiation-sensitive composition layer after exposure, and forms a coloring pattern.

<12> Solid-state image sensor provided with the color filter as described in <9>.

As a more preferred form, C.I. The colored radiation-sensitive composition which further contains Pigment Yellow 139 is mentioned. In addition, as another preferred form, C.I. The colored radiation-sensitive composition which further contains Pigment Red 254 is mentioned.

(Effects of the Invention)

ADVANTAGE OF THE INVENTION According to this invention, the coloring radiation sensitive composition which shows the outstanding film thickness uniformity, is excellent in heat resistance, and can form the coloring pattern which reduced the color shift and color nonuniformity can be provided. Moreover, according to this invention, even if it is thin, it provides the color filter which is excellent in heat resistance, and has a color pattern with little color shift and color unevenness, the manufacturing method of the said color filter, and the solid-state image sensor provided with the said color filter. can do.

Hereinafter, the colored radiation-sensitive composition, the color filter, the manufacturing method of a color filter, a solid-state image sensor, and a liquid crystal display device of this invention are demonstrated in detail. Although description of the element | module described below may be made | formed based on typical embodiment of this invention, this invention is not limited to such embodiment.

In addition, the numerical range represented using "-" in this specification means the range which includes the numerical value described before and after "-" as a lower limit and an upper limit.

In this specification, an "alkyl group" represents the alkyl group of "linear, branched, and cyclic", and may be substituted by the substituent, or may be unsubstituted.

In addition, in this specification, "(meth) acrylate" shows both an acrylate and a methacrylate, or either, and "(meth) acryl" shows both an acryl and methacryl, or either, "(Meth) acryloyl" shows both or acryloyl and methacryloyl.

In addition, in this specification, a "monomer" and a "monomer" are synonymous. Monomers in the present specification are distinguished from oligomers and polymers and refer to compounds having a weight average molecular weight of 2,000 or less. In the present specification, the polymerizable compound refers to a compound having a polymerizable functional group, and may be a monomer or a polymer. The polymerizable functional group refers to a group involved in the polymerization reaction.

In the present specification, the term "process" is included in the term as long as the desired action of the process is achieved, even if the process is not clearly distinguishable from other processes.

In the present invention, the term &quot; radiation &quot; means that it includes visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray and the like.

The present invention relates to (A) C.I. Pigment Orange 71, (B) It relates to the colored radiation-sensitive composition containing the binder represented by following General formula (1) as a copolymerization component, (C) polymeric compound, and (D) photoinitiator. .

The colored radiation-sensitive composition of the present invention is (A) C.I. Pigment Orange 71, (B) Adsorption amount of the binder to a pigment is increased by containing the binder represented by following General formula (1) as a copolymerization component, (C) polymeric compound, and (D) photoinitiator. Since it can prevent aggregation between pigment particles and dispersion instability by heat, it is considered that it shows the outstanding film thickness uniformity and is excellent in heat resistance. Therefore, the colored radiation-sensitive composition of the present invention makes it possible to provide a color filter having good film thickness uniformity and heat resistance.

≪Colored radiation-sensitive composition≫

The colored radiation-sensitive composition of the present invention is (A) C.I. Pigment Orange 71, (B) A binder comprising the compound represented by the following general formula (1) as a copolymerization component, (C) a polymerizable compound, and (D) a photoinitiator, and further other components as needed You may include it.

<(A) C.I. Pigment Orange 71>

The colored radiation-sensitive composition of the present invention is C.I. Pigment orange 71 (also referred to as "C.I. Pigment Orange 71", "CIPO71" and "PO71". The same applies to other pigments).

In the colored radiation-sensitive composition of the present invention, C.I. Pigment Orange 71 and C.I. You may use together other pigments other than pigment orange 71.

In particular, the colored radiation-sensitive composition of the present invention is the above C.I. Pigment Orange 71 and a red pigment (preferably C. I. Pigment Red 254, C. I. Pigment Red 177 or C. I. Pigment Red 224) are preferably included as other pigments.

In the present invention, the red pigment is C.I. in a color index (C.I .; issued by The Society of Dyers and Colorists. The pigment represented by pigment red is mentioned.

Moreover, from the viewpoint of obtaining the effect by this invention more effectively, the colored radiation-sensitive composition of this invention is the said C.I. It is preferable to further include Pigment Orange 71 and a yellow pigment (preferably Pigment Yellow 138, Pigment Yellow 139, Pigment Yellow 150, or Pigment Yellow 185) as other pigments.

In the present invention, as a yellow pigment, C.I. And pigments represented by pigment yellow.

Especially preferably, the colored radiation-sensitive composition of the present invention is the C.I. It is a form which further contains Pigment Orange 71 and a red pigment and a yellow pigment as other pigment.

C.I. in the present invention. The said other pigment which can be used together with pigment orange 71 can use suitably the various conventionally well-known inorganic pigments or organic pigments. Considering that the color filter in which the pigment dispersion composition of the present invention is preferably used is preferably a high transmittance, an organic pigment is preferable, and the particle size of the pigment is preferably used as small as possible.

Examples of the inorganic pigment include metal compounds represented by metal oxides or metal complex salts, and specifically, metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony and silver. Oxide, and the complex oxide of the said metal is mentioned. In addition, nitrides of titanium, silver tin compounds, silver compounds and the like can also be used.

As said organic pigment, for example,

CIPigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4 , 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3 , 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185 , 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279,

CIPigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12,13,14,15,16,17,18,20,24,31,32,34,35,35,13,36 , 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97 , 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139 , 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179 , 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214

C.I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 73

C.I. Pigment Green 7, 10, 36, 37, 58

The CI substituents of CIPigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, Thing, 80

C. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42

C. I. Pigment Brown 25, 28

C.I. Pigment Black 1 etc. are mentioned.

Among these, the following can be mentioned as a pigment which can be used preferably. However, in this invention, it is not limited to these.

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

C.I. Pigment Orange 36,

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

C.I. Pigment Violet 19, 23, 32,

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

C.I.Pigment Green 7, 36, 37, 58

C.I.Pigment Black 1

These organic pigments may be used alone or in combination in order to increase the color purity.

Moreover, 25 mass%-95 mass% of the ratio (total amount of said C.I. pigment orange 71 and the other orange pigment used by desire) which an orange pigment occupies among all the pigment used is preferable. When it is 95 mass% or more, it is difficult to suppress the light transmittance of 400 nm to 500 nm, and color purity may not be raised. Moreover, the coloring power may fall at 25 mass% or less. Especially as said mass ratio, the range of 30 mass%-90 mass% is optimal. In addition, in the case of the combination of orange pigments, it can adjust to chromaticity.

The dye which can be used as the colorant contained in the colored radiation-sensitive composition is not particularly limited, and conventionally known dyes can be used for the color filter. For example, pyrazole azo type, anilinoazo type, triphenylmethane type, anthraquinone type, anthrapyridone type, benzylidene type, oxonol type, pyrazolotriazole azo type, pyridone azo type, cyanine type, phenothiazine type, pi Dyestuffs, such as a rolopyrazole azomethine type, a xanthene type, a phthalocyanine type, a benzopyran type, an indigo type, a pyrromethene type, can be used. Further, a multimer of these dyes may be used.

In addition, when performing water development or alkali development, an acid dye and / or its derivative may be preferably used from a viewpoint of completely removing the binder and / or dye of the tailings irradiation part by image development.

In addition, direct dyes, basic dyes, mordant dyes, acid mordant dyes, azoic dyes, disperse dyes, useful dyes, food dyes, and / or derivatives thereof may also be usefully used.

Specific examples of the acidic dyes are given below, but the present invention is not limited thereto. For example, acid alizarin violet N; acid black 1, 2, 24, 48; acid blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40-45, 62, 70, 74, 80, 83, 86, 87, 90, 92, 103, 112, 113, 120, 129, 138, 147, 158, 171, 182, 192, 243, 324: 1; acid chrome violet K; acid Fuchsin; acid green 1, 3, 5, 9, 16, 25, 27, 50; acid orange 6, 7, 8, 10, 12, 50, 51, 52, 56, 63, 74, 95; acid red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 183, 198, 211, 215, 216, 217, 249, 252, 257, 260, 266, 274; acid violet 6B, 7, 9, 17, 19; acid yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 42, 54, 72, 73, 76, 79, 98, 99, 111, 112, 114, 243; Food Yellow 3; And derivatives of these dyes.

Moreover, the azo-type, xanthene type, and phthalocyanine-type acid dye of that excepting the above is also preferable, C.I. Solvent Blue 44, 38; C.I. Solvent orange 45; Acid dyes such as Rhodamine B, Rhodamine 110 and derivatives of these dyes are also preferably used.

Especially, as a coloring agent, triallyl methane type, anthraquinone type, azomethine type, benzylidene type, oxonol type, cyanine type, phenothiazine type, pyrrolopyrazole azomethine type, xanthene type, phthalocyanine type, benzopyran type, It is preferable that it is a coloring agent chosen from an indigo system, a pyrazole azo system, an anilino azo system, a pyrazolotriazole azo system, a pyridone azo system, an anth pyridone system, and a pyrromethene system. Moreover, the said coloring agent may be a multimer.

Moreover, you may use combining a pigment and dye.

C.I. in colored radiation-sensitive compositions. It is preferable that the coloring agent which can be mixed with pigment orange 71 is a pigment or dye. In particular, pigments whose average particle diameter r satisfies 20 nm ≤ r ≤ 300 nm, preferably 125 nm ≤ r ≤ 250 nm, particularly preferably 30 nm ≤ r ≤ 200 nm are preferred. By using the pigment of such an average particle diameter, the pixel of high contrast ratio and high light transmittance can be obtained. The "average particle diameter" here means the average particle diameter about the secondary particle which the primary particle (single microcrystal) of a pigment aggregated. The average primary particle diameter can be obtained by observing with SEM or TEM, measuring 100 particle sizes in the part where the particles are not aggregated, and calculating the average value.

In addition, the particle size distribution (henceforth only called "particle size distribution") of the secondary particle of the pigment which can be used in this invention is 70 mass% of the whole secondary particle which enters (average particle diameter +/- 100) nm. As mentioned above, Preferably it is 80 mass% or more. In addition, in this invention, particle diameter distribution was measured using scattering intensity distribution.

Pigments having the above average particle diameters and particle size distribution are firstly mixed with commercially available pigments (other than the average particle diameters usually exceeding 300 nm) and optionally with a dispersant and a solvent, and the pigment mixture is mixed. It can prepare and mix this, for example, grind | pulverizing, using grinders, such as a bead mill and a roll mill, for example. The pigment thus obtained usually takes the form of a pigment dispersion.

- Minification of pigments -

In the present invention, an organic pigment fine and grained as needed can be used. The miniaturization of the pigment is achieved by preparing a high viscosity liquid composition containing the pigment, the water-soluble organic solvent and the water-soluble inorganic salt, and subjecting it to stress and grinding using a wet grinding device or the like.

As a water-soluble organic solvent used for the pigment refining process, methanol, ethanol, isopropanol, n-propanol, isobutanol, n-butanol, ethylene glycol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, di Ethylene glycol monobutyl ether, propylene glycol, propylene glycol monomethyl ether acetate and the like.

In addition, other solvents having low water solubility or low water solubility, such as benzene, toluene, xylene, ethylbenzene, chlorobenzene, nitrobenzene, and aniline, are adsorbed if they are adsorbed to the pigment and are not lost in the waste water. , Pyridine, quinoline, tetrahydrofuran, dioxane, ethyl acetate, isopropyl acetate, butyl acetate, hexane, heptane, octane, nonane, decane, undecane, dodecane, cyclohexane, methylcyclohexane, halogenated hydrocarbons, acetone, Methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, dimethyl formamide, dimethyl sulfoxide, N-methylpyrrolidone, etc. may be used.

Only 1 type may be sufficient as the solvent used for the pigment refinement process, and you may mix and use two or more types as needed.

Examples of the water-soluble inorganic salt used in the pigment miniaturization step in the present invention include sodium chloride, potassium chloride, calcium chloride, barium chloride, sodium sulfate and the like.

The use amount of the water-soluble inorganic salt in the refinement | miniaturization process is 1-50 mass times of a pigment, and many have a grinding effect, but a more preferable quantity is 1-10 mass times from the point of productivity. Moreover, it is preferable to use the inorganic salt whose moisture is 1% or less.

The usage-amount of the water-soluble organic solvent in a refinement | miniaturization process is 50 mass parts-300 mass parts with respect to 100 mass parts of pigments, Preferably it is the range of 100 mass parts-200 mass parts.

There is no particular limitation on the operating conditions of the wet grinding device in the process of miniaturizing the pigment, but the operating conditions when the device is a kneader in order to effectively advance the grinding by the grinding media are the rotation of the blades in the device. The number is preferably 10 rpm to 200 rpm, and the larger the rotation ratio of the two axes is, the larger the grinding effect is. The operation time is preferably 1 hour to 8 hours in combination with the dry grinding time, and the internal temperature of the apparatus is preferably 50 ° C to 150 ° C. In addition, the water-soluble inorganic salt which is the grinding media has a sharp particle size distribution of 5 µm to 50 µm, and a spherical shape is preferable.

In addition, the colored radiation-sensitive composition of the present invention may be used not only for forming the colored region (pixel) of the color filter but also for forming the black matrix. As the black pigment used in the composition for forming the black matrix, a pigment made of a metal mixture containing a metal oxide such as titanium oxide in addition to carbon, titanium black, iron oxide, titanium oxide, silver tin, silver and the like can be mentioned. have.

The titanium black may be used in a composition for forming a black matrix as a titanium black dispersion.

The titanium black dispersion is described in detail below.

A titanium black dispersion is a dispersion containing titanium black as a colorant.

Dispersion and dispersion stability of titanium black are improved by including titanium black as a previously prepared titanium black dispersion in a colored radiation-sensitive composition.

Hereinafter, titanium black is demonstrated.

Titanium black

Titanium black is a black particle having a titanium atom. Preferably, it is low titanium oxide, titanium oxynitride, etc. Titanium black particles can modify the surface as necessary for the purpose of improving dispersibility, suppressing cohesion and the like. It is possible to coat with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, zirconium oxide, and also treatment with a water repellent material shown in Japanese Patent Laid-Open No. 2007-302836.

The particle diameter of the titanium black particles is not particularly limited, but is preferably 3 nm to 2000 nm, more preferably 10 nm to 500 nm, and more preferably 20 nm to 200 nm from the viewpoint of dispersibility and colorability.

Although the specific surface area of titanium black is not specifically limited, Since the water repellency after surface treatment of such titanium black with a water repellent becomes a predetermined performance, the value measured by the BET method is usually about 5 m 2 / g to 150 m 2 / g, especially 20 It is preferable that it is about m <2> / g-about 100 m <2> / g.

Examples of commercially available products of titanium black include, for example, titanium black 10S, 12S, 13R, 13M, 13M-C, 13R, 13R-N and Ako Kasei Co., Ltd., manufactured by Mitsubishi Materials Corporation. , TILACK D, etc., but the present invention is not limited to these.

It is preferable that content (the total amount of CI pigment orange 71 and other pigments used by desire) contained in a colored radiation-sensitive composition is 20 mass%-95 mass% in the total solid of colored radiation-sensitive composition, , 25 mass%-90 mass% are more preferable, and 30 mass%-80 mass% are more preferable.

In this invention, a total solid means the sum total of the component except the solvent in a colored radiation-sensitive composition.

By making content of a coloring agent into the said range, a suitable chromaticity is obtained when a color filter is produced with a colored radiation-sensitive composition. Moreover, since photocuring fully advances and the intensity | strength as a film | membrane can be maintained, the development latitude at the time of alkali image development can be prevented from narrowing.

C.I. contained in the colored radiation-sensitive composition. As content of pigment orange 71, it is preferable that it is 20 mass%-70 mass% in the total solid of colored radiation-sensitive composition, 25 mass%-65 mass% are more preferable, 30 mass%-60 mass% are further more preferable. Do.

Also, C.I. When mixing other pigments other than pigment orange 71, it is preferable that content of another pigment is 75 mass% or less in the gross mass of a pigment, It is more preferable that it is 60 mass% or less, It is further more preferable that it is 50 mass% or less.

In this invention, a pigment is previously disperse | distributed as needed, a pigment dispersant, an organic solvent, a pigment derivative, another component, etc. to prepare a pigment dispersion, and the obtained pigment dispersion is a compound represented by (B) General formula (1) a copolymerization component. It is preferable to mix with the binder contained as a (C) polymeric compound, the (D) photoinitiator, and the other components added as needed, and to prepare a colored radiation-sensitive composition.

The composition of a pigment dispersion liquid and the method of preparation of a pigment dispersion liquid are demonstrated in detail below.

The method of preparing the pigment dispersion is not particularly limited, but the method of dispersing is, for example, a mixture of the pigment and the pigment dispersant in advance and previously dispersed by a homogenizer or the like using zirconia beads. It can carry out by making it disperse | distribute using the beads disperser (for example, DISPERMAT made from GETZMANN).

(Pigment dispersant)

As the pigment dispersant which can be used in the present invention, a polymer dispersant [for example, polyamideamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylic Latex, (meth) acrylic copolymer, naphthalenesulfonic acid formalin condensate], and surfactants such as polyoxyethylene alkyl phosphate ester, polyoxyethylene alkylamine, alkanolamine, and pigment derivatives.

Polymeric dispersants can be further divided into linear polymers, end-modified polymers, graft-type polymers, and block-type polymers from the structure.

As a terminal modified type polymer which has an anchor moiety to a pigment surface, For example, the polymer which has a phosphoric acid group at the terminal as described in Unexamined-Japanese-Patent No. 3-112992, Unexamined-Japanese-Patent No. 2003-533455, Japanese patent The polymer which has a sulfonic acid group at the terminal described in Unexamined-Japanese-Patent No. 2002-273191, etc., the polymer which has the partial skeleton and heterocycle of the organic pigment as described in Unexamined-Japanese-Patent No. 9-77994, etc. are mentioned. Moreover, the polymer which introduce | transduced the anchor site (acidic group, basic group, partial skeleton of organic pigment, heterocyclic ring, etc.) to two or more pigment surfaces in the polymer terminal of Unexamined-Japanese-Patent No. 2007-277514 also has excellent dispersion stability, desirable.

As the graft polymer having an anchor portion on the pigment surface, for example, poly (lower alkylene) disclosed in Japanese Patent Application Laid-Open No. 54-37082, Japanese Patent Application Laid-Open No. 8-507960, Japanese Patent Application Laid-Open No. 2009-258668, and the like. Imine) and polyester, the reaction product of polyallylamine and polyester described in Japanese Patent Application Laid-open No. Hei 9-169821, etc., and the macromolecule described in Japanese Patent Application Laid-open No. Hei 10-339949, Japanese Patent Laid-Open No. 2004-37986 A copolymer of a macromonomer and a nitrogen atom monomer, having partial skeletons and heterocycles of organic pigments described in Japanese Patent Application Laid-Open No. 2003-238837, Japanese Patent Application Laid-Open No. 2008-9426, and Japanese Patent Publication No. 2008-81732; The copolymer of a macromonomer and an acidic radical containing monomer etc. which were described in a graft type polymer, Unexamined-Japanese-Patent No. 2010-106268, etc. are mentioned. In particular, the amphoteric dispersing resin having a basic group and an acidic group described in Japanese Unexamined Patent Publication No. 2009-203462 is particularly preferable in view of dispersibility, dispersion stability, and developability of the colored radiation-sensitive composition.

As a macromonomer used when producing a graft type polymer having an anchor portion on the pigment surface by radical polymerization, a known macromonomer can be used, and a macromonomer manufactured by Toa Gosei Co., Ltd. (MACROMONOMER) AA-6 (methyl methacrylate whose terminal group is methacryloyl group), AS-6 (polystyrene whose terminal group is methacryloyl group), AN-6S (styrene and acrylo whose terminal group is methacryloyl group) Copolymer of nitrile), AB-6 (butyl acrylate having terminal group methacryloyl group), PLACEL FM5 (methacrylic acid 2) manufactured by Daicel Chemical Industries, Ltd. (Daicel Chemical Industries Inc.) -5 molar equivalents of ε-caprolactone adduct of hydroxyethyl), FA10L (10 molar equivalents of ε-caprolactone of 2-hydroxyethyl acrylate), and the polyesters described in Japanese Patent Application Laid-Open No. 2-272009 And system macromonomers. Among them, a polyester macromonomer having excellent flexibility and affinity for solvents is particularly preferable in view of the dispersibility of the pigment dispersion, the dispersion stability, and the developability exhibited by the colored radiation-sensitive composition using the pigment dispersion. Most preferred is a polyester-based macromonomer represented by the polyester-based macromonomer described in 2-272009.

As a block type polymer which has an anchor part to a pigment surface, the block type polymer of Unexamined-Japanese-Patent No. 2003-49110, Unexamined-Japanese-Patent No. 2009-52010, etc. are preferable.

The pigment dispersant which can be used for this invention can also be obtained as a commercial item, As such a specific example, Disperbyk-101 (polyamide amine phosphate), 107 (carboxylic acid ester), 110 (copolymer containing an acid group) by BYKChemie company, 130 (Polyamide), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer), BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid), "EFKA4047, 4050-4010-4165 by EFKA" (Polyurethane), EFKA4330 to 4340 (block copolymer), 4400 to 4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 ( Phthalocyanine derivatives), 6750 (azo pigment derivatives), "AJISPER PB821, PB822, PB880, PB881" by Ajinomoto Fine-Techno Co., Inc., Kyoeisha Kagaku Corporation (Kyoeisha) Chemical Co., Ltd. "Florene (FLOWLEN) TG-710 (urethane oligomer)", "Paul Flow (POLYFLOW) No. 50E, No. 300 (acrylic copolymer) "," DISPARLON KS-860, 873SN, 874, # 2150 (aliphatic polyhydric carboxylic acid), # 7004 (polyether ester) by Kusumoto Chemical Co., Ltd. ), DA-703-50, DA-705, DA-725, `` DEMOL '' RN, N (naphthalenesulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid, manufactured by Kao Corporation) Formalin polycondensate) "," HOMOGENOL L-18 (polymeric polycarboxylic acid) "," EMULGEN "920, 930, 935, 985 (polyoxyethylene nonylphenyl ether)," acetamine (ACETAMIN) 86 (stearylamine acetate), "SOLSPERSE 5000" (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine) made by Nippon Lubrizol Corporation , 3000, 17000, 27000 (polymer having a functional part at the end), 24000, 28000, 32000, 38500 (grafted polymer) '', Nikko Chemicals Co., Ltd. IKKOL) T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate), Hinoact (Kawaken Fine Chemicals Co., Ltd.) Shin-Etsu Chemical Co., Ltd., such as T-8000E, organosiloxane polymer KP341, and Yusho Co., Ltd., "W001: Cationic Interface Activator ”, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, Nonionic surfactants, such as a sorbitan fatty acid ester, Anionic surfactants, such as "W004, W005, W017", "EFKA-46, EFKA-47," made by Morishita Sangyo Co., Ltd. (Morishita & Co., Ltd.) EFKA-47EA, EFKA Polymer 100, EFKA Polymer 400, EFKA Polymer 401, EFKA Polymer 450 '', Polymer dispersants, such as "DISPERSE AID 6, DISPERSE AID 8, DISPERS AID 15, DISPERS ADADE 9100" by San Nopco Ltd., ADEKA (ADEKA Corporation) `` ADEKA PLURONIC L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 '', And "IONET S-20" manufactured by Sanyo Chemical Industries Ltd., etc. may be mentioned.

In this invention, the binder which contains the compound represented by (B) General formula (1) as a copolymerization component is also mentioned as a preferable dispersing agent.

In the present invention, a graft copolymer containing a nitrogen atom may be mentioned as a preferable dispersant.

As the graft copolymer containing a nitrogen atom, one having a repeating unit containing a nitrogen atom in the main chain is preferable. Especially, it is preferable to have a repeating unit represented by Formula (A) and / or a repeating unit represented by Formula (B).

(In formula (A), R <_1> represents a C1-C5 alkylene group and A represents a hydrogen atom or any of following formula (C)-(E).)

In said formula (A), R <_1> represents linear or branched C1-C5 alkylene groups, such as a methylene group, an ethylene group, or a propylene group, Preferably it is a C2-C3 alkylene group, More preferably, Preferably an ethylene group. A represents a hydrogen atom or any of the following formulas (C) to (E), but is preferably formula (C).

In the formula (B), R ₁ and A is R ₁ and A agree with the formula (A).

In the formula (C), W ₁ represents an alkylene group linear or branched having 2 to 10 carbon atoms, particularly butyl group, a pentyl group, or hexyl groups are preferred alkylene of 4-7 carbon atoms, such as xylene group. p represents the integer of 1-20, Preferably it is an integer of 5-10.

In said formula (D), Y <_1> represents a bivalent coupling group, Especially, C1-C4 alkylene groups, such as an ethylene group and a propylene group, or C1-C4 alkyleneoxy, such as an ethyleneoxy group and a propyleneoxy group, Group is preferred. W <_2> represents linear or branched C2-C10 alkylene groups, such as an ethylene group, a propylene group, and a butylene group, Especially, C2-C3 alkylene groups, such as an ethylene group and a propylene group, are preferable. Y ₂ represents a hydrogen atom or —CO—R ₂ (R ₂ represents an alkyl group having 1 to 10 carbon atoms, such as an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group, and among these, an ethyl group, a propyl group, a butyl group, a pen) An alkyl group having 2 to 5 carbon atoms such as a methyl group is preferable). q represents the integer of 1-20, Preferably it is an integer of 5-10.

In said formula (E), W <_3> represents a C1-C50 alkyl group or C1-C50 hydroxyalkyl group which has hydroxyl groups 1-5, Among these, C10-C20 alkyl groups, such as a stearyl group, and mono The C10-20 hydroxyalkyl group which has 1-2 hydroxyl groups, such as a hydroxystearyl group, is preferable.

As for the content rate of the repeating unit represented by Formula (A) or (B) in the said "graft copolymer containing a nitrogen atom", the higher one is preferable, Usually it is 50 mol% or more, Preferably it is 70 mol% or more to be. Although both the repeating unit represented by Formula (A) and the repeating unit represented by Formula (B) may be used together, there is no restriction | limiting in particular in the content rate, Preferably, the repeating unit of Formula (A) It is more preferable to have contained a lot. The total number of repeating units represented by formula (A) or formula (B) is usually 1 to 100, preferably 10 to 70, and more preferably 20 to 50. Moreover, repeating units other than Formula (A) and Formula (B) may be included, and an alkylene group, an alkyleneoxy group, etc. can be illustrated as another repeating unit, for example. The "graft copolymer containing a nitrogen atom" is preferably the end of the -NH ₂ and -R ₁ -NH ₂ (R ₁ has the R ₁ and consent).

In addition, the said "graft copolymer containing a nitrogen atom" may be branched, even if the main chain is linear. The amine number of the said graft copolymer is 5 mgKOH / g-100 mgKOH / g normally, Preferably it is 10 mgKOH / g-70 mgKOH / g, More preferably, it is 15 mgKOH / g-40 mgKOH / g or less.

When the amine number is 5 mgKOH / g or more, dispersion stability can be further improved, and the viscosity can be made more stable. If an amine number is 100 mgKOH / g or less, a residue can be suppressed more and the fall of the electrical property after forming a liquid crystal panel can be suppressed more.

3000-100000 are preferable and, as for the weight average molecular weight measured by GPC (Gel Permeation Chromatography) of said "graft copolymer containing a nitrogen atom", 5000-50000 are especially preferable. If weight average molecular weight is 3000 or more, aggregation of a color material can be suppressed more, and high viscosity and gelation can be suppressed more. If it is 100000 or less, high viscosity of the copolymer itself can be suppressed more, and the lack of solubility to an organic solvent can be suppressed more.

The synthesis | combination method of the said dispersing agent can employ | adopt a well-known method, For example, the method of Unexamined-Japanese-Patent No. 63-30057 can be used.

In addition, as a dispersing agent in this invention, the polymer compound containing at least 1 sort (s) of repeating unit chosen from the repeating unit represented by either of following General formula (I) and General formula (II) from a viewpoint of further improving dispersion stability. (Hereinafter, it may be called "specific polymer.").

In said general formula (I) and general formula (II), R <^1> -R <^6> represents a hydrogen atom or monovalent organic group each independently, X <^1> and X <^2> respectively independently represent -CO- and -C (= O) O-, -CONH-, -OC (= O)-, or a phenylene group, L ¹ and L ² each independently represent a single bond or a divalent organic linking group, and A ¹ and A ² are each Independently, monovalent organic groups are represented, m and n each independently represent an integer of 2 to 8, and p and q each independently represent an integer of 1 to 100.

In General Formula (I) and General Formula (II), R ¹ to R ⁶ each independently represent a hydrogen atom or a monovalent organic group. As monovalent organic group, a substituted or unsubstituted alkyl group is preferable. As an alkyl group, 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 has a substituent, for example, as the substituent, a hydroxy group, an alkoxy group (preferably 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms), a methoxy group, an ethoxy group, and a cyclohexyl octane Season, etc. can be mentioned.

Specifically as a preferable alkyl group, For example, a methyl group, an ethyl group, a propyl group, n-butyl group, i-butyl group, t-butyl group, n-hexyl group, a cyclohexyl group, 2-hydroxyethyl group, 3-hydroxy A hydroxypropyl group, 2-hydroxypropyl group, 2-methoxyethyl group is mentioned.

In general formula (I) and general formula (II), as R <^1> , R <^2> , R <^4> and R <^{5>, a} hydrogen atom is preferable, As R <^3> and R <^6> , a hydrogen atom or a methyl group of the point of the adsorption efficiency to a pigment surface Is also most preferred.

In Formulas (I) and (II), X ¹ and X ² are each independently —CO—, —C (═O) O—, —CONH—, —OC (═O) —, or phenylene. Group. Especially, -C (= O) O-, -CONH-, and a phenylene group are preferable from a viewpoint of adsorption to a pigment, and -C (= O) O- is the most preferable.

In General Formula (I) and General Formula (II), L ¹ and L ² each independently represent a single bond or a divalent organic linking group. As a divalent organic coupling group, a substituted or unsubstituted alkylene group and the bivalent organic coupling group which consists of a partial structure containing the said alkylene group and hetero atom or hetero atom are preferable. Here, as an alkylene group, a C1-C12 alkylene group is preferable, A C1-C8 alkylene group is more preferable, A C1-C4 alkylene group is especially preferable. Moreover, as a hetero atom in the partial structure containing a hetero atom, an oxygen atom, a nitrogen atom, and a sulfur atom are mentioned, for example, Especially, an oxygen atom and a nitrogen atom are preferable.

Specifically as a preferable alkylene group, a methylene group, an ethylene group, a propylene group, trimethylene group, tetramethylene group is mentioned, for example.

When an alkylene group has a substituent, a hydroxyl group etc. are mentioned as said substituent, for example.

The divalent organic linking group has a partial structure containing a heteroatom or a heteroatom selected from -C (= 0)-, -OC (= 0)-, -NHC (= 0)-at the terminal of the alkylene group, It is preferable at the point of adsorption to a pigment to connect with the adjacent oxygen atom through the said hetero atom or the partial structure containing a hetero atom. Here, an adjacent oxygen atom means the oxygen atom couple | bonded with L <^1> in general formula (I) and L <^2> in general formula (II) by the side chain terminal side.

In General Formula (I) and General Formula (II), A ¹ and A ² each independently represent a monovalent organic group. As monovalent organic group, a hydroxyl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group is preferable.

Examples of the preferred alkyl group include linear, branched, and cyclic alkyl groups having 1 to 20 carbon atoms, and specific examples thereof include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octa. Tyl, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, octadecyl, eicosyl, isopropyl, isobutyl, s-butyl, t-butyl, isopentyl And neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group and 2-norbornyl group.

As the substituent of the substituted alkyl group, a group of monovalent nonmetallic atom groups except hydrogen is used. As a preferable example, a halogen atom (-F, -Br, -Cl, -I), a hydroxyl group, an alkoxy group, an aryloxy group, a mercapto group, Alkylthio group, arylthio group, alkyldithio group, aryldithio group, amino group, N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diarylamino group, N-alkyl-N- Arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N-arylcarbamoyloxy group, alkyl sulfoxy group, aryl sulfoxy group, acyloxy group, acylthio group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N'-alkyl Ureido group, N ', N'-dialkyl ureido group, N'-aryl ureido group, N', N'- diaryl ureido group, N'-alkyl-N'- aryl ureido Group, N-alkylureido group, N-arylureido group, N'-alkyl-N-alkylureido group, N'-alkyl-N-arylureido group, N ', N'-dialkyl-N-alkylureido group , N ', N'-dialkyl-N-arylureido group, N'-aryl-N-alkylureido group, N'-aryl-N-arylureido group, N', N'-diaryl-N-alkyl Ureido group, N ', N'-diaryl-N-arylureido group, N'-alkyl-N'-aryl-N-alkylureido group, N'-alkyl-N'-aryl-N-arylureido group, Alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N -Aryloxycarbonylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, alkylsulphi Neyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfo group (-SO ₃ H) and its conjugated base group (hereinafter referred to as sulfonate group), alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group , N-alkyl sulfinamoyl group, N, N-dialkyl sulfinamoyl group, N-aryl sulfinamoyl group, N, N- diaryl sulfinamoyl group, N-alkyl-N-aryl sulfinamoyl group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, phosphono group (-PO ₃ H ₂ ) and its conjugated base group (hereinafter referred to as phosphonate group), dialkylphosphono group (-PO ₃ (alkyl) ₂ ), diarylphosphono group (-PO ₃ (aryl) ₂ ), Alkylaryl phosphono group (-PO ₃ (alkyl) (aryl)), monoalkyl phosphono group (-PO ₃ H (alkyl)) and its conjugated base group (hereinafter referred to as alkyl phosphonate group), monoaryl a phosphono group (-PO ₃ H (aryl)) and its conjugated salts device (hereinafter, aryl phosphonate This is called dawn), phosphono oxy group (-OPO ₃ H ₂₎ and its conjugated salts device (referred to later, the phosphonate group), dialkyl phosphono oxy group (-OPO ₃ (alkyl) _2), Diarylphosphonooxy group (-OPO ₃ (aryl) ₂ ), alkylarylphosphonooxy group (-OPO ₃ (alkyl) (aryl)), monoalkylphosphonooxy group (-OPO ₃ H (alkyl)) and The conjugated base group (hereinafter referred to as alkylphosphonateoxy group), monoarylphosphonooxy group (-OPO ₃ H (aryl)) and the conjugated base group (hereinafter referred to as arylphosphonateoxy group), Cyano group, nitro group, aryl group, heteroaryl group, alkenyl group, alkynyl group, silyl group is mentioned.

Specific examples of the alkyl group in these substituents include the alkyl groups described above, and these may further have a substituent.

Examples of the substituent include an alkoxy group, aryloxy group, alkylthio group, arylthio group, N, N-dialkylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, acyloxy group, aryl group, hetero An aryl group, an alkenyl group, an alkynyl group, and a silyl group are preferable at the point of dispersion stability.

Specific examples of the aryl group include phenyl group, biphenyl group, naphthyl group, tolyl group, xylyl group, mesityl group, cumenyl group, chlorophenyl group, bromophenyl group, chloromethylphenyl group, hydroxyphenyl group, methoxyphenyl group, ethoxyphenyl group and phenoxy Cyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group, methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, ethoxyphenylcarbonyl group, phenoxycarbonylphenyl group , N-phenylcarbamoylphenyl group, phenyl group, cyanophenyl group, sulfophenyl group, sulfonatephenyl group, phosphonophenyl group, phosphonatephenyl group and the like.

As A ¹ and A ² , in terms of dispersion stability and developability, a straight chain having 1 to 20 carbon atoms, a branched carbon having 3 to 20 carbon atoms, and a cyclic alkyl group having 5 to 20 carbon atoms is preferable, and 4 to 15 carbon atoms are preferred. More preferably, the linear, branched, alkyl group having 4 to 15 carbon atoms, and the cyclic alkyl group having 6 to 10 carbon atoms are more preferable, and the linear alkyl group having 6 to 10 carbon atoms and branched alkyl group having 6 to 12 carbon atoms are more preferable. .

In general formula (I) and general formula (II), m and n respectively independently represent the integer of 2-8. 4-6 are preferable and 5 is the most preferable at the point of dispersion stability and developability.

In general formula (I) and general formula (II), p and q respectively independently represent the integer of 1-100. Different p and different q may be mixed. 5-60 are preferable at the point of dispersion stability and developability, 5-40 are more preferable, and 5-20 are more preferable.

It is preferable that the said specific polymer contains the repeating unit represented with the said general formula (I) from the point of dispersion stability.

Moreover, as a repeating unit represented by general formula (I), it is more preferable that it is a repeating unit represented with the following general formula (I) -2.

In said general formula (I) -2, R <^1> -R <^3> respectively independently represents a hydrogen atom or monovalent organic group, La represents a C2-C10 alkylene group, and Lb is -C (= O)- , or -NHC (= O) - represents the, a ¹ represents a monovalent organic group, m represents an integer of 2~8, p represents an integer of 1 to 100.

The repeating unit represented by general formula (I), (II), or (I) -2 is a polymer by polymerizing or copolymerizing the monomer represented by the following general formula (i), (ii), or (i) -2, respectively. It is introduced as a repeating unit of the compound.

In the general formulas (i), (ii) and (i) -2, R ¹ to R ⁶ each independently represent a hydrogen atom or a monovalent organic group, and X ¹ and X ² each independently represent -CO-. , -C (= O) O-, -CONH-, -OC (= O)-, or a phenylene group, L ¹ and L ² each independently represent a single bond or a divalent organic linking group, and La is An alkylene group having 2 to 10 carbon atoms is represented, Lb represents -C (= O)-or -NHC (= O)-, A ¹ and A ² each independently represent a monovalent organic group, and m and n are Each independently represents an integer of 2 to 8, and p and q each independently represent an integer of 1 to 100.

Although the preferable specific example [monomer (XA-1)-(XA-23)] of the monomer represented by general formula (i), (ii), or (i) -2 below is given to this, It is not limited to.

The said specific polymer should just contain at least 1 sort (s) of repeating unit selected from the repeating unit represented by either of general formula (I) and (II), may contain only 1 sort, and contains 2 or more sorts. You may also

In addition, although content of the repeating unit represented by either of general formula (I) and general formula (II) in a specific polymer does not have a restriction | limiting in particular, When the total repeating unit contained in a polymer is 100 mass%, general formula ( It is preferable to contain 5 mass% or more of repeating units represented by either of I) and general formula (II), It is more preferable to contain 50 mass%, It is further more preferable to contain 50 mass%-80 mass%.

The said specific polymer is a polymer which copolymerized the monomer which has a functional group which can adsorb | suck to a pigment for the purpose of improving the adsorption to a pigment, and the monomer represented by said general formula (i), (ii), (i) -2 mentioned above. It is preferable that it is a compound.

As a monomer which has a functional group which can adsorb | suck to a pigment, the monomer which has an acidic group, the monomer which has an organic pigment | dye structure or a heterocyclic structure, the monomer which has a basic nitrogen atom, the monomer which has an ionic group, etc. are mentioned specifically ,. Especially, the monomer which has an acidic group, the organic pigment | dye structure, or the heterocyclic structure is preferable at the point of the adsorption power to a pigment.

Examples of the monomer having an acidic group include a vinyl monomer having a carboxyl group and a vinyl monomer having a sulfonic acid group.

Examples of the vinyl monomer having a carboxyl group include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl esters, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and acrylic acid dimers. Moreover, the addition reaction product of the monomer which has a hydroxyl group, such as 2-hydroxyethyl (meth) acrylate, and cyclic anhydrides, such as maleic anhydride, a phthalic anhydride, succinic anhydride, cyclohexanedicarboxylic anhydride, omega-carboxy-polycapro Lactone 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, the monomer which has a hydroxyl group, such as 2-hydroxyethyl (meth) acrylate, and cyclic | annulars, such as maleic anhydride, a phthalic anhydride, succinic anhydride, and cyclohexane dicarboxylic anhydride, from a viewpoint of the image development removal property of an unexposed part. Addition reactants of anhydride are preferred.

Moreover, 2-acrylamide-2-methylpropanesulfonic acid etc. are mentioned as a vinyl monomer which has a sulfonic acid group, Monophosphoric acid mono (2-acryloyloxyethyl ester), Monophosphoric acid (1-methyl-) as a vinyl monomer which has a phosphoric acid group 2-acryloyloxyethyl ester) etc. are mentioned.

It is preferable that the said specific polymer contains the repeating unit derived from the monomer which has an acidic group as mentioned above. By including such a repeating unit, when the pigment dispersion composition of this invention is applied to a coloring radiation sensitive composition, the image development removal property of an unexposed part is excellent.

The said specific polymer may contain only 1 type of repeating units derived from the monomer which has an acidic group, and may contain 2 or more types.

Content of the repeating unit derived from the monomer which has an acidic group in a specific polymer becomes like this. Preferably it is 50 mgKOH / g or more, Especially preferably, it is 50 mgKOH / g-200 mgKOH / g. In other words, the content of the repeating unit derived from the monomer having an acidic group is preferably 50 mgKOH / g or more from the viewpoint of suppressing the formation of precipitates in the developing solution. In order to effectively suppress the production of secondary aggregates, which are aggregates of primary particles of pigments, or to effectively weaken the cohesion of secondary aggregates, the content of repeating units derived from monomers having acidic groups is preferably 50 mgKOH / g to 200 mgKOH / g. Do.

As a monomer which has the said organic pigment | dye structure or heterocyclic structure, For example, Paragraph No. 0048-Paragraph 0070 of Unexamined-Japanese-Patent No. 2009-256572-from the group which consists of a specific monomer, maleimide, and a maleimide derivative are described. One kind selected can be mentioned.

Examples of the monomer having a basic nitrogen atom include (meth) acrylic acid N, N-dimethylaminoethyl, (meth) acrylic acid N, N-dimethylaminopropyl, and (meth) acrylic acid 1- (N, N-dimethyl Amino) -1,1-dimethylmethyl, (meth) acrylic acid N, N-dimethylaminohexyl, (meth) acrylic acid N, N-diethylaminoethyl, (meth) acrylic acid N, N-diisopropylaminoethyl, ( Meta) N, N-di-n-butylaminoethyl acrylate, N, N-di-i-butylaminoethyl (meth) acrylate, morpholinoethyl (meth) acrylate, piperidinoethyl (meth) acrylate, ( (Meth) acrylic acid 1-pyrrolidinoethyl, (meth) acrylic acid N, N-methyl- 2-pyrrolidylaminoethyl, (meth) acrylic acid N, N-methylphenylaminoethyl, etc. are mentioned, (meth) acrylamide N- (N ', N'-dimethylaminoethyl) acrylamide, N- (N', N'-dimethylaminoethyl) methacrylamide, N- (N ', N'-diethylaminoethyl) as Drew Acrylamide, N- (N ', N'-diethylaminoethyl) methacrylamide, N- (N', N'-dimethylaminopropyl) acrylamide, N- (N ', N'-dimethylaminopropyl) Methacrylamide, N- (N ', N'-diethylaminopropyl) acrylamide, N- (N', N'-diethylaminopropyl) methacrylamide, 2- (N, N-dimethylamino) ethyl (Meth) acrylamide, 2- (N, N-diethylamino) ethyl (meth) acrylamide, 3- (N, N-diethylamino) propyl (meth) acrylamide, 3- (N, N-dimethyl Amino) propyl (meth) acrylamide, 1- (N, N-dimethylamino) -1,1-dimethylmethyl (meth) acrylamide and 6- (N, N-diethylamino) hexyl (meth) acrylamide, Morpholino (meth) acrylamide, piperidino (meth) acrylamide, N-methyl-2-pyrrolidyl (meth) acrylamide, etc. are mentioned, As styrene, N, N- dimethylamino styrene, N And N-dimethylaminomethyl styrene.

It is also possible to use a monomer having a urea group, a urethane group, a hydrocarbon group having 4 or more carbon atoms having a coordinating oxygen atom, an alkoxysilyl group, an epoxy group, an isocyanate group and a hydroxyl group. Specifically, the monomer of the following structures is mentioned, for example.

As a monomer which has an ionic group, the vinyl monomer (anionic vinyl monomer, cationic vinyl monomer) which has an ionic group is mentioned. Examples of the anionic vinyl monomers include alkali metal salts of the vinyl monomers having the acidic group, salts with organic amines (eg, tertiary amines such as triethylamine and dimethylaminoethanol), and cationic vinyls. As a monomer, the said nitrogen-containing vinyl monomer is halogenated alkyl (alkyl group: C1-18, halogen atom: chlorine atom, bromine atom, or iodine atom); Halogenated benzyl, such as benzyl chloride and benzyl bromide; Alkyl sulfonic acid esters such as methanesulfonic acid (alkyl groups: C1-18); Aryl sulfonic acid alkyl esters (alkyl groups: C1-18) such as benzene sulfonic acid and toluene sulfonic acid; The quaternized by dialkyl sulfate (alkyl group: C1-4) etc., a dialkyl diallyl ammonium salt, etc. are mentioned.

The monomer which has a functional group which can adsorb | suck to a pigment can be suitably selected according to the kind of pigment to be disperse | distributed, These may be used independently and may use 2 or more types together.

The said specific polymer may further contain the repeating unit derived from the vinyl monomer which can be copolymerized 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, ( Meta) 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. In addition, in this specification, when showing either or both of "acryl and methacryl", it may describe as "(meth) acryl."

Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, 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) acrylic acid dodecyl, (meth) acrylic acid octadecyl, (meth) acrylate acetoxyethyl, (meth) acrylate acetoacetoxyethyl, (meth) acrylate phenyl, (meth) acrylate 2-hydroxyethyl, (meth) 2-methoxyethyl acrylate, 2-ethoxyethyl (meth) acrylate, 2- (2-methoxyethoxy) ethyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, (meth ) Benzyl acrylate, (meth) acrylic acid diethylene glycol monomethyl ether, (meth) acrylic acid Ethylene 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, (meth) (Beta) -phenoxy methoxyethyl acrylate, nonylphenoxy polyethylene glycol (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyl oxyethyl (meth) acrylate, trifluoroethyl (meth) acrylate, ( (Meth) acrylic acid octafluoropentyl, (meth) acrylic acid perfluorooctylethyl, (meth) acrylic acid dicyclopentanyl, (meth) acrylic acid tribromophenyl, (meth) acrylic acid tribromophenyloxyethyl, etc. are mentioned. .

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

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

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

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

Examples of itaconic acid diesters include dimethyl itaconate, diethyl itaconate, dibutyl itaconate, 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-benzyl (meth) acrylamide, (meth) acryloyl morpholine, diacetone acrylamide, etc. are mentioned. Can be.

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

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

Preferred embodiments of the specific polymer are copolymerized at least with a monomer represented by formula (i), (ii), or (i) -2, a monomer having an acidic group, or a monomer having an organic dye structure or a heterocyclic structure. More preferably, at least the monomer represented by general formula (i) -2 mentioned above and the monomer which has an acidic radical are copolymerized.

According to this aspect, the pigment dispersion composition which is excellent by pigment adsorption and excellent in developability can be provided.

Moreover, in this invention, the dispersing agent shown below is especially preferable.

It is preferable that the preferable molecular weights of the said specific polymer are the ranges of 5000-100000 in a weight average molecular weight (Mw), and the range of 2500-50000 in a number average molecular weight (Mn). More preferably in the range of 10,000 to 50,000 in terms of weight average molecular weight (Mw) and in the range of 5000 to 30,000 in number average molecular weight (Mn).

In particular, it is most preferable that it is the range of 10000-30000 in a weight average molecular weight (Mw), and the range of 5000-15000 in a number average molecular weight (Mn).

That is, it is preferable that the weight average molecular weight (Mw) of a specific polymer is 10000 or more from a viewpoint of effectively loosening the secondary aggregate which is an aggregate of the primary particle of a pigment, or weakening reaggregation effectively. Moreover, it is preferable that the weight average molecular weight (Mw) of a specific polymer is 30000 or less from a developable viewpoint at the time of manufacturing a color filter with the colored radiation-sensitive composition containing a pigment dispersion composition.

The said specific polymer is normal, for example using the monomer represented by general formula (i), (ii), or (i) -2, and another radically polymerizable compound (various monomers mentioned above) as a copolymerization component. It can manufacture by a radical polymerization method.

Generally, suspension polymerization or solution polymerization is used. As a solvent used when synthesizing such a specific polymer, for example, ethylene chloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, propanol, butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2- Methoxyethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propylacetate, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, toluene, ethyl acetate, lactic acid Methyl, ethyl lactate, etc. are mentioned. These solvents may be used singly or in combination of two or more.

In addition, a radical polymerization initiator may be used in the radical polymerization, and a chain transfer agent (for example, 2-mercaptoethanol and dodecyl mercaptan) may be further used.

In addition, in the range which does not impair the effect of this invention, you may simultaneously use other high molecular compounds other than the specific polymer mentioned above as needed.

As another polymer compound, natural resin, modified natural resin, synthetic resin, synthetic resin modified with natural resin, etc. can be used.

Rosin is typical as a natural resin, and rosin derivatives, a cellulose derivative, a rubber derivative, a protein derivative, and these oligomers are mentioned as a modified natural resin. Examples of the synthetic resin include an epoxy resin, an acrylic resin, a maleic acid resin, a butyral resin, a polyester resin, a melamine resin, a phenol resin, and a polyurethane resin. Examples of the synthetic resin modified with natural resins include rosin-modified maleic acid resins and rosin-modified phenolic resins.

Examples of the synthetic resin include polyamide amines and their salts, polycarboxylic acids and their salts, high molecular weight unsaturated acid esters, polyurethanes, polyesters, poly (meth) acrylates, (meth) acrylic copolymers and naphthalenesulfonic acid formalin condensates. .

These pigment dispersants may be used alone or in combination of two or more. In the present invention, it is particularly preferable to use a combination of a pigment derivative and a polymeric dispersant. In addition, the pigment dispersant in the present invention may be used in combination with an alkali-soluble resin described below together with a terminal modified polymer, a graft polymer, and a block polymer having an anchor portion to the pigment surface.

It is preferable that content of the pigment dispersant in a pigment dispersion liquid is 1 mass part-80 mass parts with respect to 100 mass parts of pigments, 5 mass parts-70 mass parts are more preferable, It is further more preferable that they are 10 mass parts-60 mass parts.

When using a polymeric dispersing agent, as the usage-amount, the range of 5 mass parts-100 parts is preferable in mass conversion with respect to 100 mass parts of pigments, and it is more preferable that it is the range of 10 mass parts-80 parts.

(Pigment derivative)

The pigment dispersion composition is optionally added with a pigment derivative. A pigment derivative having affinity with a dispersant or a polar group introduced therein is adsorbed on the surface of the pigment and used as the adsorption point of the dispersant, thereby dispersing the pigment as fine particles in the colored radiation-sensitive composition and preventing reaggregation thereof. It is effective in forming a color filter having high contrast and excellent transparency.

Specifically, the pigment derivative is a compound having an organic pigment as a matrix skeleton and an acidic group, a basic group or an aromatic group as a substituent. Specific examples of the organic pigments include quinacridone pigments, phthalocyanine pigments, azo pigments, quinophthalone pigments, isoindolin pigments, isoindolinone pigments, quinoline pigments, diketopyrrolopyrrole pigments, benzoimidazolone pigments, Pigments, and the like. Light yellow aromatic polycyclic compounds, such as naphthalene series, anthraquinone series, triazine series, and quinoline series, which are not generally called dyes, are also included. As a pigment derivative, Unexamined-Japanese-Patent No. 11-49974, Unexamined-Japanese-Patent No. 11-189732, Unexamined-Japanese-Patent No. 10-245501, Unexamined-Japanese-Patent No. 2006-265528, Unexamined-Japanese-Patent No. 8-295810 Japanese Patent Laid-Open No. 11-199796, Japanese Patent Laid-Open No. 2005-234478, Japanese Patent Laid-Open No. 2003-240938, Japanese Patent Laid-Open No. 2001-356210, Japanese Patent Laid-Open No. 2009-102532, etc. You can use what you have.

As a pigment derivative in this invention, Unexamined-Japanese-Patent No. 11-49974, Unexamined-Japanese-Patent No. 11-189732, Unexamined-Japanese-Patent No. 10-245501, Unexamined-Japanese-Patent No. 2006-265528, Japan Patent Publication Japanese Patent Laid-Open No. Hei 8-295810, Japanese Patent Laid-Open No. 11-199796, Japanese Patent Laid-Open 2005-234478, Japanese Patent Laid-Open 2003-240938, Japanese Patent Laid-Open 2001-356210, Japanese Patent Laid-Open 2000-239554 The azo pigment derivative described in the publication etc. can also be used.

As an azo pigment derivative in this invention, the compound represented with the following general formula (P1) among the said azo pigment derivatives is especially preferable from a viewpoint of further improving dispersion stability.

In general formula (P1), A represents the component which can form an azo pigment with X-Y. The said A can be arbitrarily selected as long as it is a compound which can form an azo pigment by coupling with a diazonium compound. Although the specific example of said A is shown below, this invention is not limited to these specific examples at all.

In said general formula (P1), X represents group chosen from a single bond (it means that Y is connected directly to -N = N-), or the bivalent coupling group represented by the following structural formula.

In said general formula (P1), Y represents group represented by the following general formula (P2).

In General Formula (P2), Z represents a lower alkylene group. Z is represented by-(CH ₂ ) _b- , but _b represents an integer of 1 to 5, preferably 2 or 3. In the general formula (P2), -NR ₂ represents a 5~6-membered saturated heterocyclic ring comprising a lower alkyl group, or a nitrogen atom. Wherein -NR _2, if showing a lower alkyl group, is represented by _{-N (C n H 2n + 1} ) 2, n is an integer of 1 to 4 shows a preferably one or two. On the other hand, when said -NR ₂ represents a 5-6 membered saturated heterocyclic ring containing a nitrogen atom, the heterocyclic ring represented by the following structural formula is preferable.

In General Formula (P2), Z and —NR ₂ may each have a lower alkyl group or an alkoxy group as a substituent. In said general formula (P2), a represents 1 or 2, Preferably 2 is represented.

Specific examples (specific examples 1 to 22) of the compound represented by the general formula (P1) are shown below, but the present invention is not limited to these specific examples at all.

1 mass%-30 mass% are preferable with respect to the mass of a pigment, and, as for content in the pigment dispersion composition of the said pigment derivative, 3 mass%-20 mass% are more preferable. When the content is within the above range, the dispersion can be satisfactorily performed while the viscosity is kept low, and the dispersion stability after dispersion can be improved, and excellent color characteristics can be obtained with high transmittance, and good color characteristics can be obtained when producing a color filter. It can comprise with high contrast.

The dispersion method is performed by, for example, mixing the pigment and the dispersing agent in advance and dispersing it in a homogenizer or the like by undispersing it using a bead disperser (eg, dispermat manufactured by GETZMANN) using zirconia beads or the like. Can be. As dispersion time, about 3 to 6 hours are preferable.

(Organic solvent)

Generally the colored radiation-sensitive composition for color filters of this invention can be comprised using the organic solvent. The organic solvent is not particularly limited as long as it satisfies the solubility of each component and the applicability of the colored radiation-sensitive composition, but is preferably selected in consideration of the solubility, coating property, and safety of the ultraviolet absorber and the binder. Moreover, when preparing the colored radiation-sensitive composition in this invention, it is preferable to contain at least 2 type of organic solvent.

Examples of the organic solvent include esters such as ethyl acetate, acetic acid-n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, and methyl lactate. , Ethyl lactate, alkyl oxyacetate (e.g. methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (e.g. methyl methoxyacetate, methoxyacetic acid ethyl, methoxyacetic acid butyl, ethoxyacetic acid methyl, ethoxyacetic acid ethyl) ), 3-oxypropionic acid alkyl esters (e.g., methyl 3-oxypropionate, ethyl 3-oxypropionate, etc.) (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid) Methyl, 3-ethoxypropionate, etc.), 2-oxypropionic acid alkyl esters (e.g., methyl 2-oxypropionate, 2-oxypropionic acid) Ethyl, 2-oxypropionic acid propyl and the like (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionic acid, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate), Methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate (eg, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate , Ethyl pyruvate, propyl pyruvate, methyl acetoacetic acid, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, and the like, and ethers, for example, 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 Le, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate and the like, and ketones, for example, methyl ethyl ketone, cyclohexanone, 2-heptanone, Examples of 3-heptanone and the like and aromatic hydrocarbons include toluene and xylene, for example.

It is also preferable to mix 2 or more types of these organic solvents from a viewpoint of the solubility of an ultraviolet absorber and alkali-soluble resin, an improvement of a coating surface shape, etc. In this case, the methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate and 2-hep are particularly preferred. It is a mixed solution which consists of 2 or more types chosen from tanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate.

It is preferable to make content in the colored radiation-sensitive composition of the organic solvent into the quantity which becomes 5 mass%-80 mass% of total solid content concentration of a composition from an applicability viewpoint, 5 mass%-60 mass% are more preferable, 10 mass%-50 mass% are especially preferable.

(Polymer material)

In addition to the above-mentioned components, the pigment dispersion liquid contains the compound represented by the general formula (B) as a copolymerization component from the viewpoint of improving the dispersion stability and controlling the developability when the pigment dispersion is applied to the colored radiation-sensitive composition. You may further contain the binder and the polymer material of another structure.

(B) Although the binder which contains the compound represented by following General formula (1) as a copolymerization component is mentioned later, As a polymeric material of another structure, for example, polyamideamine, its salt, polycarboxylic acid, its salt, and high molecular weight. Unsaturated acid esters, modified polyurethanes, modified polyesters, modified poly (meth) acrylates, (meth) acrylic copolymers (particularly, (meth) acrylic acid copolymers containing a carboxylic acid group and a polymerizable group in the side chain are preferable). ) And naphthalene sulfonic acid formalin condensates. Since such a polymer material is adsorbed on the surface of the pigment and acts to prevent reagglomeration, end-modified polymers, graft-type polymers and block-type polymers having anchor sites on the pigment surface are preferable, and for example, contain heterocycles. And graft copolymers containing a monomer to be mentioned and a polymerizable oligomer having an ethylenically unsaturated bond as a copolymer unit.

Other polymeric materials also include polyamideamine phosphates, high molecular weight unsaturated polycarboxylic acids, polyetheresters, aromatic sulfonic acid formalin polycondensates, polyoxyethylene nonylphenyl ethers, polyesteramines, polyoxyethylene sorbitan monooleate polyoxyethylene Monostearate and the like.

The polymer material of these other structures may be used independently, and may be used in combination of 2 or more type.

20 mass%-80 mass% are preferable with respect to a pigment, as for content of the other polymer material in a pigment dispersion, 30 mass%-70 mass% are more preferable, 40 mass%-60 mass% are more preferable.

<Binder containing the compound represented by (B) General formula (1) as a copolymerization component>

The colored radiation-sensitive composition of the present invention (B) contains a binder (hereinafter referred to as "specific binder" as appropriate) containing the compound represented by the following general formula (1) as a copolymerization component. That is, the said specific binder is a copolymer containing the compound represented by following General formula (1) as a copolymerization component.

In General Formula (1), R ¹ and R ² each independently represent a hydrogen atom or an alkyl group.

The alkyl group of R ¹ and R ² in General Formula (1) may have a substituent.

As an alkyl group in General formula (1), a C1-C25 alkyl group is preferable and there is no restriction | limiting in particular, For example, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group linear or branched alkyl groups such as t-butyl, t-amyl, stearyl, lauryl and 2-ethylhexyl groups; An aryl group such as phenyl; Alicyclic groups such as cyclohexyl group, t-butylcyclohexyl group, dicyclopentadienyl group, tricyclodecanyl group, isobornyl group, adamantyl group, and 2-methyl-2-adamantyl group; Alkyl group substituted by alkoxy, such as 1-methoxyethyl group and 1-ethoxyethyl group; An alkyl group substituted with an aryl group such as benzyl; And the like. Among these, especially primary or secondary hydrocarbon groups which are hard to be detached by an acid or heat, such as a methyl group, an ethyl group, a cyclohexyl group, a benzyl group, are preferable at the point of heat resistance. In addition, the same substituent may be sufficient as R <^1> and R <^2> , and other substituent may be sufficient as it.

Examples of the compound represented by the general formula (1) include dimethyl-2,2 '-[oxybis (methylene)] bis-2-propenoate and diethyl-2,2'-[oxybis (methylene)] bis- 2-propenoate, di (n-propyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (n-butyl) -2,2'-[oxybis (methylene )] Bis-2-propenoate, di (t-butyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (isobutyl) -2,2'-[oxy Bis (methylene)] bis-2-propenoate, di (cyclohexyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (benzyl) -2,2'-[ Oxybis (methylene)] bis-2-propenoate, etc. are mentioned.

Among them, dimethyl-2,2 '-[oxybis (methylene)] bis-2-propenoate is particularly preferable.

The specific binder of this invention may contain the compound represented by General formula (1) as a polymeric component, and may contain polymeric components other than the compound represented by General formula (1).

Although there is no restriction | limiting in particular about the polymerizable components other than the compound represented by General formula (1), It is preferable to include the monomer which provides usefulness from a viewpoint of the ease of handling, such as solubility to an organic solvent, as a polymeric component. As a monomer which provides the said usefulness, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and (meth) acrylic acid (Meth) acrylic acid esters, such as isobutyl, t-butyl (meth) acrylate, methyl 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, and 2-hydroxyethyl (meth) acrylate Ryu; Aromatic vinyl compounds such as styrene, vinyltoluene, and? -Methylstyrene; N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide; Butadiene or substituted butadiene compounds such as butadiene and isoprene; Ethylene or substituted ethylene compounds such as ethylene, propylene, vinyl chloride and acrylonitrile; Vinyl esters such as vinyl acetate; And the like.

It is preferable to contain aryl (meth) acrylate or alkyl (meth) acrylate as a polymeric component among these.

Moreover, it is preferable to contain the monomer containing an acidic group as a polymerizable component from an alkali developability viewpoint. As a monomer containing the said acidic group, For example, the monomer which has carboxyl groups, such as (meth) acrylic acid and itaconic acid, the monomer which has phenolic hydroxyl groups, such as N-hydroxyphenyl maleimide, maleic anhydride, itaconic anhydride, etc. The monomer etc. which have a carboxylic anhydride group are mentioned.

It is preferable to contain (meth) acrylic acid among these as a polymeric component.

Among them, the compound represented by the general formula (1) is dimethyl-2,2 '-[oxybis (methylene)] bis-2-propenoate, benzyl (meth) acrylate, methyl (meth) methacrylate, And a binder obtained by copolymerizing (meth) crylic acid as the polymerizable component.

Moreover, since a radiation sensitive group can be provided to the specific binder of this invention by adding the compound which has a radically polymerizable double bond with respect to the binder superposed | polymerized as mentioned above, it is a more preferable aspect. Although the method of the process of adding the compound which has a radically polymerizable double bond depends on the kind of monomer which can add the compound which has a radically polymerizable double bond, For example, carboxyl groups, such as (meth) acrylic acid and itaconic acid, are added. When the monomer which has is used, epoxy groups, such as glycidyl (meth) acrylate, 3, 4- epoxycyclohexylmethyl (meth) acrylate, o- (or m-, or p-) vinylbenzyl glycidyl ether What is necessary is just to add the compound which has a radically polymerizable double bond, and when using the monomer which has carboxylic acid anhydride groups, such as maleic anhydride and itaconic anhydride, hydroxyl groups, such as 2-hydroxyethyl (meth) acrylate, and a radical What is necessary is just to add the compound which has a polymerizable double bond, glycidyl (meth) acrylate, 3, 4- epoxycyclohexyl methyl (meth) acrylate, When using a monomer having an epoxy group such as o- (or m- or p-) vinylbenzyl glycidyl ether, a compound having an acid group such as (meth) acrylic acid and a radical polymerizable double bond may be added.

As a specific binder of this invention, the most preferable combination as a copolymerization component is a structure derived from methacrylic acid in the copolymer of the compound represented by General formula (1), benzyl methacrylate, methyl methacrylate, and methacrylic acid. It is a specific binder which has radiation sensitivity by reacting a part with glycidyl methacrylate.

1 mol%-20 mol% are preferable, and, as for content of the polymeric component represented by General formula (1) in a specific binder, More preferably, they are 5 mol%-15 mol%. By setting it as this range, the effect of suppressing residue mixing and diffusion mixing can be increased.

It is preferable that 20 mol%-80 mol% are contained in the specific binder, and the polymerizable component of the oil-solubility provision in a specific binder is more preferable, It is 30 mol%-70 mol%, The solubility to a solvent improves especially.

It is preferable to contain 10 mol%-50 mol%, and, as for the polymeric component containing an acidic group in a specific binder, 20 mol%-40 mol% are more preferable. By setting it as this range, alkali developability of a colored radiation-sensitive composition improves and pattern formation becomes especially favorable.

In addition, when a specific binder contains a radiation sensitive group, 20 mol%-30 mol% of the copolymerization component which has a radiation sensitive group is preferable, and in that case, the polymeric component containing an acidic group is 5 mol It is preferable that they are% -15 mol%. By setting it as this range, since the hardenability of a colored radiation-sensitive composition becomes high, the effect of suppressing residue mixing and diffusion mixing can be further enhanced.

As for the molecular weight of a specific binder, 5000-14000 are preferable at a weight average molecular weight, 8000-13000 are more preferable, and 9000-12000 are the most preferable. By setting it as this range, developability and the viscosity stability of a solution become favorable.

The weight average molecular weight is a value measured by a gel permeation chromatograph (GPC) here and computed in polystyrene conversion. GPC used HLC-8020GPC (made by Tosoh Corporation), and measured the column as TSKgel SuperHZM-H, TSKgel SuperHZ4000, and TSKgel SuperHZ200 (made by Tosoh Corporation).

A specific binder can be synthesize | combined according to the method described in Unexamined-Japanese-Patent No. 2004-300204.

A specific binder may add one part or all part in preparation of said pigment dispersion liquid.

Although one specific binder may be included in the colored radiation-sensitive composition of the present invention, two or more types may be included.

1 mass%-40 mass% are preferable with respect to the total solid of a colored radiation sensitive composition, and, as for content of the specific binder in the colored radiation-sensitive composition of this invention, 3 mass%-30 mass% are more preferable. By setting it in this range, the effect of this invention will be exhibited without regret.

&Lt; (C) Polymerizable compound >

The colored radiation-sensitive composition of the present invention contains the (C) polymerizable compound.

The polymerizable compound (C) is specifically selected from compounds having at least one, preferably two or more terminal ethylenically unsaturated bonds. Especially, the tetrafunctional or more than polyfunctional polymerizable compound is preferable, and 5-functional or more is more preferable.

Such compound groups are widely known in the industrial field, and in the present invention, these can be used without particular limitation. These may be, for example, any of chemical forms such as monomers, prepolymers, ie dimers, trimers and oligomers, or mixtures thereof and multimers thereof. The polymeric compound in this invention may be used individually by 1 type, and may use 2 or more types together.

More specifically, examples of the monomer and its prepolymer include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, amides, and these A multimer is mentioned, Preferably they are ester of unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, the amide of unsaturated carboxylic acid and an aliphatic polyamine compound, and these multimers. Further, it is also possible to use an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, an amino group or a mercapto group, an addition reaction product of a monofunctional or polyfunctional isocyanate or an epoxy, a monofunctional or polyfunctional carboxylic acid A dehydration condensation reaction product of a carboxylic acid is also preferably used. Moreover, the addition reaction product of unsaturated carboxylic acid ester or amide which has electrophilic substituents, such as an isocyanate group and an epoxy group, monofunctional or polyfunctional alcohol, amines, and thiols, and also detachable substituents, such as a halogen group and a tosyloxy group, Substituted reactants of unsaturated carboxylic acid esters or amides having monofunctional or polyfunctional alcohols, amines and thiols are also preferable. As another example, a compound group substituted with a vinylbenzene derivative such as unsaturated phosphonic acid and styrene, vinyl ether, allyl ether, or the like may be used instead of the above unsaturated carboxylic acid.

As these specific compounds, the compound described in Paragraph No. 0095-0108 of Unexamined-Japanese-Patent No. 2009-288705 can also be used suitably also in this invention.

Moreover, as said polymeric compound, the compound which has an ethylenically unsaturated group which has a boiling point of 100 degreeC or more under the normal pressure which has at least 1 addition-polymerizable ethylene group is also preferable. Examples thereof include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and phenoxyethyl (meth) acrylate; Polyethylene glycol di (meth) acrylate, trimethol ethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipenta Erythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimetholpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocy (Meth) acrylated after addition of ethylene oxide or propylene oxide to polyfunctional alcohols such as anurate, glycerin or trimetholethane, Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 50-6034 , Urethane (meth) acrylates described in Japanese Patent Laid-Open No. 51-37193, Japanese Patent Laid-Open No. 48-64183, Japanese Patent Laid-Open No. 49-43191 And polyfunctional acrylates and methacrylates such as the polyester acrylates described in Japanese Patent Application Laid-open No. 52-30490, epoxy acrylates which are reaction products of epoxy resins and (meth) acrylic acids, and these And mixtures.

(Meth) acrylate obtained by reacting a polyfunctional carboxylic acid with a compound having a cyclic ether group such as glycidyl (meth) acrylate and an ethylenic unsaturated group.

Moreover, the compound which has a fluorene ring as described in Unexamined-Japanese-Patent No. 2010-160418, Unexamined-Japanese-Patent No. 2010-129825, the specification of Unexamined-Japanese-Patent No. 4364216, etc., and has an ethylenically unsaturated group bifunctional or more as another preferable polymeric compound. It is also possible to use cardo resin.

Moreover, as a compound which has a boiling point of 100 degreeC or more under normal pressure, and has an ethylenically unsaturated group which can be at least 1 addition polymerization, the compound of Paragraph No. [0254]-[0257] of Unexamined-Japanese-Patent No. 2008-292970 is also preferable.

In addition to the above, radically polymerizable monomers represented by the following General Formulas (MO-1) to (MO-5) can also be preferably used. In addition, in formula, when T is an oxyalkylene group, the terminal at the side of a carbon atom couple | bonds with R.

In said general formula, n is 0-14, m is 1-8. Two or more R and T in one molecule may be same or different, respectively.

At least one of two or more R in each of the polymerizable compounds represented by general formulas (MO-1) to (MO-5) is -OC (= 0) CH = CH ₂ , or -OC (= 0). The group represented by) C (CH ₃ ) = CH ₂ is represented.

As a specific example of the polymeric compound represented by said general formula (MO-1)-(MO-5), Paragraph No. 0248-Paragraph No. 0251 of Unexamined-Japanese-Patent No. 2007-269779 are preferable also in this invention. Can be used.

In addition, (meth) acrylate after adding ethylene oxide or propylene oxide to the polyfunctional alcohol described in Japanese Patent Application Laid-open No. Hei 10-62986 with the specific examples as the general formulas (1) and (2). The compound can also be used as the polymerizable compound.

Especially, as a polymeric compound, it is dipentaerythritol triacrylate (KAYARAD D-330 as a commercial item; Nippon Kayaku Co., Ltd. product), dipentaerythritol tetraacrylate (KAYARAD D as a commercial item) -320; Nippon Kayaku Co., Ltd.) dipentaerythritol pentaacrylate (as a commercial item KAYARAD D-310; Nippon Kayaku Co., Ltd.), dipentaerythritol hexaacrylate (KAYARAD DPHA as a commercial product; Nippon Kayaku Co., Ltd.) Shigisha Co., Ltd., dipentaerythritol hexaacrylate (A-DPH-12E; Shin-Nakamura Chemical Co., Ltd. make) and these (meth) acryloyl groups Preference is given to structures in which the ethylene glycol and the propylene glycol residues are interposed. These oligomer types can also be used. The form of a preferable polymeric compound is shown below.

As a polymerizable compound, you may have acid groups, such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group, as a polyfunctional monomer. As long as the ethylenic compound has an unreacted carboxyl group as in the case of a mixture as described above, it can be used as it is, but if necessary, the acid group is caused by reacting a non-aromatic carboxylic anhydride with the hydroxyl group of the above-mentioned ethylenic compound. You may introduce. In this case, specific examples of the non-aromatic carboxylic acid anhydrides to be used include anhydrous tetrahydrophthalic acid, alkylated tetrahydrophthalic acid, anhydrous hexahydrophthalic acid, alkylated anhydrous hexahydrophthalic acid, succinic anhydride, and maleic anhydride.

In the present invention, the monomer having an acid group is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and the non-reactive hydroxyl group of the aliphatic polyhydroxy compound is made to react with a non-aromatic carboxylic anhydride to give an acid group. Polyfunctional monomers are preferred. Especially preferably, in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol. As a commercial item, M-510, M-520, etc. which are polybasic acid modified acrylic oligomers of Toa Gosei Co., Ltd. are mentioned, for example.

Although these monomers may be used individually by 1 type, it is difficult to use a single compound in manufacture, You may mix and use 2 or more types. Moreover, you may use together the polyfunctional monomer which does not have an acidic radical, and the polyfunctional monomer which has an acidic radical as needed.

As a preferable acid value of the polyfunctional monomer which has an acidic radical, it is 0.1 mgKOH / g-40 mgKOH / g, Especially preferably, it is 5 mgKOH / g-30 mgKOH / g. If the acid value of the polyfunctional monomer is too low, the development and dissolution characteristics are inferior. If the acid value of the polyfunctional monomer is too high, manufacturing and handling become difficult, resulting in poor photopolymerization performance and poor curability such as surface smoothness of the pixel. Therefore, when using together 2 or more types of polyfunctional monomers of another acidic radical, or when using the polyfunctional monomer which does not have an acidic radical, it is preferable to adjust so that the acidic radical as a whole polyfunctional monomer may fall in the said range.

Moreover, it is also a preferable aspect to contain the polyfunctional monomer which has a caprolactone structure as a polymerizable monomer.

The polyfunctional monomer having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in its molecule, but examples thereof include trimetholethane, ditrimethyrolethane, trimetholpropane, ditrimetholpropane, Ε-caprolactone-modified polyfunctional (meth) obtained by esterifying polyhydric alcohols such as pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerol, and trimetholmelamine, and (meth) acrylic acid and ε-caprolactone Acrylate is mentioned. Especially, the polyfunctional monomer which has a caprolactone structure represented by the following general formula (Z-1) is preferable.

In general formula (Z-1), all 6 R is group represented by the following general formula (Z-2), or 1-5 of 6 R is represented by the following general formula (Z-2) The remainder is a group represented by the following general formula (Z-3). The six R's may be the same as or different from each other.

In general formula (Z-2), R <^1> represents a hydrogen atom or a methyl group, m represents the number of 1 or 2, and it shows that "*" is a bond.

R <^1> represents a hydrogen atom or a methyl group in general formula (Z-3), and "*" shows a bond.)

The polyfunctional monomer which has such a caprolactone structure is marketed as KAYARAD DPCA series by Nippon Kayaku Co., Ltd., for example, and DPCA-20 (m = 1, Formula (1) in said Formula (1)-(3). 2) the number of groups represented by 2) and R ¹ are all hydrogen atoms), DPCA-30 (formula, m = 1, the number of groups represented by formula (2) = 3, R ¹ are all hydrogen) A compound which is an atom), DPCA-60 (the compound represented by the formula, m = 1, the number of groups represented by Formula (2) = 6, R ¹ are all hydrogen atoms), DPCA-120 (m = 2 in the formula) , The number of groups represented by Formula (2) = 6, the compound in which R <^1> is all hydrogen atoms, etc. are mentioned.

In this invention, the polyfunctional monomer which has a caprolactone structure can be used individually or in mixture of 2 or more types.

Moreover, it is preferable that it is at least 1 sort (s) chosen from the group of the compound represented by the following general formula (Z-4) or general formula (Z-5) as a polymeric compound in this invention.

In the general formulas (Z-4) and (Z-5), E is independently-((CH ₂ ) yCH ₂ O)-, or-((CH ₂ ) yCH (CH ₃ ) O)- And each independently represents an integer of 0 to 10, and each X independently represents an acryloyl group, a methacryloyl group, a hydrogen atom, or a carboxyl group.

In the general formula (Z-4), the sum of the acryloyl group and the methacryloyl group is three or four, and a plurality of m each independently represents an integer of 0 to 10, and the sum of each m is 0. It is an integer of -40. However, when the sum of each m is 0, any one of X is a carboxyl group.

In said general formula (ii), the sum total of acryloyl group and methacryloyl group is 5 or 6 pieces, n exists in multiple numbers each independently represents the integer of 0-10, and the sum total of each n is 0-60. Is an integer. However, when the sum of each n is 0, any one of X is a carboxyl group.

In the general formula (Z-4), m is preferably an integer of 0 to 6, more preferably an integer of 0 to 4.

Moreover, the integer of 2-40 is preferable, as for the sum total of each m, the integer of 2-16 is more preferable, and the integer of 4-8 is especially preferable.

In the general formula (Z-5), n is preferably an integer of 0 to 6, more preferably an integer of 0 to 4.

Moreover, the integer of 3-60 is preferable, the integer of 3-24 is more preferable, and, as for the sum total of each n, the integer of 6-12 is especially preferable.

Further, the formula (Z-4) or general formula (Z-5) of _{- ((CH 2) yCH 2} O) - or _{- ((CH 2) yCH (} CH 3) O) - is a terminal on the side of oxygen atom The form which couple | bonds with this X is preferable.

The compounds represented by the general formula (Z-4) or (Z-5) may be used singly or in combination of two or more. In particular, in general formula (ii), the form whose all 6 X is acryloyl group is preferable.

Moreover, as total content in the polymeric compound of the compound represented by general formula (Z-4) or general formula (Z-5), 20 mass% or more is preferable, and 50 mass% or more is more preferable.

Compound represented by the general formula (Z-4) or (Z-5) is a pentaerythritol or dipentaerythritol, which is a conventionally known process to bond the ring-opening skeleton by ring-opening addition reaction of ethylene oxide or propylene oxide It can synthesize | combine from a process and the process of introducing a (meth) acryloyl group by making (meth) acryloyl chloride react with the terminal hydroxyl group of a ring-opening skeleton, for example. Each step is a well known step, and a person skilled in the art can easily synthesize a compound represented by formula (i) or (ii).

Among the compounds represented by the general formula (Z-4) or (Z-5), pentaerythritol derivatives and / or dipentaerythritol derivatives are more preferable.

Specifically, the compound (henceforth a "exemplary compound (a)-(f)") represented by following formula (a)-(f) is mentioned, Especially, exemplary compound (a), (b) , (e) and (f) are preferred.

As a commercial item of the polymeric compound represented by general formula (Z-4) and (Z-5), for example, SR-494 which is a tetrafunctional acrylate which has four ethyleneoxy chains of the Sartomer Company, Nippon TPA-330, a trifunctional acrylate having three isobutyleneoxy chains and DPCA-60, which is a six-functional acrylate having six pentyleneoxy chains manufactured by Nippon Kayaku Co., Ltd. Etc. can be mentioned.

Moreover, as a polymeric compound, urethane acrylates described in Unexamined-Japanese-Patent No. 48-41708, Unexamined-Japanese-Patent No. 51-37193, Unexamined-Japanese-Patent No. 2-32293, and Unexamined-Japanese-Patent No. 2-16765, Also preferred are urethane compounds having an ethylene oxide-based skeleton described in Japanese Patent Publication No. 58-49860, Japanese Patent Publication No. 56-17654, Japanese Patent Publication No. 62-39417, and Japanese Patent Publication No. 62-39418. As the polymerizable compound, addition polymerizable compounds having an amino structure or sulfide structure in the molecules described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 can be used. By using it, the coloring radiation sensitive composition which is very excellent in the photosensitive speed can be obtained.

As a commercial item of a polymeric compound, urethane oligomer UAS-10, UAB-140 (made by Nippon Paper Industries Co., Ltd.), UA-7200 "(made by Shin-nakamura Chemical Co. Ltd., DPHA) -40H (made by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (made by Kyoeisha), etc. are mentioned.

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 final performance design of a colored radiation-sensitive composition. For example, a structure with many unsaturated group content per molecule is preferable from a viewpoint of a sensitivity, and in many cases, bifunctional or more is preferable. In addition, from the viewpoint of increasing the strength of the colored radiation-sensitive composition film, a trifunctional or higher functional group may be used, and those of other functional groups and other polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrene compound, and vinyl ether compound) may be used. The method of adjusting both sensitivity and intensity by using together is also effective. In addition, it is preferable to use a polymerizable compound having a different ethylene oxide chain length in combination with a trifunctional or higher functional group from the viewpoint that the developability of the colored radiation-sensitive composition can be adjusted and an excellent pattern forming ability can be obtained.

In addition, the selection and use of the polymerizable compound are also important factors in terms of compatibility and dispersibility with other components (eg, photopolymerization initiator, dispersion, alkali-soluble resin, etc.) contained in the colored radiation-sensitive composition. For example, compatibility may be improved by using a low purity compound or using 2 or more types together. Moreover, a specific structure can also be selected from a viewpoint of improving adhesiveness with hard surfaces, such as a support body.

As for content of the polymeric compound in the colored radiation-sensitive composition of this invention, 0.1 mass%-70 mass% are preferable with respect to the total solid in a colored radiation-sensitive composition, 1.0 mass%-50 mass% are further more preferable, 2.0 mass%-40 mass% are especially preferable.

<(D) Photoinitiator>

It is preferable that the colored radiation-sensitive composition of this invention contains the (D) photoinitiator.

As (D) photoinitiator (it may only call "polymerization initiator" hereafter) in this invention, what is known as a photoinitiator demonstrated below can be used.

There is no restriction | limiting in particular as a photoinitiator in this invention as long as it has the ability to start superposition | polymerization of the said polymeric compound, It can select suitably from well-known photoinitiators. For example, it is preferable to have photosensitivity to visible light from an ultraviolet region. Moreover, it may be an activator which generates an active radical by generating any action with a photoexcited sensitizer, or may be an initiator that initiates cationic polymerization depending on the type of monomer.

The photopolymerization initiator preferably contains at least one compound having a molecular extinction coefficient of at least about 50 in the range of about 300 nm to 800 nm (330 nm to 500 nm is more preferable).

As (D) photoinitiator in this invention, acylphosphine compounds, such as a halogenated hydrocarbon derivative (for example, having a triazine skeleton, having an oxadiazole skeleton, etc.), acylphosphine oxide, etc. And oxime compounds such as hexaarylbiimidazole and oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketooxime ethers, aminoacetophenone compounds and hydroxyacetophenones. Among these, an oxime compound is preferable.

As a halogenated hydrocarbon compound which has the said triazine skeleton, For example, Wakabayashi etc., Bull. Chem. Soc. J. by the compound described in Japan, 42, 2924 (1969), the compound described in British Patent 1388492 specification, the compound described in Japanese Patent Laid-Open No. 53-133428, the compound described in German Patent 3337024, FC Schaefer and the like. Org. Chem .; 29, 1527 (1964), the compound described in JP 62-58241, the compound described in JP 5-281728, the compound described in JP 5-34920 A, US The compound described in patent 4212976 specification, etc. are mentioned.

As a compound described in the said US patent 4212976, the compound which has an oxadiazole skeleton (for example, 2-trichloromethyl-5-phenyl-1,3,4-oxadiazole, 2 -Trichloromethyl-5- (4-chlorophenyl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (1-naphthyl) -1,3,4-oxadiazole, 2 -Trichloromethyl-5- (2-naphthyl) -1,3,4-oxadiazole, 2-tribromomethyl-5-phenyl-1,3,4-oxadiazole, 2-tribromo Methyl-5- (2-naphthyl) -1,3,4-oxadiazole; 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (4-chlorstyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (4-methoxystyryl) -1,3,4-oxadiazole, 2-trichloromethyl -5- (1-naphthyl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (4-n-butoxystyryl) -1,3,4-oxadiazole, 2 -Tribromomethyl-5-styryl-1,3,4-oxadiazole etc.) etc. are mentioned.

Moreover, as a polymerization initiator of that excepting the above, an acridine derivative (For example, 9-phenylacridine, 1,7-bis (9,9'- acrindinyl) heptane, etc.), N-phenylglycine, Poly, etc. Halogen compounds (e.g., carbon tetrabromide, phenyltribromomethylsulfone, phenyltrichloromethylketone, etc.), coumarins (e.g. 3- (2-benzofuranoyl) -7-diethylaminocoumarin, 3- (2-benzofuroyl) -7- (1-pyrrolidinyl) coumarin, 3-benzoyl-7-diethylaminocoumarin, 3- (2-methoxybenzoyl) -7-diethylaminocoumarin, 3 -(4-dimethylaminobenzoyl) -7-diethylaminocoumarin, 3,3'-carbonylbis (5,7-di-n-propoxycoumarin), 3,3'-carbonylbis (7-di Ethylaminocoumarin), 3-benzoyl-7-methoxycoumarin, 3- (2-furoyl) -7-diethylaminocoumarin, 3- (4-diethylaminocinnamoyl) -7-diethylaminocoumarin, 7-methoxy-3- (3-pyridylcarbonyl) coumarin, 3-benzoyl-5,7-dipropoxycoumarin, 7-benzotriazole-2-ylcouma Rin also discloses Japanese Patent Application Laid-Open No. 5-19475, Japanese Patent Application Laid-Open No. 7-271028, Japanese Patent Application Laid-Open No. 2002-363206, Japanese Patent Application Laid-Open No. 2002-363207, Japanese Patent Application Laid-Open No. 2002-363208 , Coumarin compounds and the like described in JP-A-2002-363209 and the like), acylphosphine oxides (for example, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dime) Methoxybenzoyl) -2,4,4-trimethyl-pentylphenylphosphine oxide, LucirinTPO and the like), metallocenes (for example, bis (η5-2,4-cyclopentadien-1-yl) -bis (2 , 6-difluoro-3- (1H-pyrrole-1-yl) -phenyl) titanium, η5-cyclopentadienyl-η6-cumenyl-iron (1 +)-hexafluorophosphate (1-) and the like ), Japanese Patent Application Laid-Open No. 53-133428, Japanese Patent Publication No. 57-1819, Japanese Patent Application Laid-Open No. 57-6096, and the compound described in US Patent No. 3615455 specification.

As said ketone compound, for example, benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 4-methoxybenzophenone, 2-chlorobenzophenone, 4-chlorobenzophenone, 4- Bromobenzophenone, 2-carboxybenzophenone, 2-ethoxycarbonylbenzophenone, benzophenone tetracarboxylic acid or tetramethyl ester thereof, 4,4'-bis (dialkylamino) benzophenone (for example , 4,4'-bis (dimethylamino) benzophenone, 4,4'-bisdicyclohexylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4,4'-bis (di Hydroxyethylamino) benzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 4,4'-dimethoxybenzophenone, 4-dimethylaminobenzophenone, 4-dimethylaminoacetophenone, benzyl, anthraquinone, 2-t-butylanthraquinone, 2-methylanthraquinone, phenanthraquinone, xanthone, thioxanthone, 2-chlor- thioxanthone, 2,4-diethyl thioxanthone, fluolenone, 2-benzyl -dimethyl Amino-1- (4-morpholinophenyl) -1-butanone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propaneone, 2-hydroxy- 2-methyl- [4- (1-methylvinyl) phenyl] propanol oligomer, benzoin, benzoin ethers (for example, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether) , Benzoin phenyl ether, benzyl dimethyl ketal), acridon, chloroacridone, N-methylacridone, N-butylacridone, N-butyl-chloroacridone and the like.

As the polymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can also be preferably used. More specifically, for example, the aminoacetophenone initiators described in JP-A-10-291969 and the acylphosphine oxide initiators described in JP-A-4225898 can be used.

As the hydroxyacetophenone-based initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (trade names: all manufactured by BASF) can be used. As the aminoacetophenone-based initiator, commercial products IRGACURE-907, IRGACURE-369, and IRGACURE-379 (all trade names, manufactured by BASF) can be used. As an aminoacetophenone type initiator, the compound of Unexamined-Japanese-Patent No. 2009-191179 which the absorption wavelength matched to longwave light sources, such as 365 nm or 405 nm, can also be used. Moreover, as an acyl phosphine type initiator, IRGACURE-819 and DAROCUR-TPO (all of brand names: BASF Corporation make) which are commercial items can be used.

More preferably, an oxime compound is mentioned as a polymerization initiator. As a specific example of an oxime compound, the compound of Unexamined-Japanese-Patent No. 2001-233842, the compound of Unexamined-Japanese-Patent No. 2000-80068, and the compound of Unexamined-Japanese-Patent No. 2006-342166 can be used.

Examples of oxime compounds such as oxime derivatives which are preferably used as the polymerization initiator in the present invention include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one and 3-propionyloxyiminobutane. 2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4 -Toluenesulfonyloxy) iminobutan-2-one, 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one, etc. are mentioned.

Examples of oxime compounds are JCS Pervinin II (1979) pp. 1653-1660), JCS Pervinin II (1979) pp.156-162, Journal of Photopolymer Science and Technology (1995) pp.202-232, Japanese Patent Publication 2000 The compound of Unexamined-Japanese-Patent No. -66385, Unexamined-Japanese-Patent No. 2000-80068, Unexamined-Japanese-Patent No. 2004-534797, Unexamined-Japanese-Patent No. 2006-342166, etc. are mentioned.

In a commercial item, IRGACURE OXE-01 (made by BASF Corporation) and IRGACURE OXE-02 (made by BASF Corporation) are also used preferably.

In addition, the compound described in JP-A-2009-519904 in which an oxime is linked to the N position of carbazole as the oxime compound other than the above, the compound described in U.S. Patent 7626957 in which a hetero substituent is introduced into the benzophenone moiety, and the nitro to the pigment moiety. A compound containing the compounds described in Japanese Patent Application Laid-Open No. 2010-15025 and US Patent Publication No. 2009-292039, a ketooxime compound described in International Publication No. 2009-131189, a triazine skeleton and an oxime skeleton in the same molecule The compound described in U.S. Patent 7556910, the compound described in JP-A-2009-221114, which has an absorption maximum at 405 nm and has a good sensitivity to a g-ray light source, may be used.

Preferably, it can also use suitably also about the cyclic oxime compound of Unexamined-Japanese-Patent No. 2007-231000, and Unexamined-Japanese-Patent No. 2007-322744. Among the cyclic oxime compounds, in particular, the cyclic oxime compounds condensed with the carbazole dyes described in JP 2010-32985 A and JP 2010-185072 A have high light absorptivity and are preferable from the viewpoint of high sensitivity.

Moreover, the compound described in Unexamined-Japanese-Patent No. 2009-242469 which has an unsaturated bond in the specific site of an oxime compound can also achieve high sensitivity by regenerating an active radical from a polymerization inert radical, and can use it preferably.

Most preferably, the oxime compound which has a specific substituent shown by Unexamined-Japanese-Patent No. 2007-269779, and the oxime compound which has a thioaryl group shown by Unexamined-Japanese-Patent No. 2009-191061 are mentioned.

Specifically, as an oxime compound, the compound represented by a following formula (OX-1) is preferable. The N-O bond of the oxime may be an oxime compound of the (E) form or an oxime compound of the (Z) form, or a mixture of the form (E) form and the form (Z) form.

(In the formula (OX-1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group.

In the formula (OX-1), the monovalent substituent represented by R is preferably a monovalent nonmetallic atom group.

Examples of the monovalent nonmetallic atom group include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group and an arylthiocarbonyl group. In addition, these groups may have one or more substituents. Further, the substituent described above may be further substituted with another substituent.

Examples of the substituent include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group and an aryl group.

As an alkyl group which may have a substituent represented by R, a C1-C30 alkyl group is preferable, and specifically a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, an octadecyl group , Isopropyl group, isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, cyclopentyl group, cyclohexyl group, trifluoromethyl group, 2-ethylhexyl group, phenacyl group, 1-naph Toylmethyl group, 2-naphthoylmethyl group, 4-methylsulfanylphenacyl group, 4-phenylsulfanylphenacyl group, 4-dimethylaminophenacyl group, 4-cyanophenacyl group, 4-methylphenacyl group, 2-methylphenacyl group , 3-fluorophenacyl group, 3-trifluoromethylphenacyl group, and 3-nitrophenacyl group can be illustrated.

As an aryl group which may have a substituent represented by R, a C6-C30 aryl group is preferable, Specifically, a phenyl group, a biphenyl group, 1-naphthyl group, 2-naphthyl group, 9- anthryl group, 9-phenan Trilyl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azulenyl group, 9-fluorenyl group, terphenyl group, quarterphenyl group, o-tolyl group, m-tolyl group, p-tol Aryl group, xylyl group, o-cumenyl group, m-cumenyl group and p-cumenyl group, mesityl group, pentalenyl group, vinaphthalenyl group, ternaphthalenyl group, quarter naphthalenyl group, heptarenyl group, biphenylen Neyl group, indasenyl group, fluoranthhenyl group, acenaphthylenyl group, aceanthrylenyl group, penalenyl group, fluolenyl group, anthryl group, bianthracenyl group, teranthracenyl group, quarterantracenyl group, anthraqui Nolyl group, phenanthryl group, triphenylenyl group, philenyl group, chrysenyl group, naphthacenyl group, preadenyl group, picenyl group, perylenyl group, Pentaphenyl group, pentaxenyl group, tetraphenylenyl group, hexaphenyl group, hexasenyl group, rubisenyl group, colonenyl group, trinaphthylenyl group, heptaphenyl group, heptathenyl group, pyrantrenyl group, and ovalenyl group Can be.

As an acyl group which may have a substituent represented by R, a C2-C20 acyl group is preferable, Specifically, an acetyl group, propanoyl group, butanoyl group, trifluoroacetyl group, pentanyl group, benzoyl group, 1- Naphthoyl group, 2-naphthoyl group, 4-methylsulfanylbenzoyl group, 4-phenylsulfanylbenzoyl group, 4-dimethylaminobenzoyl group, 4-diethylaminobenzoyl group, 2-chlorobenzoyl group, 2-methyl Benzoyl group, 2-methoxybenzoyl group, 2-butoxybenzoyl group, 3-chlorobenzoyl group, 3-trifluoromethylbenzoyl group, 3-cyanobenzoyl group, 3-nitrobenzoyl group, 4-fluorobenzo Diary, 4-cyanobenzoyl group, and 4-methoxybenzoyl group can be illustrated.

As an alkoxycarbonyl group which may have a substituent represented by R, a C2-C20 alkoxycarbonyl group is preferable, Specifically, a methoxycarbonyl group, an ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, hexyloxycarbonyl group, octyloxycarbonyl group , Decyloxycarbonyl group, octadecyloxycarbonyl group, and trifluoromethyloxycarbonyl group can be illustrated.

Specific examples of the aryloxycarbonyl group which may have a substituent represented by R include a phenoxycarbonyl group, 1-naphthyloxycarbonyl group, 2-naphthyloxycarbonyl group, 4-methylsulfanylphenyloxycarbonyl group, 4-phenylsulfanylphenyl Oxycarbonyl group, 4-dimethylaminophenyloxycarbonyl group, 4-diethylaminophenyloxycarbonyl group, 2-chlorophenyloxycarbonyl group, 2-methylphenyloxycarbonyl group, 2-methoxyphenyloxycarbonyl group, 2-butoxyphenyloxycarbonyl group, 3 -Chlorophenyloxycarbonyl group, 3-trifluoromethylphenyloxycarbonyl group, 3-cyanophenyloxycarbonyl group, 3-nitrophenyloxycarbonyl group, 4-fluorophenyloxycarbonyl group, 4-cyanophenyloxycarbonyl group, and 4-meth A oxyphenyl oxycarbonyl group can be illustrated.

As the heterocyclic group which may have a substituent represented by R, an aromatic or aliphatic heterocycle including a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom is preferable.

Specifically, thienyl group, benzo [b] thienyl group, naphtho [2, 3-b] thienyl group, thianthrenyl group, furyl group, pyranyl group, isobenzofuranyl group, clomenyl group, xanthenyl group, phenoxa Thiynyl group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolidinyl group, isoindolinyl group, 3H-indolyl group, Indolyl group, 1H-indazolyl group, prinyl group, 4H-quinolidinyl group, isoquinolyl group, quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxalinyl group, quinazolinyl group, cinnaolinyl group, Pterridinyl group, 4aH-carbazolyl group, carbazolyl group, β-carbolinyl group, phenantridinyl group, acridinyl group, perimidinyl group, phenanthrolinyl group, phenazinyl group, phenarsazinyl group, Isothiazolyl group, phenothiadinyl group, isoxazolyl group, prazanyl group, phenoxazinyl group, isochromenyl group, chromanyl group, pyrrolidinyl group, py Linyl, imidazolidinyl, imidazolinyl, pyrazolidinyl, pyrazolinyl, piperidyl, piperazinyl, indolinyl, isoindolinyl, quinukridinyl, morpholinyl, And thioxanthryl groups.

Specific examples of the alkylthiocarbonyl group which may have a substituent represented by R include methylthiocarbonyl group, propylthiocarbonyl group, butylthiocarbonyl group, hexylthiocarbonyl group, octylthiocarbonyl group, decylthiocarbonyl group, octadecylthiocarbonyl group, and trifluoro. A methylthiocarbonyl group can be illustrated.

Specific examples of the arylthiocarbonyl group which may have a substituent represented by R include 1-naphthylthiocarbonyl group, 2-naphthylthiocarbonyl group, 4-methylsulfanylphenylthiocarbonyl group, 4-phenylsulfanylphenylthiocarbonyl group, 4 -Dimethylaminophenylthiocarbonyl group, 4-diethylaminophenylthiocarbonyl group, 2-chlorophenylthiocarbonyl group, 2-methylphenylthiocarbonyl group, 2-methoxyphenylthiocarbonyl group, 2-butoxyphenylthiocarbonyl group, 3-chlorophenylthio Carbonyl group, 3-trifluoromethylphenylthiocarbonyl group, 3-cyanophenylthiocarbonyl group, 3-nitrophenylthiocarbonyl group, 4-fluorophenylthiocarbonyl group, 4-cyanophenylthiocarbonyl group, and 4-methoxyphenylthiocarbonyl group Can be mentioned.

In the formula (OX-1), the monovalent substituent represented by B represents an aryl group, a heterocyclic group, an arylcarbonyl group or a heterocyclic carbonyl group. In addition, these groups may have one or more substituents. As the substituent, the above-mentioned substituent can be exemplified. Further, the substituent described above may be further substituted with another substituent.

Especially, especially preferably, it is a structure shown below.

In the following structure, Y, X, and n are synonymous with Y, X, and n in Formula (OX-2) mentioned later, and a preferable example is also the same.

In said Formula (OX-1), a C1-C12 alkylene group, a cycloalkylene group, an alkynylene group is mentioned as a bivalent organic group represented by A. In addition, these groups may have one or more substituents. As the substituent, the above-mentioned substituent can be exemplified. Further, the substituent described above may be further substituted with another substituent.

Especially, as A in Formula (OX-1), since it improves a sensitivity and suppresses coloring by heat-time-lapse, an unsubstituted alkylene group, an alkyl group (for example, a methyl group, an ethyl group, tert- butyl group, Alkylene group substituted with dodecyl group), Alkylene group substituted with alkenyl group (for example, vinyl group, allyl group), aryl group (for example, phenyl group, p-tolyl group, xylyl group, cumenyl group, naph Preference is given to alkylene groups substituted with a butyl group, anthryl group, phenanthryl group, styryl group).

As said aryl group represented by Ar in said Formula (OX-1), a C6-C30 aryl group is preferable and may have a substituent. As a substituent, the thing similar to the substituent introduce | transduced into the substituted aryl group listed as the specific example of the aryl group which may have a substituent can be illustrated.

Especially, a substituted or unsubstituted phenyl group is preferable at the point which raises a sensitivity and suppresses coloring by heating time-lapse.

In the formula (OX-1), it is preferable from the viewpoint of sensitivity that the structure of "SAr" formed from Ar in the formula (OX-1) and S adjacent thereto is the following structure. Me represents a methyl group, and Et represents an ethyl group.

It is preferable that an oxime compound is a compound represented by a following formula (OX-2).

(In the formula (OX-2), each of R and X independently represents a monovalent substituent, A and Y each independently represent a divalent organic group, Ar represents an aryl group, and n represents an integer of 0 to 5)

R, A, and Ar in Formula (OX-2) are synonymous with R, A, and Ar in Formula (OX-1), and preferred examples thereof are also the same.

Examples of the monovalent substituent represented by X in the above formula (OX-2) include alkyl, aryl, alkoxy, aryloxy, acyloxy, acyl, alkoxycarbonyl, amino, heterocyclic and halogen . In addition, these groups may have one or more substituents. As the substituent, the above-mentioned substituent can be exemplified. Further, the substituent described above may be further substituted with another substituent.

Among them, X in the formula (OX-2) is preferably an alkyl group in terms of solvent solubility and absorption efficiency in a long wavelength region.

In addition, n in Formula (2) represents the integer of 0-5, and the integer of 0-2 is preferable.

In the formula (OX-2), examples of the divalent organic group represented by Y include the structures shown below. In addition, in the group shown below, "*" shows a coupling | bonding position with the carbon atom adjacent to Y in said Formula (OX-2).

Especially, the structure shown below from the viewpoint of high sensitivity is preferable.

Moreover, it is preferable that an oxime compound is a compound represented by a following formula (OX-3).

(In the formula (OX-3), each of R and X independently represents a monovalent substituent, A represents a divalent organic group, Ar represents an aryl group, and n represents an integer of 0 to 5)

R, X, A, Ar and n in formula (OX-3) are respectively the same as R, X, A, Ar and n in formula (OX-2)

Hereinafter, although the specific example of the oxime compound used preferably is shown below, this invention is not limited to these.

The oxime compound has a maximum absorption wavelength in the wavelength region of 350 nm to 500 nm, preferably has an absorption wavelength in the wavelength region of 360 nm to 480 nm, and particularly preferably has high absorbance at 365 nm and 455 nm.

The oxime compound preferably has a molar extinction coefficient at 365 nm or 405 nm from 1,000 to 300,000, more preferably from 2,000 to 300,000, and particularly preferably from 5,000 to 200,000 from the viewpoint of sensitivity.

Although the molar extinction coefficient of a compound can use a well-known method, Specifically, it is measured by the ultraviolet visible spectrophotometer (Carry-5 spctrophotometer by Varian company) using the ethyl acetate solvent at the density | concentration of 0.01 g / L, for example. desirable.

You may use the polymerization initiator used for this invention in combination of 2 or more type as needed.

As a (D) polymerization initiator used for the colored radiation-sensitive composition of this invention, a trihalomethyl triazine compound, the benzyl dimethyl ketal compound, the (alpha)-hydroxy ketone compound, the (alpha)-amino ketone compound, the acyl phos from the viewpoint of exposure sensitivity. Fin compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes And a salt, a halomethyloxadiazole compound, or a compound selected from the group consisting of a 3-aryl substituted coumarin compound.

More preferably, they are a trihalomethyl triazine compound, an α-amino ketone compound, an acyl phosphine compound, a phosphine oxide compound, an oxime compound, a triarylimidazole dimer, an onium compound, a benzophenone compound, an acetophenone compound, At least one compound selected from the group consisting of a trihalomethyltriazine compound, an α-aminoketone compound, an oxime compound, a triarylimidazole dimer, and a benzophenone compound is most preferred.

In particular, when the colored radiation-sensitive composition of the present invention is used for the production of a color filter of a solid-state imaging device, it is important to form a fine pattern in a sharp shape, and therefore it is important to develop the unexposed portion without any residue with curability. It is especially preferable to use an oxime compound as a polymerization initiator from such a viewpoint. In particular, in the case of forming a fine pattern in a solid-state imaging device, stepper exposure is used for curing exposure, but this exposure machine may be damaged by halogen, and the addition amount of the polymerization initiator needs to be kept low, so these points In consideration of the above, it is most preferable to use an oxime compound as the (D) polymerization initiator in order to form the same fine pattern as the solid-state imaging device.

It is preferable that content of the (D) polymerization initiator contained in the colored radiation-sensitive composition of this invention is 0.1 mass% or more and 50 mass% or less with respect to the total solid of a colored radiation sensitive composition, More preferably, it is 0.5 mass% or more. It is mass% or less, More preferably, it is 1 mass% or more and 15 mass% or less. Within this range, good sensitivity and pattern formability are obtained.

<Increase / decrease>

The colored radiation-sensitive composition of the present invention may contain a sensitizer for the purpose of improving the generation efficiency of the initiator and increasing the wavelength of the photosensitive wavelength. As a sensitizer, the sensitizer which has an absorption wavelength in the wavelength range of 300 nm-450 nm is mentioned.

As the sensitizer, for example, phenanthrene, anthracene, pyrene, perylene, triphenylene, polynuclear aromatics such as 9,10-dialkoxyanthracene, fluorescein, eosin, erythrosin, rhodamine B, rose bengal and Same xanthenes, thioxanthones, cyanines, merocyanines, phthalocyanines, thionines, methylene blue, thiazines such as toluidine blue, acridines, anthraquinones, squalanes, coumarins, phenoti Azines, phenazines, styrylbenzenes, azo compounds, diphenylmethane, triphenylmethane, distyrylbenzenes, carbazoles, porphyrins, spiro compounds, quinacridones, indigo, styryls, pyryllium compounds, fatigue Heterocycles such as methene compounds, pyrazolotriazole compounds, benzothiazole compounds, barbituric acid derivatives, thiobarbituric acid derivatives, aromatic ketone compounds such as acetophenone, benzophenone, mihilerketone, and N-aryloxazolidinoneThere may be mentioned compounds and the like.

<Chain transfer agent>

It is preferable to add a chain transfer agent to the colored radiation-sensitive composition of the present invention depending on the photopolymerization initiator to be used. Examples of the chain transfer agent include N, N-dialkylaminobenzoic acid alkyl esters and thiol compounds, and examples of the thiol compounds include 2-mercaptobenzothiazole, 2-mercapto-1-phenylbenzimidazole, and 3-mercapto. Propionic acid etc. can be used individually or in mixture of 2 or more types.

<Alkali-soluble resin>

It is also preferable that the colored radiation-sensitive composition of this invention contains alkali-soluble resin further. Developability and pattern formability improve by containing alkali-soluble resin.

As alkali-soluble resin, it is a linear organic high molecular polymer different from a specific binder, Alkali-soluble resin which has group which promotes at least 1 alkali solubility in a molecule | numerator (preferably an acryl-type copolymer and the molecule which has a styrene-type copolymer as a main chain). You can choose from among them. From the viewpoint of heat resistance, polyhydroxy styrene resin, polysiloxane resin, acrylic resin, acrylamide resin, and acryl / acrylamide copolymer resin are preferable, and acryl resin, acrylamide resin, acryl / Acrylamide copolymer resins are preferred.

Examples of the group which promotes alkali solubility (hereinafter also referred to as an acid group) include carboxyl groups, phosphoric acid groups, sulfonic acid groups, phenolic hydroxyl groups, and the like, but those which are soluble in an organic solvent and developable by a weak alkaline aqueous solution are preferable. (Meth) acrylic acid is mentioned as a especially preferable thing. These acid groups may be only one type, or may be two or more types.

As a monomer which can provide an acidic radical after the said superposition | polymerization, the monomer which has hydroxyl groups, such as 2-hydroxyethyl (meth) acrylate, the monomer which has epoxy groups, such as glycidyl (meth) acrylate, 2-isocyanate, for example The monomer etc. which have isocyanate groups, such as ethyl (meth) acrylate, etc. are mentioned. There may be only one type of monomers for introducing these acid groups, or two or more types thereof. In order to introduce an acid group into the alkali-soluble binder, for example, a monomer having an acid group and / or a monomer capable of imparting an acid group after polymerization (hereinafter sometimes referred to as a "monomer for introducing an acid group") is polymerized as a monomer component. You can do it. Moreover, when introduce | transducing an acidic radical as a monomer component the monomer which can provide an acidic radical after superposition | polymerization, the process for providing an acidic radical mentioned later, for example after polymerization is needed.

For the production of alkali-soluble resin, for example, a method by a known radical polymerization method can be applied. The polymerization conditions such as temperature, pressure, the kind and amount of the radical initiator, the kind of the solvent, and the like when preparing the alkali-soluble resin by the radical polymerization method can be easily set by those skilled in the art, and the conditions can be determined experimentally. .

As the linear organic polymer used as the alkali-soluble resin, a polymer having carboxylic acid in the side chain is preferable, and methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partial ester Alkyl-soluble phenol resins, such as maleic acid copolymer and a novolak-type resin, etc., and what added acid anhydride to the acidic cellulose derivative which has a carboxylic acid in a side chain, and the polymer which has a hydroxyl group are mentioned. In particular, the copolymer of (meth) acrylic acid and the other monomer copolymerizable with this is preferable as alkali-soluble resin. As another monomer copolymerizable with (meth) acrylic acid, an alkyl (meth) acrylate, an aryl (meth) acrylate, a vinyl compound, etc. are mentioned. As alkyl (meth) acrylate and aryl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, Pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, As vinyl compounds, such as cyclohexyl (meth) acrylate, styrene, (alpha) -methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl methacrylate , N-phenylmaleimide, N- as the N-position ring maleimide monomer described in Japanese Patent Application Laid-Open No. 10-300922, such as polystyrene macromonomer and polymethylmethacrylate macromonomer Claw-hexyl may be mentioned maleimide and the like. In addition, the other monomer copolymerizable with these (meth) acrylic acid may be only 1 type, or 2 or more types may be sufficient as it.

Moreover, you may use alkali-soluble resin which has a polymeric group in order to improve the crosslinking efficiency of the colored radiation-sensitive composition in this invention. As alkali-soluble resin which has a polymeric group, alkali-soluble resin etc. which contained an allyl group, a (meth) acryl group, an allyloxyalkyl group, etc. in a side chain are useful. Examples of the polymer containing the above-mentioned polymerizable group include DIANAL NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer6173 (COOH-containing polyurethane acrylic oligomer, Diamond Shamrock Co. Ltd.) VISCOAT R-264, KS RESIST 106 (all made by Osaka Organic Chemical Industry Ltd.), CyCLOMER P series PLACEL CF200 series (both manufactured by Daicel Kagaku Kogyo Co., Ltd.) and Ebecryl3800 (DICEL UCB Co., Ltd.) ), And the like.

As alkali-soluble resin containing these polymerizable groups, urethane modification obtained by reacting an isocyanate group and an OH group previously, leaving one unreacted isocyanate group, and also by reaction of the compound containing a (meth) acryloyl group and the acrylic resin containing a carboxyl group is carried out. A polymerizable double bond-containing acrylic resin, an acrylic group containing a carboxyl group and an unsaturated group-containing acrylic resin obtained by the reaction of a compound having both an epoxy group and a polymerizable double bond in a molecule, an acid pendant epoxy acrylate resin, and an OH group A polymerizable double bond-containing acrylic resin obtained by reacting an acrylic resin with a dibasic acid anhydride having a polymerizable double bond, an acrylic resin containing an OH group, and a resin obtained by reacting a compound having an isocyanate with a polymerizable group, Japanese Patent Laid-Open No. 2002-229207 Hobo Gazette and Japan Resin obtained by performing basic treatment with resin which has ester group which has a leaving group, such as a halogen atom or a sulfonate group, in a side position or (beta) position described in Unexamined-Japanese-Patent No. 2003-335814 in a side chain is preferable.

Especially as a alkali-soluble resin, the multicomponent copolymer which consists of a benzyl (meth) acrylate / (meth) acrylic acid copolymer and benzyl (meth) acrylate / (meth) acrylic acid / another monomer is preferable. In addition, 2-hydroxyethyl methacrylate copolymerized and 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid described in JP-A-7-140654 Copolymer, 2-hydroxy-3-phenoxypropylacrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methylmethacrylate Methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, and the like.

The acid value of the alkali-soluble resin is preferably 30 mgKOH / g to 200 mgKOH / g, more preferably 50 mgKOH / g to 150 mgKOH / g, and most preferably 70 to 120 mgKOH / g.

The weight average molecular weight (Mw) of the alkali-soluble resin is preferably 2,000 to 50,000, more preferably 5,000 to 30,000, and most preferably 7,000 to 20,000.

As for content in the colored radiation-sensitive composition of alkali-soluble resin, 1-15 mass% is preferable with respect to the total solid of the said composition, More preferably, it is 2 mass%-12 mass%, Especially preferably, it is 3 It is mass%-10 mass%. However, it is preferable that it is 50 mass% or less with respect to content of the specific binder of this invention.

<Polymerization inhibitor>

In the colored radiation-sensitive composition of the present invention, it is preferable to add a small amount of a polymerization inhibitor in order to prevent unnecessary thermal polymerization of the polymerizable compound during the production or storage of the colored radiation-sensitive composition.

Examples of the polymerization inhibitor that can be used in the present invention include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3 -Methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine 1st cerium salt, etc. are mentioned.

As for the addition amount of a polymerization inhibitor, about 0.01 mass%-about 5 mass% are preferable with respect to the mass of a colored radiation-sensitive composition.

<Substrate adhesive>

In addition, in this invention, you may add the board | substrate adhesive agent which can improve board | substrate adhesiveness to a colored radiation-sensitive composition.

It is preferable to use a silane coupling agent, a titanate coupling agent, and an aluminum coupling agent as a board | substrate adhesive agent. As the silane coupling agent, for example, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, and γ-acryloxypropyltriethoxysilane , γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, phenyltrimethoxysilane and the like. Especially, as a board | substrate adhesive agent, (gamma) -methacryloxypropyl trimethoxysilane is preferable.

It is preferable that content of a board | substrate adhesive agent is 0.1 mass% or more and 30 mass% or less with respect to the total solid of the colored radiation-sensitive composition of this invention from a viewpoint that a residue does not remain in an unexposed part when exposing and developing colored radiation-sensitive composition. It is more preferable that they are 0.5 mass% or more and 20 mass% or less, and it is especially preferable that they are 1 mass% or more and 10 mass% or less.

<Surfactant>

You may add various surfactant to the colored radiation-sensitive composition of this invention from a viewpoint of further improving applicability | paintability. As the surfactant, various surfactants such as a fluorine surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone surfactant can be used.

In particular, the colored radiation-sensitive composition of the present invention further improves the uniformity and liquid saving property of the coating thickness in that the liquid characteristic (particularly, fluidity) when prepared as a coating liquid is further improved by containing a fluorine-based surfactant. Can be.

That is, when forming a film using the coating liquid to which the colored radiation-sensitive composition containing a fluorine-type surfactant is formed, the wettability to a to-be-coated surface is improved by reducing the interfacial tension of a to-be-coated surface and a coating liquid, and apply | coating to a to-be-coated surface. Sex is improved. For this reason, even when a thin film of about several micrometers is formed with a small amount of liquid, it is effective at the point which can form film of uniform thickness with a small thickness nonuniformity more preferably.

The fluorine content in the fluorine-based surfactant is preferably 3% by mass to 40% by mass, more preferably 5% by mass to 30% by mass, particularly preferably 7% by mass to 25% by mass. The fluorine-based surfactant having a fluorine content in this range is effective in terms of uniformity and liquid saving of the thickness of the coating film, and has good solubility in the colored radiation-sensitive composition.

As a fluorine type surfactant, MEGAFACE F171, copper F172, copper F173, copper F176, copper F177, copper F141, copper F142, copper F143, copper F144, copper R30, copper F437, copper F475, copper F479 , F482, F554, F780, F781 (above, made by DIC Corporation), Fluorad (FLUORAD) FC430, FC431, East FC171 (above, Sumitomo 3M Co., Ltd. (Sumitomo 3M Limited) ))) Suplon (SURFLON) S-382, East SC-101, East SC-103, East SC-104, East SC-105, East SC1068, East SC-381, East SC-383, East S393, East KH-40 (above, Asahi Glass Co., Ltd. product) etc. are mentioned.

Specific examples of the nonionic surfactants include glycerol, trimetholpropane, trimetholethane and ethoxylates and propoxylates thereof (for example, glycerol propoxylate, glycerin ethoxylate, etc.) and polyoxyethylene. Lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (BASF PLURONIC L10, L31, L61, L62, 10R5, 17R2, 25R2, Tetronic (304, 701, 704, 901, 904, 150R1), SOLSPERSE 20000 (Nippon Lubric) Sol (The Lubrizol Corporation) etc. are mentioned.

Specific examples of the cationic surfactant include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), and organosiloxane polymer KP341 (Shin-Etsu Kagaku Kogyo Co., Ltd.) (Shin- Manufactured by Etsu Chemical Co., Ltd.), (meth) acrylic acid-based (co) polymer polyflow (POLYFLOW) No. 75, No. 90, No. 95 (made by Kyoeisha Kagaku Co., Ltd.), W001 (made by Yusho Corporation), etc. are mentioned.

Specific examples of the anionic surfactants include W004, W005, and W017 (manufactured by Yusho Corporation).

Examples of the silicone-based surfactants include "Toray Silicon DC3PA", "Toray Silicon SH7PA", "Toray Silicon DC11PA", "Toray Silicon DC11PA" manufactured by Doray Corning Toray Silicone Co., Ltd. Silicon SH21PA, Toray Silicon SH28PA, Toray Silicon SH29PA, Toray Silicon SH30PA, Toray Silicon SH8400, Momentive Performance Materials Inc., TSF-4440, TSF -4300 "," TSF-4445 "," TSF-4460 "," TSF-4452 "," KP341 "," KF6001 "," KF6002 "made by Shin-Etsu Silicone Co., Ltd." BYK307 "made by BYK Chemie , "BYK323", "BYK330", etc. are mentioned.

The surfactant may be used alone or in combination of two or more.

As for the addition amount of surfactant, 0.001 mass%-2.0 mass% are preferable with respect to the total mass of a colored radiation-sensitive composition, More preferably, it is 0.005 mass%-1.0 mass%.

<Other ingredients>

In the colored radiation-sensitive composition of the present invention, if necessary, chain transfer agents such as alkyl esters of N, N-dialkylaminobenzoic acid and 2-mercaptobenzothiazole, thermal polymerization initiators such as azo compounds and peroxide compounds, and thermal polymerization UV absorbers such as polyfunctional thiols, epoxy compounds, alkoxybenzophenones, plasticizers such as dioctylphthalate, developability enhancers such as low molecular weight organic carboxylic acids, other fillers, and the above-described specific compounds for the purpose of improving the strength and sensitivity of the component, the film. Various additives, such as a high molecular compound other than a binder and alkali-soluble resin, antioxidant, an aggregation inhibitor, can be contained.

In addition, a thermosetting agent may be added in order to increase the degree of curing of the film by post-heating after development. As a thermosetting agent, thermal polymerization initiators, such as an azo compound and a peroxide, a novolak resin, a resol resin, an epoxy compound, a styrene compound, etc. are mentioned.

Preparation of colored radiation-sensitive composition

It is preferable to prepare the colored radiation-sensitive composition of this invention using the organic solvent with each said component.

Examples of the organic solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, isoamyl acetate, isobutyl acetate, amyl formate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, Ethyl lactate, methyl oxyacetic acid, ethyl oxyacetate, oxyacetic acid butyl, methoxyacetic acid methyl, methoxyacetic acid ethyl, methoxyacetic acid butyl, ethoxyacetic acid methyl, ethoxyacetic acid ethyl, 3-oxypropionic acid, 3-oxypropionic acid Ethyl, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, 2- Methyl methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionic acid, 2-ethoxypropionic acid Methyl, 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate Methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate and the like; Ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, 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 and the like; Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and the like; Aromatic hydrocarbons such as toluene, xylene and the like.

Of these solvents, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone , Ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether acetate and the like are preferable.

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

Moreover, in preparation of the colored radiation-sensitive composition which concerns on this invention, after mixing each component for the purpose of removal of a foreign material, reduction of a defect, etc., it is preferable to filter by a filter. The filter is conventionally used without being particularly limited and used for filtration purposes. Specifically, for example, polyolefin resin such as fluorine resin such as PTFE (polytetrafluoroethylene), polyamide resin such as nylon-6, nylon-6,6, polyethylene, polypropylene (PP) (high density, And ultra high molecular weights). Among these filter materials, polyamide-based resins such as nylon-6 and nylon-6,6 and polypropylene (including high density polypropylene) are preferable.

The pore diameter of the filter is preferably about 0.01 to 7.0 µm, preferably about 0.01 to 2.5 µm, and more preferably about 0.01 to 2.0 µm. By setting it as this range, the fine foreign material which inhibits preparation of a uniform colored radiation-sensitive composition in a post process is reliably removed, and formation of a uniform and smooth colored radiation-sensitive composition is attained.

When using a filter, other filters may be combined. In that case, the filtering using a 1st filter may be performed only once, and may be performed twice or more. Further, within the above-described range, the first filter may be composed of a plurality of filters by combining filters having different pore diameters, so that the first filtering may be performed. The hole diameter here can refer to the nominal value of the filter manufacturer. Examples of commercially available filters include Nippon-Paul Co., Ltd., Advantec Toyo kaisha Ltd., Nihon Integris KK (formerly Nihon Microless Co., Ltd.) It can select from the various filters provided by Shikisha, Kitz Micro Filter Corporation, etc.

The second filter may be formed of the same material as the first filter described above.

For example, the filtering in a 1st filter may be performed only about a pigment dispersion, and after mixing another component with the said pigment dispersion to make a colored radiation-sensitive composition, you may perform 2nd filtering.

The colored radiation-sensitive composition of the present invention can be applied to color filters for liquid crystal display devices, printing inks, ink jet inks and the like in addition to color filters used for solid-state imaging devices.

The colored radiation-sensitive composition of the present invention has excellent pigment dispersion stability and developability even when it contains a high concentration of fine pigments, and thus can form a colored region having high fineness and color characteristics. It can be said that the effect is remarkable also when manufacturing, especially when forming the pixel of 0.8 micrometer or less, Preferably it is the range of 0.1 micrometer-0.5 micrometer.

Since the colored radiation-sensitive composition of the present invention has excellent dispersion stability, it is advantageous in that a thin film can be formed when it is applied to the formation of a color filter included in a liquid crystal display device having excellent color reproducibility or a solid-state imaging device having excellent resolution. In view of the above, it is preferable to prepare a form containing a pigment at a high concentration.

As the pigment concentration in the colored radiation-sensitive composition of the present invention, the total solid content of the colored radiation-sensitive composition (that is, a component except a solvent such as a pigment, a dispersion component, a resin component, a polymerizable compound, a photopolymerization initiator, and other additives) 40 mass% or more is preferable with respect to the mass of the sum total, and 45 mass% or more is more preferable.

≪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 area (coloring pattern) which uses the coloring radiation sensitive composition of this invention on a board | substrate. It is characterized by the above-mentioned.

Hereinafter, the color filter of this invention is demonstrated in detail through the manufacturing method (the manufacturing method of the color filter of this invention).

Moreover, the color filter in this invention has the colored cured film which uses the colored radiation-sensitive composition of this invention, It is preferable that the film thickness of the said colored cured film is 1.0 micrometer or less, It is more preferable that it is 0.1 micrometer-0.9 micrometer It is preferable and it is more preferable that they are 0.2 micrometer-0.8 micrometer.

Since the high resolution and high adhesiveness can be obtained by making a film thickness into 1.0 micrometer or less, it is preferable.

In the manufacturing method of the color filter in this invention, the coloring radiation sensitive composition of this invention mentioned above is used.

By using the colored radiation-sensitive composition of the present invention, excellent developability, high sensitivity and good high hardness are obtained, and thus a color filter composed of fine patterns with good shape and high resolution can be easily produced.

The manufacturing method of the color filter in this invention is provided by providing the process which pattern-exposes, develops, and forms a pattern after apply | coating the colored radiation-sensitive composition of this invention on a board | substrate. Specifically, the colored radiation-sensitive composition of the present invention is applied onto a support by a coating method such as rotational coating, flexible coating, roll coating, or the like to form a colored radiation-sensitive composition layer, and the layer is formed through a predetermined mask pattern. It can produce preferably by forming a negative coloring pattern by exposing and developing with a developing solution (image formation process). Moreover, the hardening process which hardens the coloring pattern formed as needed by heating and / or exposure may be included.

In the production of a color filter, a color filter having a desired color can be produced by repeating the image forming step (and curing step, if necessary) by the desired number of colors. As light or radiation used at this time, particularly ultraviolet rays such as g-rays, h-rays, and i-rays are preferably used.

The manufacturing method of the color filter of this invention apply | coats the colored radiation-sensitive composition of this invention on a board | substrate, and forms the colored radiation-sensitive composition layer (coloring layer) (color layer formation process), and the said colored radiation-sensitive And a step (exposure step) of exposing the composition layer in a pattern shape (exposure step) and developing and pattern-forming the colored radiation-sensitive composition layer after exposure.

<Color layer forming process>

In a colored layer formation process, the colored radiation-sensitive composition of this invention is apply | coated on a board | substrate, and the colored layer (colored radiation-sensitive composition layer) which consists of said colored radiation-sensitive composition is formed.

As a substrate which can be used for this process, the photoelectric conversion element substrate in a charge-coupled device (CCD), a complementary metal oxide semiconductor (CMOS) used for a solid-state image sensor, a silicon substrate, a liquid crystal display device, etc. are used, for example. The alkali free glass, soda glass, PYREX (R) glass, quartz glass used, and the thing which adhered the transparent conductive film to these are mentioned. These board | substrates may be provided with the black matrix which isolate | separates each pixel.

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

As a coating method of the colored radiation-sensitive composition of this invention on a board | substrate, various coating methods, such as a slit coating, an inkjet method, a rotary coating, cast coating, roll coating, and screen printing, can be applied.

As a film thickness immediately after application of the colored radiation-sensitive composition, from the viewpoint of the film thickness uniformity of the coating film and the ease of drying of the coating solvent, in terms of film thickness after drying, 0.1 µm or more and 10 µm or less are preferable, and 0.2 µm or more and 5 µm or less The following are more preferable, and 0.2 micrometer or more and 3 micrometers or less are more preferable.

Drying (prebaking) of the colored layer (colored radiation-sensitive composition layer) apply | coated on the board | substrate can be performed in 10 to 300 second at the temperature of 50 degreeC-140 degreeC in a hotplate, oven, etc.

<Exposure Step>

In an exposure process, the colored layer (colored radiation sensitive composition layer) formed in the said colored layer formation process is exposed by pattern shape.

In exposure in this process, it is preferable to perform exposure of a colored layer by exposing through a predetermined | prescribed mask pattern and hardening only the coating film part irradiated with light. Especially as radiation which can be used in exposure, radiation, such as g line | wire, h line | wire, i line | wire, is used preferably. 30mJ / cm <2> -1500mJ / cm <2> is preferable, 50mJ / cm <2> -1000mJ / cm <2> is more preferable, 80mJ / cm <2> -500mJ / cm <2> is the most preferable.

<Development Process>

By performing an alkali developing process (development process) following an exposure process, the uncured part after exposure is eluted with a developing solution, and the photocured part remains. By this developing step, a patterned film composed of pixels of each color (for example, three colors or four colors) can be formed.

The developing method may be any of a dip method, a shower method, a spray method, a puddle method and the like, and a swing method, a spin method, an ultrasonic method, or the like may be combined therewith.

Before the contact with the developing solution, the surface to be developed may be wetted with water or the like to prevent developing staining.

As a developing solution, the organic alkali developing solution which does not cause damage to a circuit of an underlayer etc. is preferable. As image development temperature, it is 20 degreeC-30 degreeC normally, and developing time is 20 to 90 second.

As an alkaline agent which a developing solution contains, for example, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1, 8-dia Organic alkaline compounds, such as xacyclo- [5,4,0] -7-undecene, inorganic compounds, such as sodium hydroxide, potassium hydroxide, sodium hydrogencarbonate, potassium hydrogencarbonate, etc. are mentioned.

As a developing solution, the alkaline aqueous solution which diluted these alkaline agents with the pure water so that a density | concentration may be 0.001 mass%-10 mass%, Preferably 0.01 mass%-1 mass% is used preferably. In addition, when the developing solution which consists of such alkaline aqueous solution is used, it generally washes (rinses) with water after image development.

Subsequently, the excess developer is washed off and dried.

Moreover, the manufacturing method of this invention includes the hardening process which hardens the coloring pattern formed as needed after a post-heating (post-baking) or after exposure, after performing the above-mentioned colored layer formation process, exposure process, and image development process. You may do it. Post-baking is the heat processing after image development for making hardening perfect, and the thermosetting process of 100 degreeC-270 degreeC is normally performed. In the case of using light, it may be performed by g-ray, h-ray, i-ray, excimer laser such as KrF or ArF, electron beam, X-ray, etc. It is preferable to carry out, and irradiation time is 10 second-180 second, Preferably it is 30 second-60 second. In the case of the combination of post-exposure and post-heating, it is preferable to perform post-exposure first.

The color filter which consists of a desired color is produced by repeating the above-mentioned colored layer formation process, exposure process, and image development process (more, the hardening process as needed) by the desired number of colors.

Since the color filter of this invention is manufactured using the coloring radiation sensitive composition of this invention which is also excellent in exposure sensitivity, the hardened composition in an exposure part is excellent in adhesiveness and developability with a board | substrate, Adhesiveness is high and the pattern which gives a desired cross-sectional shape has a fine colored pixel.

The colored radiation-sensitive composition of the present invention can be easily removed by using a known cleaning liquid even if it is attached to, for example, a nozzle of a coating device discharge part, a pipe part of a coating device, a coating device, or the like. In this case, in order to perform more efficient washing removal, it is preferable to use the above-mentioned organic solvent as a washing | cleaning liquid as the organic solvent contained in the colored radiation-sensitive composition of this invention.

Further, Japanese Patent Laid-Open No. 7-128867, Japanese Patent Laid-Open No. 7-146562, Japanese Patent Laid-Open No. 8-278637, Japanese Patent Laid-Open No. 2000-273370, Japanese Patent Laid-Open No. 2006-85140, The cleaning liquids described in Japanese Patent Application Laid-Open No. 2006-291191, Japanese Patent Application Laid-Open No. 2007-2101, Japanese Patent Application Laid-Open No. 2007-2102, Japanese Patent Application Laid-Open No. 2007-281523, and the like also wash and remove the colored radiation-sensitive composition of the present invention. It can be used preferably as a washing | cleaning liquid.

It is preferable to use alkylene glycol monoalkyl ether carboxylate or alkylene glycol monoalkyl ether as a washing | cleaning liquid.

These organic solvents which can be used as washing | cleaning liquid may be used individually, or may mix and use 2 or more types.

When mixing 2 or more types of organic solvents, the mixed solvent which mixes the organic solvent which has a hydroxyl group, and the organic solvent which does not have a hydroxyl group is preferable. The mass ratio of the organic solvent which has a hydroxyl group and the organic solvent which does not have a hydroxyl group is 1 / 99-99 / 1, Preferably it is 10 / 90-90 / 10, More preferably, it is 20 / 80-80 / 20. As a mixed solvent, it is a mixed solvent of propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME), It is especially preferable that the ratio is 60/40.

Moreover, in order to improve the permeability of the washing | cleaning liquid with respect to a colored radiation-sensitive composition, you may add surfactant mentioned above as surfactant which a colored radiation-sensitive composition can contain to a washing | cleaning liquid.

Moreover, the color filter of this invention manufactured by the manufacturing method of the color filter of this invention can be used suitably for solid-state image sensors, such as CCD and CMOS, and also image display devices, such as an electronic paper and an organic EL, And liquid crystal display devices. It is especially suitable for the solid-state image sensor of CCD and CMOS of high resolution exceeding 1 million pixels. The color filter of the present invention can also be used, for example, as a color filter disposed between the light receiving portion of each pixel constituting the CCD element and a micro lens for condensing.

&Lt; Solid state imaging device &

The solid-state image sensor in this invention is equipped with the color filter of this invention mentioned above. As a structure of the solid-state image sensor in this invention, if it is a structure with the color filter in this invention, and it is a structure which functions as a solid-state image sensor, there is no limitation in particular, For example, the following structures are mentioned.

And a transfer electrode made of a plurality of photodiodes, polysilicons, and the like constituting a light receiving region of a solid-state imaging device (CCD image sensor, CMOS image sensor, etc.) on a substrate, wherein the photodiode and the transfer electrode It has a light shielding film which consists of tungsten etc. which opened only the light-receiving part of a photodiode on it, It has a device protective film which consists of silicon nitride etc. formed on the light-shielding film and covers the light-shielding film whole surface and a photodiode light-receiving part, The solid-state imaging of this invention on the said device protective film. It is a structure which has a color filter for elements.

Moreover, the structure which has condensing means (for example, the same as a microlens etc. below) on the said device protective layer and below a color filter (side close to a support body), the structure which has a light converging means on a color filter, etc. may be sufficient.

&Quot; Liquid crystal display device &

The color filter in this invention can be used not only for the said solid-state image sensor but a liquid crystal display device, and is especially suitable for the use of a liquid crystal display device. When used for a liquid crystal display device, while containing the metal complex dye which is excellent in spectral characteristics and heat resistance as a coloring agent, there are few orientation defects of the liquid crystal molecule accompanying the fall of specific resistance, and the color tone of a display image is favorable and it is excellent in display characteristics.

For this reason, the liquid crystal display device provided with the color filter of this invention can display the high quality image which was favorable in the color tone of a display image, and was excellent in display characteristics.

For details of the definition of the display device and the details of each display device, for example, "Electronic display device (Sasaki Teruozer, Kogyo Chosakai Publishing Co., Ltd. 1990 issuance)", "Display device ( Ibuki Sumiakiser, Sangyo Tosho Publishing Co., Ltd. (issued in 1989), and the like. In addition, about a liquid crystal display device, it describes in the "next-generation liquid crystal display technology (Tatsuo Uchida editorial, 1994, high school chosakai Co., Ltd.)." 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."

You may use the color filter in this invention for the liquid crystal display device of a color TFT (thin film transistor) system. About the liquid crystal display device of a color TFT system, it describes in a "color TFT liquid crystal display (Kyoritsu Shuppan Co., Ltd. 1996 issuance), for example." In addition, the present invention provides a liquid crystal display device having an enlarged viewing angle such as a lateral electric field driving method such as IPS (In-Plane Switching), a pixel segmentation method such as MVA (Multi-domain Vertical Alignment), a super twisted nematic (STN), TN (Twisted Nematic), VA (Vertical Alignment), OCS (Optically Compensated Splay), FFS (Fringe Field Switching), R-OCB (Reflective Optically Compensated Bend), and the like.

Furthermore, the color filter in this invention can also be provided also in a bright and high-definition color-filter on array (COA) system. In the COA type liquid crystal display device, the required characteristics for the color filter layer may be required for the interlayer insulating film, that is, low dielectric constant and peeling liquid resistance, in addition to the usual required characteristics as described above. In the color filter of the present invention, since the dye multimer having excellent color is used, the color purity, light transmittance, etc. are good, and the color pattern (pixel) has excellent color tone. Can provide. Moreover, in order to satisfy the required characteristic of low dielectric constant, you may form a resin film on a color filter layer.

These image display methods are described, for example, on page 43 of `` EL, PDP, LCD Display Technology and Market Trends (Toray Research Center Research Group 2001) ''. It is described.

The liquid crystal display device provided with the color filter in this invention consists of various members, such as an electrode substrate, a polarizing film, retardation film, a backlight, a spacer, a viewing angle guarantee film, in addition to the color filter in this invention. . The color filter of this invention can be applied to the liquid crystal display device comprised from these well-known members. About these members, for example, "The market of liquid crystal display peripheral materials and chemicals (Kenta Shima Kentaro Co., Ltd. 1994 issue) of 1994 liquid crystal display", "The present situation of the liquid crystal display market and Future prospects (the lower volume) (Fuji Chimera Research Institute, Inc., 2003).

Regarding the backlight, see SID meeting Digest 1380 (2005) (A.Konno et.al), pages 18 to 24 (Shima Yasuhiro), December 25, 2005 issue of Monthly Display, and pages 25 to 30 (Yaki Takaaki). And the like.

When the color filter of the present invention is used in a liquid crystal display device, high contrast can be realized when combined with the three wavelength tubes of a conventionally known cold cathode tube, and red, green, and blue LED light sources (RGB-LEDs) are also used. By setting it as a backlight, the liquid crystal display device with high luminance, high color purity, and good color reformation can be provided.

(Example)

An Example is given to the following and this invention is demonstrated to it further more concretely. Materials, reagents, ratios, instruments, operations, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the following specific examples. In addition, in the following Examples, unless otherwise indicated, "%" and "part" represent "mass%" and "mass part", and molecular weight shows a weight average molecular weight.

Synthesis of (B) Binder

&Lt; Synthesis Example 1 &

A solution of the following composition was prepared in a dropping vessel for the monomer.

Dimethyl-2,2 '-[oxybis (methylene)] bis-2-propenoate (hereinafter referred to as "DM"). Part 13

Benzyl methacrylate (hereinafter referred to as "BzMA"); Part 63

Methyl methacrylate (hereinafter referred to as "MMA")... Part 15

· Methacrylic acid (hereinafter referred to as "MAA"). Part 38

T-butylperoxy-2-ethylhexanoate... Part Two

Diethylene glycol dimethyl ether... Part 32

The solution of the following contents was prepared in the container for dripping of a chain transfer agent.

N-dodecanethiol... Part 6

Diethylene glycol dimethyl ether... 20 copies

188 parts of diethylene glycol dimethyl ether was placed in a reaction vessel (separable flask with a cooling tube), and after nitrogen substitution, the temperature of the reaction vessel was raised to 90 ° C.

After confirming temperature stability, dropping was started from the monomer dropping container and the chain transfer agent dropping container, and the dropping of the monomer and the chain transfer agent was completed for 140 minutes while maintaining the temperature of 90 degreeC.

60 minutes after completion | finish of dripping was heated up again, the temperature of the reaction container was raised to 110 degreeC, and it maintained at 110 degreeC for 180 minutes as it is. Thereafter, the reaction vessel was replaced with air.

Next, the compound of the following compositions was thrown into the reaction container, and it was made to react for 9 hours in the state of the temperature of 110 degreeC.

· Glycidyl methacrylate (hereinafter referred to as "GMA")... Part 41

2,2'-methylenebis (4-methyl-6-t-butylphenol)... 0.2 part

Triethylamine... 0.4 part

27 parts of diethylene glycol dimethyl ethers were added after completion | finish of reaction, it cooled to room temperature, and obtained the binder (B-1).

&Lt; Synthesis Example 2 &

A solution of the following composition was prepared in a dropping vessel for the monomer.

DM… Part 22

BzMA… 70 copies

MMA… 10 copies

MAA… Part 34

T-butylperoxy-2-ethylhexanoate... Part Two

Diethylene glycol dimethyl ether... Part 34

The solution of the following contents was prepared in the container for dripping of a chain transfer agent.

N-dodecanethiol... Part 6

Diethylene glycol dimethyl ether... 20 copies

188 parts of diethylene glycol dimethyl ether was put into the reaction container (separable flask with a cooling tube), and it heated after nitrogen substitution, and raised the temperature of the reaction container to 90 degreeC.

After confirming temperature stability, dropping was started from the monomer dropping container and the chain transfer agent dropping container, and the dropping of the monomer and the chain transfer agent was completed for 140 minutes while maintaining the temperature of 90 degreeC.

60 minutes after completion | finish of dripping was heated up again, the temperature of the reaction container was raised to 110 degreeC, and it maintained at 110 degreeC for 180 minutes as it is. Thereafter, the reaction vessel was replaced with air.

Subsequently, the compound of the following compositions was thrown into the reaction container, and it was made to react at 110 degreeC for 9 hours.

· GMA… Part 43

2,2'-methylenebis (4-methyl-6-t-butylphenol)... 0.2 part

Triethylamine... 0.4 part

39 parts of diethylene glycol dimethyl ether was added after completion | finish of reaction, it cooled to room temperature, and obtained the binder (B-2).

&Lt; Synthesis Example 3 &

A solution of the following composition was prepared in a dropping vessel for the monomer.

DM… Part 22

BzMA… Part 86

MMA… Part 9

MAA… Part 27

T-butylperoxy-2-ethylhexanoate... Part Two

Diethylene glycol dimethyl ether... Part 25

The solution of the following contents was prepared in the container for dripping of a chain transfer agent.

N-dodecanethiol... Part 6

Diethylene glycol dimethyl ether... 20 copies

157 parts of diethylene glycol dimethyl ether was placed in a reaction vessel (separable flask with a cooling tube), heated after nitrogen substitution, and the temperature of the reaction vessel was raised to 90 ° C.

After confirming temperature stability, dropping was started from the monomer dropping container and the chain transfer agent dropping container, and the dropping of the monomer and the chain transfer agent was completed for 140 minutes while maintaining the temperature of 90 degreeC.

60 minutes after completion | finish of dripping was heated up again, the temperature of the reaction container was raised to 110 degreeC, and it maintained at 110 degreeC for 180 minutes as it is. Thereafter, the reaction vessel was replaced with air.

Subsequently, the compound of the following compositions was thrown into the reaction container, and it was made to react at 110 degreeC for 9 hours.

· GMA… Part 31

2,2'-methylenebis (4-methyl-6-t-butylphenol)... 0.2 part

Triethylamine... 0.4 part

72 parts of diethylene glycol dimethyl ethers were added after completion | finish of reaction, it cooled to room temperature, and obtained the binder (B-3).

&Lt; Synthesis Example 4 &

A solution of the following composition was prepared in a dropping vessel for the monomer.

DM… Part 31

BzMA… Part 73

MMA… Part 8

MAA… Part 31

T-butylperoxy-2-ethylhexanoate... Part Two

Diethylene glycol dimethyl ether... Part 36

The solution of the following contents was prepared in the container for dripping of a chain transfer agent.

N-dodecanethiol... Part 7

Diethylene glycol dimethyl ether... 20 copies

188 parts of diethylene glycol dimethyl ether was put into the reaction container (separable flask with a cooling tube), and it heated after nitrogen substitution, and raised the temperature of the reaction container to 90 degreeC.

After confirming temperature stability, dropping was started from the monomer dropping container and the chain transfer agent dropping container, and the dropping of the monomer and the chain transfer agent was completed for 140 minutes while maintaining the temperature of 90 degreeC.

It heated up again 60 minutes after completion | finish of dripping, the temperature of the reaction container was raised to 110 degreeC, and it maintained at 110 degreeC for 180 minutes as it is. Thereafter, the reaction vessel was replaced with air.

Subsequently, the compound of the following compositions was thrown into the reaction container, and it was made to react at 110 degreeC for 9 hours.

· GMA… Part 31

2,2'-methylenebis (4-methyl-6-t-butylphenol)... 0.2 part

Triethylamine... 0.4 part

30 parts of diethylene glycol dimethyl ether was added after completion | finish of reaction, and it cooled to room temperature, and obtained the binder (B-4).

&Lt; Synthesis Example 5 &

A solution of the following composition was prepared in a dropping vessel for the monomer.

BzMA… 100 copies

MMA… Part 16

MAA… Part 23

T-butylperoxy-2-ethylhexanoate... Part Two

Diethylene glycol dimethyl ether... Part 36

The solution of the following contents was prepared in the container for dripping of a chain transfer agent.

N-dodecanethiol... Part 4

Diethylene glycol dimethyl ether... 20 copies

188 parts of diethylene glycol dimethyl ether was put into the reaction container (separable flask with a cooling tube), and it heated after nitrogen substitution, and raised the temperature of the reaction container to 90 degreeC.

After confirming temperature stability, dropping was started from the monomer dropping container and the chain transfer agent dropping container, and the dropping of the monomer and the chain transfer agent was completed for 140 minutes while maintaining the temperature of 90 degreeC.

It heated up again 60 minutes after completion | finish of dripping, the temperature of the reaction container was raised to 110 degreeC, and it maintained at 110 degreeC for 180 minutes as it is. Thereafter, the reaction vessel was replaced with air.

Subsequently, the compound of the following compositions was thrown into the reaction container, and it was made to react at 110 degreeC for 9 hours.

· GMA… Part 15

2,2'-methylenebis (4-methyl-6-t-butylphenol)... 0.2 part

Triethylamine... 0.4 part

It cooled to room temperature after completion | finish of reaction, and obtained the binder (B-5).

&Lt; Synthesis Example 6 &

A solution of the following composition was prepared in a dropping vessel for the monomer.

BzMA… 106 copies

MMA… Part 22

MAA… Part 15

T-butylperoxy-2-ethylhexanoate... Part Two

Diethylene glycol dimethyl ether... Part 36

The solution of the following contents was prepared in the container for dripping of a chain transfer agent.

N-dodecanethiol... Part 4

Diethylene glycol dimethyl ether... 20 copies

167 parts of diethylene glycol dimethyl ether were put into a reaction vessel (separable flask with a cooling tube), heated after nitrogen substitution, and the temperature of the reaction vessel was raised to 90 ° C.

After confirming temperature stability, dropping was started from the monomer dropping container and the chain transfer agent dropping container, and the dropping of the monomer and the chain transfer agent was completed for 140 minutes while maintaining the temperature of 90 degreeC.

60 minutes after completion | finish of dripping was heated up again, the temperature of the reaction container was raised to 110 degreeC, and it maintained at 110 degreeC for 180 minutes as it is. It cooled to room temperature after completion | finish of reaction, and obtained binder (B-6).

Solid content of the binder (B-1)-binder (B-6) obtained from the said synthesis example was measured. In addition, the component derived from each raw material monomer was analyzed using ¹ H-NMR. In addition, the weight average molecular weight was measured by GPC. The evaluation results are shown in Table 1 below.

&Lt; Example 1 >

&Lt; Preparation of pigment dispersion >

As a colorant (A) C.I. Pigment Orange 71, part 7.8, C.I. Pigment Red 254, part 2.0, C.I. Pigment Yellow 139 is 2.0 parts, and the compound represented by following formula (1) as a pigment derivative is 1.2 weight part, and 30 wt% propylene glycol monomethyl ether acetate of a compound represented by following formula (2) as a dispersing agent (henceforth "PGMEA" The mixture consisting of 17.3 parts of solution and 69.7 parts of PGMEA as a solvent was uniformly stirred and mixed, and then dispersed in a bead mill for 12 hours using a zirconia beads of 0.5 mm in diameter to prepare a pigment dispersion.

Equation (1)

Equation (2)

<Preparation of colored radiation-sensitive composition>

11.7 parts of pigment dispersion, 2.4 parts of binder (B-1), 0.2 parts of A-DPH-12E (manufactured by Shin-Nakamura Kagaku Kogyo Co., Ltd.) as a polymerizable compound, and (D) IRGACURE as a photopolymerization initiator. 0.1 parts of OXE 01 (1.2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyl oxime)], BASF Japan Co., Ltd.), and p-methoxyphenol as a polymerization inhibitor 0.01 part, 1.0% PGMEA solution of Megapack F781 (manufactured by DIC Corporation) as a fluorine-based surfactant, 0.8 part of PGMEA as a solvent, 4.8 parts of PGMEA as a solvent, and after mixing and stirring them, a nylon filter having a pore diameter of 0.5 µm It was filtered by Paul Co., Ltd., and the coloring radiation sensitive composition was prepared.

<Film Thickness Uniformity Evaluation>

The colored radiation-sensitive composition prepared above was applied to a glass substrate by using a spin coater (manufactured by Mikasa Ltd.) to form a coating film. And the heat processing (prebaking) was performed for 120 second using the 100 degreeC hotplate so that the dry film thickness of this coating film might be set to 1.0 micrometer. The film thickness difference of the 1 cm part from the center part of this coating film, and the circumference | surroundings was measured by Dektak (made by Veeco Instruments Inc.). Based on the measured value, film thickness uniformity was evaluated according to the following evaluation criteria. It can be said that the smaller the numerical value, the better the film thickness uniformity. The evaluation results are shown in Table 2 below.

<Evaluation Criteria>

◎: film thickness difference is 30 nm or less

○: film thickness difference is greater than 30 nm and less than 50 nm

X: film thickness difference is larger than 50 nm

&Lt; Evaluation of heat resistance &

Subsequently, this coating film was irradiated with an exposure dose of 500 mJ / cm 2 using a proxy exposure machine (manufactured by Ushio Inc., Ushio Inc.), and then heated (postbaked) for 8 minutes using a 200 ° C hotplate. .

The obtained coating film was heat-processed for 60 minutes using the hotplate of 220 degreeC in air | atmosphere, and the color difference ((DELTA) E ^* ab) before and behind that was spectrophotometer MCPD-3000 (Otsuka Electronics Co., Ltd.) Measured). Based on the measured color difference (ΔE * ab), heat resistance was evaluated according to the following evaluation criteria. It can be said that heat resistance is so good that this numerical value is small. The evaluation results are shown in Table 2 below.

<Evaluation Criteria>

◎: ΔE ^* ab is 3 or less

○: ΔE ^* ab is greater than 3 and less than or equal to 10

×: ΔE ^* ab is greater than 10

<Examples 2-11, Comparative Examples 1-4>

In Example 1, except having changed the pigment dispersion liquid and the binder as shown in Table 2, it carried out similarly to Example 1, the pigment dispersion liquid, the coloring radiation sensitive composition was prepared, and the same evaluation as Example 1 was performed.

In Table 1, for example, O71 is C.I. Pigment orange 71, and R254 is C.I. Pigment Red 254, Y150 C.I. It means pigment yellow 150, respectively.

As shown in the said Table 2, the coating film produced using the colored radiation-sensitive composition of Examples 1-11 containing CI pigment orange 71 (O71) and a specific binder was excellent in film thickness uniformity and heat resistance.

Claims (13)

(A) a binder containing CI pigment orange 71, at least one selected from a red pigment and a yellow pigment, (B) a compound represented by the following general formula (1) as a copolymerization component, (C) a polymerizable compound, and (D) A colored radiation-sensitive composition containing a photoinitiator.

[In general formula (1), R <^1> and R <^2> respectively independently represents a hydrogen atom or an alkyl group.] The method of claim 1,
The said (B) binder is a colored radiation sensitive composition characterized by the binder further containing aryl (meth) acrylate or alkyl (meth) acrylate as a polymeric component. The method of claim 1,
The said (B) binder is a binder which further contains (meth) acrylic acid as a polymeric component, The colored radiation-sensitive composition characterized by the above-mentioned. 3. The method of claim 2,
The said (B) binder is a binder which further contains (meth) acrylic acid as a polymeric component, The colored radiation-sensitive composition characterized by the above-mentioned. delete delete The method of claim 1,
The said (D) photoinitiator is a colored radiation sensitive composition characterized by the above-mentioned. The colored cured film obtained by hardening | curing the colored radiation-sensitive composition in any one of Claims 1-4 and 7. The colored cured film of Claim 8 was provided. The color filter characterized by the above-mentioned. The colored radiation-sensitive composition layer forming process of providing the colored radiation-sensitive composition in any one of Claims 1-4 and 7 on a board | substrate, and forming a colored radiation-sensitive composition layer,
An exposure step of exposing the colored radiation-sensitive composition layer in a pattern;
And a coloring pattern forming step of developing the colored radiation-sensitive composition layer after exposure to form a colored pattern. The colored radiation-sensitive composition layer forming process of providing the colored radiation-sensitive composition in any one of Claims 1-4 and 7 on a board | substrate, and forming a colored radiation-sensitive composition layer,
An exposure step of exposing the colored radiation-sensitive composition layer in a pattern;
It has a coloring pattern formation process which develops the said colored radiation-sensitive composition layer after exposure, and forms a coloring pattern, The manufacturing method of the color filter characterized by the above-mentioned. A solid-state image sensor comprising the color filter according to claim 9.
The method of claim 1,
The colored radiation sensitive composition containing CI pigment orange 71, a red pigment, and a yellow pigment as said (A).