JP4884833B2 - Dye-containing negative curable composition, color filter and method for producing the same - Google Patents

Description

  The present invention relates to a dye-containing negative curable composition suitable for forming a colored image constituting a color filter used in a liquid crystal display device or a solid-state imaging device, a dye-containing color filter, and a method for producing the same.

  As a method for producing a color filter used for a liquid crystal display element (LCD) or a solid-state imaging element (CCD, CMOS, etc.), a dyeing method, a printing method, an electrodeposition method, and a pigment dispersion method are known.

  Among these, the pigment dispersion method is a method for producing a color filter by a photolithography method using a colored radiation-sensitive composition in which a pigment is dispersed in various photosensitive compositions. It has the advantage of being stable to heat and the like. Further, since patterning is performed by a photolithography method, it has been widely used as a suitable method for manufacturing a color filter for a large-screen, high-definition color display with high positional accuracy.

  When producing a color filter by a pigment dispersion method, a radiation sensitive composition is applied on a glass substrate with a spin coater or a roll coater and dried to form a coating film, and then this coating film is subjected to pattern exposure and development. A colored filter is formed, and a color filter is obtained by repeating this operation for each color according to the desired number of hues. As such a pigment dispersion method, there is one in which an example using a negative photosensitive composition in which a photopolymerizable monomer and a photopolymerization initiator are used in combination with an alkali-soluble resin is described (for example, Patent Documents 1 to 4). reference).

  On the other hand, in recent years, there has been a demand for higher definition in color filters for solid-state imaging devices. However, it is difficult to further improve the resolution with conventional pigment dispersion systems, and there are problems such as color unevenness caused by coarse particles of the pigment, so that it is used for applications that require fine patterns such as solid-state imaging devices. Was not suitable.

In view of such a problem, a technique for using a dye instead of a pigment has been proposed (for example, see Patent Document 5).
JP-A-2-181704 JP-A-2-199403 Japanese Patent Laid-Open No. 5-273411 JP-A-7-140654 JP-A-6-75375

However, a curable composition using a dye has a problem that the solubility of the dye is poor, and in general, it is inferior to a pigment in various performances such as light resistance, heat resistance and coating uniformity.
In addition, in the case of the use for producing a color filter for a solid-state image sensor, a film thickness of 1.0 μm or less is required, and therefore a large amount of dye must be added to the curable composition, and therefore, There is also a tendency that the pattern forming property is remarkably deteriorated such that the adhesion and the degree of curing are insufficient, or the dye is removed at the exposed portion forming the filter.

  The present invention has been made in view of the above, and is suitable for a constitution using a dye as a colorant, and has high sensitivity and can form a fine pattern having a rectangular cross section with high sensitivity. Composition, a color filter (especially a color filter for a solid-state image sensor) having a sharp pattern (especially a rectangle with a good cross-sectional shape) and a high resolution, and a method for producing the same It aims at providing and makes it a subject to achieve this objective.

Specific means for achieving the above object are as follows.
<1> As an (A) dye, (B) an oxime photopolymerization initiator, and (C) a radical polymerizable monomer, the acid value is 25 to 200 mgKOH / g and the viscosity is 12,000 to 100,000 mPa · s (25 ° C. The dye-containing negative curable composition containing at least an acid group-containing polyfunctional (meth) acrylic compound.
<2> The dye-containing negative curable composition according to <1>, further comprising (D) a binder resin.
<3> The dye-containing negative curable composition according to <1> or <2>, wherein the (A) dye is a mixture of at least two dyes having different absorption characteristics.
<4> Any one of the above <1> to <3>, wherein the acidic group-containing polyfunctional (meth) acrylic compound is a compound obtained by reacting a hydroxyl group of a hydroxyl group-containing pentafunctional acrylic compound to introduce the acidic group. The dye-containing negative curable composition described in 1.
<5> In any one of the above items <1> to <4>, wherein the acidic group-containing polyfunctional (meth) acrylic compound is obtained by replacing the OH moiety of dipentaerythritol pentaacrylate with a carboxyl group-containing substituent. It is a dye-containing negative curable composition as described.
<6> The dye-containing negative curable composition according to any one of <1> to <5>, wherein the content of the dye relative to the total solid content of the dye is 38% by mass or more.
<7> A color filter formed using the dye-containing negative curable composition according to any one of <1> to <6>.
<8> After applying the dye-containing negative curable composition according to any one of the above <1> to <6> on a support, exposing to light through a mask, and developing to form a pattern This is a method for manufacturing a color filter.

ADVANTAGE OF THE INVENTION According to this invention, it is suitable to set it as the structure which used dye for the coloring agent, and is high sensitivity, and the dye containing negative curable composition in which the formation of a fine pattern with a rectangular cross section is possible, and high It is possible to provide a color filter (especially a color filter for a solid-state imaging device) which is manufactured with high productivity (high cost performance), has a sharp pattern (especially, a rectangle having a good cross-sectional shape), and has a high resolution, and a manufacturing method thereof.
This is particularly effective when a pattern is formed by stepper exposure.

  Hereinafter, the dye-containing negative curable composition of the present invention, a color filter constituted using the dye-containing negative curable composition, and a method for producing the same will be described in detail.

<< Dye-containing negative curable composition >>
The dye-containing negative curable composition of the present invention contains at least (A) a dye, (B) an oxime-based photopolymerization initiator, and (C) a radical polymerizable monomer. An acidic group-containing polyfunctional (meth) acrylic compound having an acid value of 25 to 200 mgKOH / g and a viscosity of 12,000 to 100,000 mPa · s (25 ° C.) is used. Moreover, it can generally comprise using (E) organic solvent, Preferably (D) Binder resin is contained further. Furthermore, other components such as a crosslinking agent may be included as necessary.

  In the present invention, a higher sensitivity can be obtained by selecting a polyfunctional (meth) acrylic compound containing an acidic group having an acid value of 25 mgKOH / g or more as the radical polymerizable monomer of the curable dye-based composition. It is effective for forming a fine rectangular pattern.

(A) Dye The dye-containing negative curable composition of the present invention contains at least one dye. The dye can be used without any particular limitation, and can be selected from conventionally known dyes for use in color filters. Of the dyes, organic solvent-soluble dyes that are soluble in organic solvents are preferred.

  For example, Japanese Patent Application Laid-Open No. 64-90403, Japanese Patent Application Laid-Open No. 64-91102, Japanese Patent Application Laid-Open No. 1-94301, Japanese Patent Application Laid-Open No. 6-11614, No. 2592207, US Pat. No. 4,808,501. Specification, US Pat. No. 5,667,920, US Pat. No. 5,059,500, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115 And dyes described in JP-A-6-194828.

  Chemical structures include pyrazole azo, anilino azo, aryl azo, pyrazolo triazole azo, pyridone azo, etc., triphenylmethane, anthraquinone, anthrapyridone, benzylidene, oxonol, cyanine, phenothiazine, pyrrolo. Dyes such as pyrazole azomethine, xanthene, phthalocyanine, benzopyran, and indigo can be used. Particularly preferred are pyrazole azo dyes, anilinoazo dyes, pyrazolotriazole azo dyes, pyridone azo dyes, anthraquinone dyes and anthrapyridone dyes.

In the case where the resist system is developed with water or alkali, acidic dyes and / or derivatives thereof are preferable from the viewpoint of completely removing the binder and / or dye by development. In addition, direct dyes, basic dyes, mordant dyes, acid mordant dyes, azoic dyes, disperse dyes, oil-soluble dyes, food dyes, and / or derivatives thereof can also be used effectively.
Hereinafter, the acidic dye and its derivative will be described.

-Acid dyes and their derivatives-
The acidic dye is not particularly limited as long as it is a dye having an acidic group such as a sulfonic acid, a carboxylic acid, or a phenolic hydroxyl group, but is soluble in an organic solvent or a developing solution used at the time of development processing, and forms a salt with a basic compound. It is selected in consideration of all required performances such as properties, absorbance, interaction with other components in the curable composition, light resistance, heat resistance and the like.

Specific examples of acid dyes are given below. However, the present invention is not limited to these. For example,
acid alizarin violet N;
acid black 1, 2, 24, 48;
acid blue 1,7,9,15,18,23,25,27,29,40,42,45,51,62,70,74,80,83,86,87,90,92,96,103, 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, 324: 1, 335, 340;
acid chroma violet K;
acid Fuchsin;
acid green 1,3,5,9,16,25,27,50,58,63,65,80,104,105,106,109;
acid orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173;

acid red 1,4,8,14,17,18,26,27,29,31,34,35,37,42,44,50,51,52,57,66,73,80,87,88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217, 227,228,249,252,257,258,260,261,266,268,270,274,277,280,281,195,308,312,315,316,339,341,345,346,349, 382, 383, 394, 401, 412, 417, 418, 422, 426;
acid violet 6B, 7, 9, 17, 19;
acid yellow 1,3,7,9,11,17,23,25,29,34,36,38,40,42,54,65,72,73,76,79,98,99; 111,112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184 190,193,196,197,199,202,203,204,205,207,212,214,220,221,228,230,232,235,238,240,242,243,251;

Direct Yellow 2,33,34,35,38,39,43,47,50,54,58,68,69,70,71,86,93,94,95,98,102,108,109,129, 136, 138, 141;
Direct Orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;
Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;
Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;

Direct Blue 57, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119,137,149,150,153,155,156,158,159,160,161,162,164,166,167,170,171,172,173,188,189,190,192,193 194,196,198,199,200,207,209,210,212,213,214,222,228,229,237,238,242,243,244,245,247,248,250,251,252, 256, 257, 259, 260, 268, 274, 275, 293;
Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82;

Modern Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 50, 61, 62, 65;
Modern Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;
Modern Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95;
Modern Violet 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58;
Modern Blue 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83, 84;
Modern Green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53;
Food Yellow 3;
And derivatives of these dyes.

Among the above acid dyes,
acid black 24;
acid blue 23, 25, 29, 62, 80, 86, 87, 92, 138, 158, 182, 243, 324: 1;
acid orange 8, 51, 56, 74, 63, 74;
acid red 1,4,8,34,37,42,52,57,80,97,114,143,145,151,183,217,249;
acid violet 7;
acid yellow 17, 25, 29, 34, 42, 72, 76, 99, 111, 112, 114, 116, 134, 155, 169, 172, 184, 220, 228, 230, 232, 243;
acid green 25;
And the like and derivatives of these dyes are preferred.

In addition to the above,
Azo, xanthene, and phthalocyanine acid dyes are also preferred. I. Solvent Blue 44, 38; I. Solvent Orange 45; Rhodamine B, Rhodamine 110, 3-[(5-chloro-2-phenoxyphenyl) hydrazono] -3,4-dihydro-4-oxo-5-[(phenylsulfonyl) amino] -2,7-naphthyl, etc. These acid dyes and derivatives of these dyes can also be suitably used.

  As the derivative of the acidic dye, an inorganic salt of an acidic dye having an acidic group such as sulfonic acid or carboxylic acid, a salt of an acidic dye and a nitrogen-containing compound, an amide compound such as a sulfonamide of an acidic dye, or the like may be used. The dye-containing negative curable composition is not particularly limited as long as it can be dissolved when it is prepared in solution, and is soluble in the organic solvent and the developer used in the development process, absorbance, and composition. It is selected in consideration of all necessary performances such as interaction with other components, light resistance, heat resistance and the like.

The “salt of an acid dye and a nitrogen-containing compound” will be described. The method of forming a salt of an acid dye and a nitrogen-containing compound may be effective for improving the solubility of the acid dye (providing solubility in an organic solvent) and improving heat resistance and light resistance.
Nitrogen-containing compounds that form salts with acid dyes, and nitrogen-containing compounds that form amide bonds with acid dyes are soluble in salt or amide compounds in organic solvents and developers, salt-forming properties, dye absorbance / color value, It is selected in consideration of all of the interaction with other components in the composition, heat resistance as a colorant, light resistance, and the like. When selecting only from the viewpoint of absorbance and color value, the nitrogen-containing compound is preferably as low as possible in molecular weight, more preferably a molecular weight of 300 or less, more preferably a molecular weight of 280 or less, and a molecular weight of 250 or less. Particularly preferred.

  The molar ratio of nitrogen-containing compound / acid dye (hereinafter abbreviated as “n”) in “salt of acid dye and nitrogen-containing compound” will be described. n is a value that determines the molar ratio between the acidic dye molecule and the nitrogen-containing compound (amine compound) forming a counter ion, and can be freely selected according to the salt forming conditions of the acidic dye-amine compound. Specifically, a number between 0 <n ≦ 5 of the number of functional groups of the acid in the acid dye is practically used, and the solubility in organic solvents and developers, salt formation, absorbance, and curable composition It is selected in consideration of all necessary performance such as interaction with other components, light resistance, heat resistance and the like. When selecting from the standpoint of absorbance only, n is preferably a value between 0 <n ≦ 4.5, more preferably a value between 0 <n ≦ 4, and 0 <n. It is particularly preferable to take a numerical value between ≦ 3.5.

  Since the above acidic dye is an acidic dye due to the introduction of an acidic group in its structure, it can be converted to a non-acidic dye by changing its substituent. In other words, the acid dye may suitably act during alkali development, but on the other hand, it may be over-developed, and a non-acid dye may be preferably used. As the non-acidic dye, those having no acidic group of the above acidic dye can be suitably used.

  The above-mentioned dyes can be used as monochromatic dyes when constituting complementary colors such as yellow, magenta, and cyan, respectively, but when constituting primary colors such as red, green, and blue, generally two or more kinds of dyes are used. It can be used in combination. In the present invention, it can be suitably used as a mixed system (mixture) in which at least two kinds of dyes having different absorption characteristics are combined, and a primary color hue can be suitably configured.

  The content of the dye in the dye-containing negative curable composition varies depending on the dye, but is preferably 0.5 to 80% by mass, more preferably 10 to 60% by mass with respect to the total solid components of the composition. . When mixing two or more kinds of dyes, the amount of the dye to be added in the smallest amount is preferably at least 10% when the total dye amount is 100%.

(B) Photopolymerization initiator The dye-containing negative curable composition of the present invention contains at least one oxime-based photopolymerization initiator. When the dye-containing negative curable composition is formed into a negative type, the photopolymerization initiator can be contained and polymerized and cured together with a radical polymerizable monomer described later.

  The photopolymerization initiator is not particularly limited as long as it can polymerize a radical polymerizable monomer described later, but is preferably selected from the viewpoints of properties, initiation efficiency, absorption wavelength, availability, cost, and the like.

  Examples of the photopolymerization initiator include at least one active halogen compound selected from a halomethyl oxadiazole compound and a halomethyl-s-triazine compound, a 3-aryl-substituted coumarin compound, a lophine dimer, a benzophenone compound, and an acetophenone compound. And derivatives thereof, cyclopentadiene-benzene-iron complex and salts thereof, and oxime compounds.

  Examples of halomethyloxadiazole compounds that are active halogen compounds include 2-halomethyl-5-vinyl-1,3,4-oxadiazole compounds described in JP-B-57-6096, 2-trichloromethyl- 5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (p-cyanostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (p-methoxystyryl) ) -1,3,4-oxadiazole.

  Examples of the halomethyl-s-triazine compound which is an active halogen compound include vinyl-halomethyl-s-triazine compounds described in JP-B-59-1281 and 2- (2) described in JP-A-53-133428. Naphth-1-yl) -4,6-bis-halomethyl-s-triazine compound and 4- (p-aminophenyl) -2,6-di-halomethyl-s-triazine compound.

  Specifically, 2,4-bis (trichloromethyl) -6-p-methoxystyryl-s-triazine, 2,6-bis (trichloromethyl) -4- (3,4-methylenedioxyphenyl) -1 , 3,5-triazine, 2,6-bis (trichloromethyl) -4- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (1-p -Dimethylaminophenyl-1,3-butadienyl) -s-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyryl-s-triazine, 2- (naphth-1-yl) -4,6- Bis-trichloromethyl-s-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-ethoxy-naphth-1-yl)- , 6-Bis-trichloromethyl-s-triazine, 2- (4-butoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2-methoxyethyl) -Naphth-1-yl] -4,6-bis-trichloromethyl-s-triazine,

2- [4- (2-Ethoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2-butoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- (2-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-methoxy-5- Methyl-naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-methoxy-naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2 -(5-Methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4,7-dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl -S-triazine, 2- 6-Ethoxy-naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4,5-dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s -Triazine,

4- [pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-methyl-pN, N-di (ethoxycarbonyl) Methyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine 4- [o-methyl-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (pN-chloroethylaminophenyl) -2 , 6-Di (trichloromethyl) -s-triazine, 4- (p-N-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- [p-N, -Di (phenyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (pN-chloroethylcarbonylaminophenyl) -2,6-di (trichloromethyl) -s-triazine ,

4- [pN- (p-methoxyphenyl) carbonylaminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [mN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-bromo-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s- Triazine, 4- [m-chloro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-fluoro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-bromo-pN, N-di (ethoxycarbonylmethyl) Minophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-chloro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl)- s-triazine,

4- [o-fluoro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-bromo-pN, N- Di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-chloro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloro Methyl) -s-triazine, 4- [o-fluoro-p-N, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-bromo-p -N, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-chloro-pN, N-di (chloroethyl) aminophenyl] -2, 6-di (trick Romechiru) -s- triazine,

4- [m-Fluoro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (m-bromo-pN-ethoxycarbonylmethylamino) Phenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-chloro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4 -(M-Fluoro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN-ethoxycarbonylmethylaminophenyl) -2 , 6-Di (trichloromethyl) -s-triazine, 4- (o-chloro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloro) Methyl) -s-triazine,

4- (o-Fluoro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-bromo-pN-chloroethylaminophenyl) -2 , 6-Di (trichloromethyl) -s-triazine, 4- (m-chloro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-fluoro -PN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) ) -S-triazine, 4- (o-chloro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-fluoro-pN-chloro) Ethylamino) -2,6-di (trichloromethyl) -s-triazine.

  In addition, TAZ series (for example, TAZ-107, TAZ-110, TAZ-104, TAZ-109, TAZ-140, TAZ-204, TAZ-113, TAZ-123) manufactured by Midori Chemical, T manufactured by PANCHIM Series (for example, T-OMS, T-BMP, TR, TB), Irgacure series (for example, Irgacure 651, Irgacure 184, Irgacure 500, Irgacure 1000, Irgacure 149, Ciba Specialty Chemicals) Irgacure 819, Irgacure 261), Darocur series (eg Darocur 1173), 4,4'-bis (diethylamino) -benzophenone, 2-benzyl-2-dimethylamino-4-morpholinobutyrophenone, 2,2-dimethoxy-2- Phenyl Acetophenone,

2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-methoxyphenyl) -4,5 -Diphenylimidazolyl dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (2, 4-Dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-methylmercaptophenyl) -4,5-diphenylimidazolyl dimer, benzoin isopropyl ether, and the like are also useful.

  As the oxime compound, oxime initiators described in JP-A No. 2000-80068, WO-02 / 100903A1, and JP-A No. 2001-233842 are known. Specific examples include 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-butanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio). Phenyl] -1,2-pentanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-hexanedione, 2- (O-benzoyloxime) -1- [4 -(Phenylthio) phenyl] -1,2-pentanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 2- (O-benzoyloxime)- 1- [4- (methylphenylthio) phenyl] -1,2-butanedione, 2- (O-benzoyloxime) -1- [4- (ethylphenylthio) phenyl] -1, -Butanedione, 2- (O-benzoyloxime) -1- [4- (butylphenylthio) phenyl] -1,2-butanedione, 1- (O-acetyloxime) -1- [9-ethyl-6- ( 2-Methylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9-methyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone 1- (O-acetyloxime) -1- [9-propyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9- Ethyl-6- (2-methylethylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9-ethyl-6- (2-butylbenzoyl) 9H- carbazol-3-yl] ethanone, and the like. However, it is not limited to these.

These photopolymerization initiators may be used alone or in combination of two or more.
Among these, from the viewpoint of sensitivity, at least one is preferably a triazine photopolymerization initiator or an oxime photopolymerization initiator. In the present invention, an oxime photopolymerization initiator is used .
From the same point as above, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione (preferably manufactured by Ciba Specialty Chemicals) (preferably 1- (O-acetyloxime) -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone (commercially available from Ciba Specialty Chemicals) and combinations thereof were used. The configuration is most preferred.

A sensitizer and a light stabilizer can be used in combination with the photopolymerization initiator.
Specific examples thereof include benzoin, benzoin methyl ether, 9-fluorenone, 2-chloro-9-fluorenone, 2-methyl-9-fluorenone, 9-anthrone, 2-bromo-9-anthrone, and 2-ethyl-9-anthrone. 9,10-anthraquinone, 2-ethyl-9,10-anthraquinone, 2-t-butyl-9,10-anthraquinone, 2,6-dichloro-9,10-anthraquinone, xanthone, 2-methylxanthone, 2- Methoxyxanthone, 2-ethoxyxanthone, thioxanthone, 2,4-diethylthioxanthone, acridone, 10-butyl-2-chloroacridone, benzyl, dibenzylacetone, p- (dimethylamino) phenylstyryl ketone, p- (dimethylamino) ) Phenyl-p-methylstyryl ketone Examples include benzophenone, p- (dimethylamino) benzophenone (or Michler's ketone), p- (diethylamino) benzophenone, benzoanthrone, benzothiazole compounds described in Japanese Patent Publication No. 51-48516, tinuvin 1130, 400, and the like. It is done.

In addition to the above photopolymerization initiator, other known initiators can be used in the dye-containing negative curable composition of the present invention.
Specifically, the vicinal polykettle aldonyl compound described in US Pat. No. 2,367,660, the α described in US Pat. Nos. 2,367,661 and 2,367,670 A carbonyl compound, an acyloin ether described in US Pat. No. 2,448,828, an aromatic acyloin compound substituted with an α-hydrocarbon described in US Pat. No. 2,722,512, Polynuclear quinone compounds described in US Pat. Nos. 3,046,127 and 2,951,758, triallylimidazole dimer / p-aminophenyl ketone described in US Pat. No. 3,549,367 Benzothiazole compounds / trihalomethyl-s-triazine compounds described in Japanese Patent Publication No. 51-48516, and the like. .

  The total content of the photopolymerization initiator (and the known initiator) in the dye-containing negative curable composition is 0.01 to 50% by mass with respect to the solid content (mass) of the radical polymerizable monomer described later. Is preferable, 1-30 mass% is more preferable, and 1-20 mass% is especially preferable. When the content is within the above range, polymerization and curing can be performed satisfactorily, and the polymerization rate increases, but the molecular weight does not decrease and the film strength does not decrease.

(C) Radical polymerizable monomer The dye-containing negative curable composition of the present invention has an acid value of 25 to 200 mgKOH / g and a viscosity of 12,000 to 100,000 mPa · s (25 ° C.) as a radical polymerizable monomer. It contains at least one kind of acidic group-containing polyfunctional (meth) acrylic compound. Since this polymerizable monomer is selectively used, it is possible to obtain a pixel pattern having a fine and fine rectangular pattern profile with high sensitivity.

The radical polymerizable monomer according to the present invention is an acidic group-containing polyfunctional (meth) acrylic compound having a boiling point of 100 ° C. or higher under normal pressure and an acid value of 25 to 200 mgKOH / g .

  As an acidic group of an acidic group-containing polyfunctional (meth) acrylic compound, a carboxyl group, a sulfo group, a phosphoric acid group and the like are preferable, a carboxyl group and a sulfo group are more preferable, and a carboxyl group is particularly preferable.

The acid value is 25 to 200 mgKOH / g . An acid value of 25 mgKOH / g or more is effective in terms of solubility in unexposed areas. Among them, the acid value is preferably 25 mgKOH / g to 200 mgKOH / g, more preferably 26 mgKOH / g to 100 mgKOH / g, and still more preferably 50 mgKOH / g to 100 mgKOH / g.

  The acid value is measured by a conventional method. For example, it is measured using a titration measurement with a burette or a potentiometric automatic measuring machine AT-310 (manufactured by Kyoto Electronics Co., Ltd.).

  The above-mentioned “acidic group-containing polyfunctional (meth) acrylic compound having a boiling point of 100 ° C. or higher under normal pressure and having an acid value of 25 mgKOH / g or more” is not particularly limited. A compound in which the hydroxyl group is reacted to introduce the acidic group (preferably a carboxyl group or a sulfo group, particularly a carboxyl group) (such as those obtained by replacing the OH site of dipentaerythritol pentaacrylate with a carboxyl group-containing substituent). It is done.

The polyfunctional (meth) acrylic compound containing an acidic group with an acid value of 25 to 200 mgKOH / g is preferably higher in viscosity, and specifically has a viscosity (25 ° C.) of 11,500 mPa · s or more. Those are preferred. When the viscosity is 11,500 mPa · s or more, it is effective for adjusting the viscosity of the resist solution.
Among them, the viscosity is preferably 11,500 to 100,000 mPa · s (25 ° C.), more preferably 12,000 to 100,000 mPa · s (25 ° C.), and further preferably 20,000 to 100,000 mPa · s. s (25 ° C.).

  A viscosity is measured by a conventional method in the state which adjusted the temperature of the curable composition to 25 degreeC. For example, it is measured using a rotary viscometer (for example, manufactured by Toki Sangyo Co., Ltd.) and a vibration type viscometer (for example, SV-10 (manufactured by AND Corporation)).

  Of the above, TO-2359, TO-2360, TO-2348, or TO-2349 manufactured by Toa Synthetic Chemical Co., Ltd. is preferably used as an example of a preferable radical polymerizable monomer.

  Among the above, in terms of obtaining a pixel pattern having a fine but good rectangular pattern profile with high sensitivity, an oxime-based photopolymerization initiator is reacted with a hydroxyl group of a hydroxyl group-containing pentafunctional acrylic compound (preferably Are preferably combined with a compound in which a carboxyl group or a sulfo group, particularly a carboxyl group) is introduced, and in particular, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2- Octanedione or 1- (O-acetyloxime) -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone (both manufactured by Ciba Specialty Chemicals) or these And TO-2359, TO-2360, TO-2348, or TO-2349 manufactured by Toa Synthetic Chemical Co., Ltd. Preferably the composition is a combination of these.

  The content of the radical polymerizable monomer in the dye-containing negative curable composition is preferably 1 to 60% by mass and more preferably 10 to 50% by mass with respect to the solid content of the composition. When the content is within the above range, good curability can be ensured while keeping the elution of the unexposed portion good.

(D) Binder resin The dye-containing negative curable composition of the present invention can contain at least one binder resin as required. The binder resin can be appropriately selected from known resin components as long as it is soluble in an organic solvent, and an organic polymer is suitably used. Among these, an alkali-soluble binder is suitable, and the alkali-soluble binder is not particularly limited as long as it is water-soluble or alkali-soluble, and is preferably selected from the viewpoints of heat resistance, developability, availability, and the like.

  The alkali-soluble binder is preferably a linear organic polymer, soluble in an organic solvent, and developable with a weak alkaline aqueous solution. Examples of such linear organic high molecular polymers include polymers having a carboxylic acid in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, and JP-B-54-25957. Methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, as described in JP-A-59-53836 and JP-A-59-71048. Examples thereof include a polymer, a maleic acid copolymer, and a partially esterified maleic acid copolymer. In particular, an acidic cellulose derivative having a carboxylic acid in the side chain is useful.

  In addition to the above, an acid anhydride added to a polymer having a hydroxyl group, a polyhydroxystyrene resin, a polysiloxane resin, poly (2-hydroxyethyl (meth) acrylate), polyvinylpyrrolidone, polyethylene oxide, Polyvinyl alcohol is also useful.

  In addition, a monomer having a hydrophilic group may be copolymerized, and examples thereof include alkoxyalkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, glycerol (meth) acrylate, (meth) acrylamide, and N-methylolacrylamide. Secondary or tertiary alkylacrylamide, dialkylaminoalkyl (meth) acrylate, morpholine (meth) acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, vinyltriazole, methyl (meth) acrylate, ethyl (meth) Examples include acrylate, branched or linear propyl (meth) acrylate, branched or linear butyl (meth) acrylate, phenoxyhydroxypropyl (meth) acrylate, and the like.

  In addition to the above, as a monomer having a hydrophilic group, a tetrahydrofurfuryl group, a phosphoric acid site, a phosphate ester site, a quaternary ammonium salt site, an ethyleneoxy chain, a propyleneoxy chain, a sulfonic acid or its salt site, a morpholinoethyl group Monomers containing these are also useful.

  In order to improve the crosslinking efficiency, a polymerizable group may be included in the side chain, and a polymer containing an allyl group, a (meth) acryl group, an allyloxyalkyl group or the like in the side chain is also useful. Examples of the polymer containing a polymerizable group include KS resist-106 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series (manufactured by Daicel Chemical Industries, Ltd.), and the like. In addition, in order to increase the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are also useful.

  Of the various alkali-soluble binders described above, from the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferable, and developability control is also possible. From the above viewpoint, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferable.

  Examples of the acrylic resin include a copolymer composed of monomers selected from benzyl (meth) acrylate, (meth) acrylic acid, hydroxyethyl (meth) acrylate, (meth) acrylamide, and the like, and KS resist-106 (Osaka Organic Chemical). Kogyo Co., Ltd.) and Cyclomer P series (Daicel Chemical Industries, Ltd.) are preferred.

The alkali-soluble binder is preferably a polymer having a mass average molecular weight (polystyrene conversion value measured by GPC method) of 1000 to 2 × 10 ⁵ , more preferably 2000 to 1 × 10 ⁵ , and 5000 to ⁵ ×. 10 ⁴ polymers are particularly preferred.

  The binder resin is not necessarily an essential component in the present invention, but may be added for the purpose of modifying the film surface state. In this case, the addition amount is preferably 1 to 40% by mass and more preferably 1 to 30% by mass with respect to the solid content of the dye-containing negative curable composition. When the binder resin is contained within the above range, the uniformity of the coating film surface can be effectively improved, and it is also effective in suppressing the elution of the exposed portion. In addition, when there is too much quantity of binder resin, the elution suppression property of an exposure part may deteriorate remarkably.

(E) Organic solvent In preparing the dye-containing negative curable composition of the present invention, generally at least one organic solvent can be used. Each organic solvent to be used is not particularly limited as long as it satisfies the solubility of each component and the coating property of the dye-containing negative curable composition, but particularly the solubility, coating property, and safety of the dye and binder. Is preferably selected in consideration of

  Specific examples of the organic solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, and alkyl esters. , Methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc .;

3-oxypropionic acid alkyl esters such as methyl 3-oxypropionate and ethyl 3-oxypropionate, such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy Ethyl propionate, etc .; 2-oxypropionic acid alkyl esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, such as methyl 2-methoxypropionate, 2-methoxypropion Acid ethyl, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, 2-methoxy- 2-methylpropio Methyl acid, 2-ethoxy-2-methylpropionic acid ethyl, etc; methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc .;

Ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl Ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc .;

Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone are preferred; aromatic hydrocarbons such as toluene and xylene are preferred.

  The dye-containing negative curable composition of the present invention constituted by using the above components can provide a high-sensitivity and good rectangular pattern, and is also excellent in high transmittance and wide development latitude.

(F) Other components-thermal polymerization inhibitor-
In addition to the above, it is preferable to add a thermal polymerization inhibitor to the dye-containing negative curable composition of the present invention. For example, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,2 ' -Methylenebis (4-methyl-6-tert-butylphenol), 2-mercaptobenzimidazole, etc. are useful.

~ Crosslinking agent ~
In the present invention, it is also possible to obtain a film that is further cured by using a cross-linking agent. In this case, it can comprise using at least 1 type of the crosslinking agent shown below.
The crosslinking agent is not particularly limited as long as the film can be cured by a crosslinking reaction. For example, at least selected from (a) an epoxy resin, (b) a methylol group, an alkoxymethyl group, and an acyloxymethyl group. A phenol compound substituted with at least one group selected from a melamine compound, a guanamine compound, a glycoluril compound, or a urea compound substituted with one group, (c) a methylol group, an alkoxymethyl group, and an acyloxymethyl group , A naphthol compound, or a hydroxyanthracene compound. Of these, polyfunctional epoxy resins are particularly preferred.

~ Other various additives ~
In the dye-containing negative curable composition of the present invention, various additives such as a filler, a polymer compound other than the above, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber, An anti-aggregation agent or the like can be blended.

  Specific examples of the various additives include fillers such as glass and alumina; polymer compounds other than binder resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylate; nonionic, cationic And anionic surfactants: vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2 -Aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ) Ethyltrimetoki Adhesion promoters such as silane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl- 6-t-butylphenol), 2,6-di-t-butylphenol and other antioxidants; 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxybenzophenone, etc. And an anti-aggregation agent such as sodium polyacrylate.

Further, when the alkali solubility of the dye-containing negative curable composition is promoted and the developability is further improved, an organic carboxylic acid, preferably a low molecular weight organic carboxylic acid having a molecular weight of 1000 or less, is added to the composition. Additions can be made.
Specifically, for example, aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid; oxalic acid, malonic acid, succinic acid, Aliphatic dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid; Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, camphoric acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, Aromatic polycarboxylic acids such as trimesic acid, melophanoic acid, pyromellitic acid; phenylacetic acid Hydratropic acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetic acid, coumaric acid, other carboxylic acids such as umbellic acid.

  For the exposure of the dye-containing negative curable composition of the present invention, any of a proximity method, a mirror projection method, and a stepper method can be applied, and in particular, a stepper method (reduction using a reduction projection exposure machine). It is preferable to perform exposure by a projection exposure method. In this stepper method, a pattern is formed by performing exposure while varying the exposure amount in stages, and the rectangularity of the pattern, which is one of the effects of the present invention, is particularly improved when performing stepper exposure. Can be good. As an exposure apparatus used for stepper exposure, for example, an i-line stepper (trade name: FPA-3000i5 +, manufactured by Canon Inc.) can be used.

  The dye-containing negative curable composition of the present invention is used for forming a colored pixel such as a color filter used in a liquid crystal display (LCD), a solid-state imaging device (for example, CCD, CMOS, etc.), a printing ink, It can be suitably used as a production application for ink-jet inks and paints.

<< Color filter and manufacturing method thereof >>
Next, the color filter of the present invention will be described in detail through its manufacturing method.
In the method for producing a color filter of the present invention, the above-described dye-containing negative curable composition of the present invention is used. By using the dye-containing negative curable composition of the present invention, it is possible to obtain a high degree of hardness with excellent developability and sensitivity, so that a color filter composed of a fine pattern with a good shape and high resolution can be easily obtained. Can be produced.

  The method for producing a color filter of the present invention comprises a step of applying the dye-containing negative curable composition of the present invention on a support, exposing through a mask, and developing to form a pattern. . Specifically, the radiation-sensitive composition layer is formed by coating the dye-containing negative curable composition of the present invention on a support by a coating method such as spin coating, cast coating, roll coating, and the like. Is exposed to light through a predetermined mask pattern and developed with a developing solution to form a negative colored pattern (image forming step). Moreover, the hardening process which hardens | cures the formed coloring pattern by heating and / or exposure as needed may be included.

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

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

  Any developer can be used as long as it has a composition that dissolves the dye-containing negative curable composition (uncured part) of the present invention but does not dissolve the irradiated cured part. Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used. As said organic solvent, the above-mentioned organic solvent used when preparing the dye-containing negative curable composition of this invention is mentioned.

Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide. , Choline, pyrrole, piperidine, alkaline compounds such as 1,8-diazabicyclo- [5.4.0] -7-undecene, the concentration is 0.001 to 10% by mass, preferably 0.01 to 1% by mass. An alkaline aqueous solution obtained by dissolution is preferable.
When a developer composed of such an alkaline aqueous solution is used, it is generally washed with water after development.

  The color filter of the present invention can be used for a solid-state imaging device such as a liquid crystal display device or a CCD, and is particularly suitable for a high-resolution CCD device or a CMOS that exceeds 1 million pixels. The color filter of the present invention can be used as, for example, a color filter disposed between a light receiving portion of each pixel constituting a CCD and a microlens for condensing light.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof.

(Examples 1-5, 7-9 and Comparative Examples 1-3 , Reference Example 1 )
1) Preparation of dye-containing negative curable composition The compounds having the compositions shown in Table 1 below were mixed and dissolved to prepare the present invention and a comparative dye-containing negative curable composition.

The details of the compositions (A) to (E) in Table 1 are as follows.
* Resin A: benzyl methacrylate / methacrylic acid copolymer (= 80/20 [molar ratio])
* Monomer A: TO-2359 manufactured by Toagosei Co., Ltd. (acid value: 26.3 mgKOH / g, viscosity (25 ° C.): 12,400 mPa · s)
* Monomer B: TO-2360 (acid value: 66.8 mgKOH / g, viscosity (25 ° C.): 44,200 mPa · s) manufactured by Toa Gosei Chemical Co., Ltd.
* Monomer C: TO-1382 manufactured by Toagosei Co., Ltd. (acid value: 23.6 mg KOH / g, viscosity (25 ° C.): 10,900 mPa · s)
* Monomer D: Kayrad DPHA manufactured by Nippon Kayaku Co., Ltd. (acid value: 0 mgKOH / g, viscosity (25 ° C.): 7,000 mPa · s)
* Monomer E: TO-2349 manufactured by Toagosei Co., Ltd. (acid value: 67.8 mgKOH / g, viscosity (25 ° C.): 43,300 mPa · s)
* Monomer F: TO-2348 manufactured by Toagosei Co., Ltd. (acid value: 25.8 mg KOH / g, viscosity (25 ° C.): 12,400 mPa · s)
* TAZ-107: Midori Chemical Co., Ltd. * Oxime A: Ciba Specialty Chemicals Co., Ltd.
2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione * Oxime B: manufactured by Ciba Specialty Chemicals Co., Ltd.
1- (O-acetyloxime) -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone

2) Preparation of glass substrate with undercoat layer Resist CT-2000L solution (manufactured by FUJIFILM Electronics Materials Co., Ltd.) was applied onto a silicon wafer substrate using a spin coater so as to have a film thickness of 2 μm. A cured film (undercoat layer) was formed by heating and drying for 1 hour.

3) Exposure and development of dye-containing negative curable composition (image formation)
Each of the dye-containing negative curable compositions obtained in 1) is sequentially applied to a spin coater so that the film thickness becomes 1 μm on the undercoat layer of the silicon wafer substrate with the undercoat layer obtained in 2). And prebaked at 100 ° C. for 120 seconds.
Next, using an i-line reduction projection exposure apparatus, the coating film was irradiated with a wavelength of 365 nm through a mask having a line width of 2 μm while changing the exposure amount. After the irradiation, development was performed using a developer of 100% CD-2000 (manufactured by FUJIFILM Electronics Materials) at 23 ° C. for 60 seconds. Next, after rinsing with running water for 20 seconds, spin drying was performed to obtain a pattern image (color filter). The formation of the image was confirmed by an ordinary method using an optical microscope and SEM photograph observation.

4) Evaluation The following evaluation was performed on each pattern image obtained using the dye-containing negative curable composition obtained in each Example and Comparative Example. The evaluation results are shown in Table 2 below.

-1. Sensitivity
In a 2 μm width pattern, the exposure amount at which the dot-to-space width was 1: 1 was defined as an appropriate exposure amount, and the exposure amount was defined as sensitivity. Smaller values indicate higher sensitivity, indicating better sensitivity.

-2. Profile
1 above. Using a SEM image at an appropriate exposure amount, the cross-sectional shape of the pattern image (the cross-section when cut by a plane including the line width direction) is visually observed. (×) is the shape with a round shape.

  As shown in Table 2, in the example, high sensitivity was obtained, and the cross-sectional shape of the formed pattern image was a good rectangle. On the other hand, in the comparative example, the sensitivity and the cross-sectional rectangularity of the pattern image were significantly inferior.

  In addition, in addition to the radical polymerizable monomer used in the above-mentioned examples, the present invention is also applied to the case where the above-described other “acid group-containing polyfunctional (meth) acrylic compound having an acid value of 25 mgKOH / g or more” is used. An effect similar to that of the example can be exhibited, high sensitivity can be obtained in the same manner as described above, and a pattern having a good rectangular cross section can be formed.

Claims (8)

As (A) dye, (B) oxime photopolymerization initiator, and (C) radical polymerizable monomer, the acid value is 25 to 200 mgKOH / g and the viscosity is 12,000 to 100,000 mPa · s (25 ° C.) . A dye-containing negative curable composition containing at least a group-containing polyfunctional (meth) acrylic compound.   The dye-containing negative curable composition according to claim 1, further comprising (D) a binder resin.   The dye-containing negative curable composition according to claim 1 or 2, wherein the (A) dye comprises a mixture of at least two dyes having different absorption characteristics.   The dye according to any one of claims 1 to 3, wherein the acidic group-containing polyfunctional (meth) acrylic compound is a compound in which the hydroxyl group of a hydroxyl group-containing pentafunctional acrylic compound is reacted to introduce the acidic group. Containing negative curable composition.   The dye-containing composition according to any one of claims 1 to 4, wherein the acidic group-containing polyfunctional (meth) acrylic compound is obtained by replacing the OH moiety of dipentaerythritol pentaacrylate with a carboxyl group-containing substituent. Negative curable composition.   The dye-containing negative curable composition according to any one of claims 1 to 5, wherein the content of the dye with respect to the total solid content of the dye is 38% by mass or more.   A color filter formed using the dye-containing negative curable composition according to any one of claims 1 to 6.   It has the process of exposing through a mask, developing, and forming a pattern, after apply | coating the dye-containing negative curable composition of any one of Claims 1-6 on a support body, It is characterized by the above-mentioned. A method for manufacturing a color filter.