JP2006267274A - Dye-containing negative curable composition, and color filter and method for manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a dye-containing negative curable composition having high sensitivity, capable of forming a rectangular fine pattern, and ensuring high in-plane uniformity of a film in coating, and to provide a color filter using the composition and a method for manufacturing the color filter. <P>SOLUTION: The dye-containing negative curable composition contains at least (A) an organic solvent-soluble dye, (B) a photopolymerization initiator, (C) a radical polymerizable monomer and (D) an organic solvent, wherein the dye-containing negative curable composition contains two or more photopolymerization initiators (B) and contains at least one oxime compound as the photopolymerization initiators (B). <P>COPYRIGHT: (C)2007,JPO&INPIT

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 (LCD), a solid-state image pickup device (CCD, CMOS, etc.), and the dye-containing negative. The present invention relates to a color filter using a mold curable composition and a method for producing the same.

  As a method for producing a color filter used for a liquid crystal display device or a solid-state imaging device, 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 the pigment dispersion method, a radiation-sensitive composition is applied on a glass substrate by a spin coater or roll coater and dried to form a coating film, and the coating film is subjected to pattern exposure and development. Colored pixels are formed by the above, and a color filter can be obtained by repeating this operation for each color.

  Examples of the pigment dispersion method include a negative photosensitive composition in which a photopolymerizable monomer and a photopolymerization initiator are used in combination with an alkali-soluble resin (see, for example, Patent Documents 1 to 4).

  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 order to solve this problem, a technique of using a dye instead of a pigment has been conventionally proposed (for example, see Patent Document 5). However, the dye-containing curable composition has a problem that it is generally inferior to the pigment in various performances such as light resistance, heat resistance, solubility, and coating uniformity. In particular, in the case of the use for producing a color filter for a solid-state imaging device, a film thickness of 1.5 μm or less is required, so that a large amount of dye must be added to the curable composition. When the adhesion becomes insufficient, sufficient curing cannot be obtained, or the dye is lost even in the exposed area, there is a problem that the pattern formability is extremely difficult.

JP-A-2-181704 JP-A-2-199403 Japanese Patent Laid-Open No. 5-273411 JP-A-7-140654 JP-A-6-75375

In order to solve the above-mentioned problems, an object of the present invention is to provide a curable composition suitable for the use of a dye. Specifically, a highly sensitive rectangular fine pattern can be formed, and at the time of coating. An object of the present invention is to provide a dye-containing negative curable composition having high in-plane uniformity.
It is another object of the present invention to provide a color filter having excellent performance and high cost performance, particularly a color filter suitable for a solid-state imaging device and a manufacturing method thereof.

Specific means for solving the above problems are as follows.
<1> A dye-containing negative curable composition containing at least (A) an organic solvent-soluble dye, (B) a photopolymerization initiator, (C) a radical polymerizable monomer, and (D) an organic solvent. And
A dye-containing negative curable composition containing two or more types of (B) photopolymerization initiators and at least one oxime compound as the photopolymerization initiator (B).

  <2> The dye-containing negative curable composition according to <1>, further comprising (E) a binder.

  <3> The dye-containing negative curable composition according to <1> or <2>, wherein the (C) radical polymerizable monomer is a polyfunctional (meth) acrylic compound.

  <4> The dye-containing negative curable composition according to <2> or <3>, wherein the binder (E) is an alkali-soluble resin.

  <5> The dye-containing negative curable composition according to <1> to <4>, wherein the (A) organic solvent-soluble dye comprises a mixture of two or more dyes having different absorption characteristics.

  <6> A color filter comprising the dye-containing negative curable composition according to <1> to <5>.

  <7> A color filter comprising the steps of applying the dye-containing negative curable composition of <1> to <5> on a support, exposing through a mask, and developing to form a pattern. It is a manufacturing method.

  According to the present invention, a highly sensitive rectangular fine pattern can be formed (particularly when patterning is performed by stepper exposure), and within the coating film surface when applied to a support (for example, glass or silicon wafer). A dye-containing negative curable composition with high uniformity can be provided. Further, according to the present invention, it is possible to provide a color filter excellent in pattern formability and high cost performance, and a manufacturing method thereof.

  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 (hereinafter sometimes referred to as “the composition of the present invention”) includes (A) an organic solvent-soluble dye, (B) a photopolymerization initiator, and (C). A dye-containing negative curable composition comprising at least a radically polymerizable monomer and (D) an organic solvent, wherein the (B) two or more photopolymerization initiators are contained, and the (B) light It contains at least one oxime compound as a polymerization initiator.
The dye-containing negative curable composition of the present invention may further contain other components such as a binder and a crosslinking agent in addition to the organic solvent-soluble dye, the photopolymerization initiator, the radical polymerizable monomer, and the organic solvent. .

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

<(A) Organic solvent soluble dye>
The organic solvent-soluble dye can be used without any particular limitation, and includes conventionally known dyes for color filters. For example, Japanese Patent Application Laid-Open No. 64-90403, Japanese Patent Application Laid-Open No. 64-91102, Japanese Patent Application Laid-Open No. 1-94301, Japanese Patent Application Laid-Open No. 6-11614, No. 2592207, US Pat. No. 4,808,501. Specification, US Pat. No. 5,667,920, US Pat. No. 5,059,500, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115 And dyes described in JP-A-6-194828. From the viewpoint of chemical structure, dyes such as triphenylmethane, anthraquinone, benzylidene, oxonol, cyanine, phenothiazine, pyrrolopyrazole 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 of a resist system that performs water or alkali development, an acid dye and / or a derivative thereof may be preferably used 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.

(Acid dyes)
The acid dye will be described. The acidic dye is not particularly limited as long as it is a dye having an acidic group such as sulfonic acid, carboxylic acid, phenolic hydroxyl group, etc., but is soluble in an organic solvent or a developer, salt-forming with a basic compound, absorbance, curability. It is selected in consideration of all required performance such as interaction with other components in the composition, light resistance, heat resistance and the like.

Hereinafter, specific examples of the acid dye will be given. 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, 163, 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 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.

  Other than the above, azo, xanthene and phthalocyanine acid dyes are also preferred. I. Solvent Blue 44, 38; C; Solvent Orange 45, Rhodamine B; Rhodamine 110; 2,7-Naphthalendisulfonic acid; 3-[(5-chloro-2-phenoxyphenyl) hydrazono] -3,4-dihydro-4-oxol-5- [foliol] Acid dyes such as-, and derivatives of these dyes can also be suitably used.

  As the derivative of the acid dye, an inorganic salt of an acid dye having an acid group such as sulfonic acid or carboxylic acid, a salt of an acid dye and a nitrogen-containing compound, a sulfonamide of an acid dye, etc. can be used, and a curable composition solution Is not particularly limited as long as it can be dissolved, but it requires solubility in organic solvents and developers, absorbance, interaction with other components in the curable composition, light resistance, heat resistance, etc. It is selected considering all of the performance.

  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.

The nitrogen-containing compound that forms a salt with the acid dye and the nitrogen-containing compound that forms an amide bond with the acid dye will be described.
Nitrogen-containing compounds are the solubility of salts or amide compounds in organic solvents and developers, salt-forming properties, dye absorbance / color value, interaction with other components in the curable composition, and heat resistance as a colorant. In addition, it is selected in consideration of all of light resistance and the like. When selecting only in terms of absorbance and color value, the nitrogen-containing compound is preferably as low as possible in molecular weight, more preferably having a molecular weight of 300 or less, more preferably having a molecular weight of 280 or less, and a molecular weight of 250 or less. Those are particularly preferred.

  The molar ratio (hereinafter referred to as “n”) of the nitrogen-containing compound / acid dye in the salt of the acid dye and the nitrogen-containing compound will be described. n is a value that determines the molar ratio between the acid dye molecule and the amine compound that is a counter ion, and can be freely selected according to the salt forming conditions of the acid 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 acidic dye shown above is an acidic dye due to the introduction of an acidic group in its structure, it can be made a non-acidic dye by changing its substituent.
In some cases, the acid dye works favorably during alkali development, but on the other hand, it may become over-developed, and a non-acid dye may be preferably used. As the non-acidic dye, the above-described dyes having no acidic group are preferably used.

  These dyes use single color dyes when forming complementary colors such as yellow, magenta and cyan, respectively, but when forming primary colors such as red, green and blue, two or more types of dyes can be combined. Used. In the present invention, it is preferable to assemble a primary color system by combining two or more kinds of dyes.

  The organic solvent-soluble dye is preferably composed of a mixture of at least two dyes having different absorption characteristics. As described above, the use of two or more dyes having different absorption characteristics facilitates color adjustment according to the purpose. Examples of such combinations include a combination of magenta and yellow, a combination of cyan and yellow, a combination of cyan and violet, and a combination of two types of magenta and yellow, and two types of magenta and yellow. A combination of 2 types of cyan and yellow, a combination of 2 types of cyan and yellow, a combination of 2 types of cyan and violet, a combination of 2 types of cyan and violet, and the like.

  The content concentration of the organic solvent-soluble dye will be described. The concentration of the organic solvent-soluble dye in the total solid component of the dye-containing negative curable composition of the present invention varies depending on the dye, but is preferably 0.5 to 80% by mass, more preferably 10 to 60% by mass. . When mixing two or more dyes to adjust the color, the amount of the dye added in the smallest amount is preferably at least 10% of the total amount when the total dye amount is 100%.

<(B) Photopolymerization initiator>
Next, the photopolymerization initiator will be described. A photoinitiator is contained with the radically polymerizable monomer mentioned later, when comprising a negative type curable composition containing a dye. The photopolymerization initiator is not particularly limited as long as it can polymerize a radical polymerizable monomer, but is preferably selected from the viewpoints of characteristics, initiation efficiency, absorption wavelength, availability, cost, and the like.

In the present invention, at least two kinds of photopolymerization initiators are contained, and at least one of them is an oxime compound (oxime photopolymerization initiator). Of the at least two photopolymerization initiators, the photopolymerization initiator other than the oxime compound is not particularly limited, and any photopolymerization initiator may be contained.
Further, the type of the photopolymerizable compound used in the present invention is not particularly limited as long as it is 2 or more. Specifically, 2 to 5 types are preferably used, and 2 to 3 types are more preferably used.

  Examples of the oxime compound (oxime photopolymerization initiator) include 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione manufactured by Ciba Specialty Chemicals Co., Ltd. 1- (O-acetyloxime) -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, and the like can be preferably used. These other oxime compounds may be used as the oxime compound.

  Among the two or more kinds of photopolymerization initiators, examples of the photopolymerization initiator other than the oxime compound include at least one active halogen compound selected from halomethyloxadiazole compounds and halomethyl-s-triazine compounds, 3- Examples include aryl-substituted coumarin compounds, lophine dimers, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, and the like.

  Examples of the active halogen compound that is the halomethyloxadiazole compound include 2-halomethyl-5-vinyl-1,3,4-oxadiazole compounds described in JP-B-57-6096, 2-trichloromethyl, and the like. -5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (p-cyanostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (p-methoxy) Styryl) -1,3,4-oxadiazole, and the like.

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

  Specific examples of the halomethyl-s-triazine compound include 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- (naphtho) -1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-tria 2- (4-Ethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-butoxy-naphth-1-yl) -4,6-bis-trichloro Methyl-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.

  Other photopolymerization initiators include TAZ series (for example, TAZ-107, TAZ-110, TAZ-104, TAZ-109, TAZ-140, TAZ-204, TAZ-113, TAZ-123, manufactured by Midori Chemical Co., Ltd. ), T series (for example, T-OMS, T-BMP, TR, TB) manufactured by PANCHIM, Irgacure series (for example, Irgacure 651, Irgacure 184, manufactured by Ciba Specialty Chemicals) Irgacure 500, Irgacure 1000, Irgacure 149, Irgacure 819, Irgacure 261), Darocur series (eg Darocur 1173), 4,4′-bis (diethylamino) -benzophenone, 2-benzyl-2-dimethylamino-4-morpholinobutyrophenone , 2,2- Dimethoxy-2-phenylacetophenone,

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.

A sensitizer and a light stabilizer can be used in combination with these photopolymerization initiators.
Specific examples thereof include benzoin, benzoin methyl ether, benzoin, 9-fluorenone, 2-chloro-9-fluorenone, 2-methyl-9-fluorenone, 9-anthrone, 2-bromo-9-anthrone, 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-methoxyxanthone, thioxanthone, 2,4-diethylthioxanthone, acridone, 10-butyl-2-chloroacridone, benzyl, dibenzylacetone, p- (dimethylamino) phenylstyryl ketone, p- ( Dimethylamino) phenyl-p-methyls Rilketone, 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, etc. Can be mentioned.

In addition to the above-mentioned 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 disclosed in US Pat. No. 2,367,660, disclosed in US Pat. Nos. 2,367,661 and 2,367,670. Substituted α-carbonyl compounds, acyloin ethers disclosed in US Pat. No. 2,448,828, α-hydrocarbons disclosed in US Pat. No. 2,722,512 Aromatic acyloin compounds, polynuclear quinone compounds disclosed in US Pat. Nos. 3,046,127 and 2,951,758, disclosed in US Pat. No. 3,549,367. Triarylimidazole dimer / p-aminophenylketone combination, benzothiazole compound disclosed in Japanese Patent Publication No. 51-48516 / tri And halomethyl-s-triazine compounds.

As the photopolymerization initiator combined with the oxime compound as two or more kinds of photopolymerization compounds, triazine compounds, acetophenone compounds, triarylimidazole dimers and benzophenone compounds are preferable, and triazine compounds and triarylimidazole dimers are more preferable. .
Further, as a specific combination of two or more kinds of photopolymerizable compounds, a combination of 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione and a triazine compound. , 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione and triarylimidazole dimer, 1- (O-acetyloxime) -1- [9- A combination of ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone and a triazine compound, 1- (O-acetyloxime) -1- [9-ethyl-6- (2-methyl) A combination of benzoyl) -9H-carbazol-3-yl] ethanone and triarylimidazole dimer, and 2- (O— Combination of emissions benzoyl oxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione and triazine compounds are preferred.

The total amount of the photopolymerization initiator (and known initiator) used is preferably 0.01% by mass to 50% by mass and preferably 1% by mass to 30% with respect to the radical polymerizable monomer solid content (mass) described later. % By mass is more preferable, and 1% by mass to 20% by mass is particularly preferable. When the amount used is in the range of 0.01% by mass to 50% by mass, it is possible to prevent the polymerization from becoming difficult to proceed and to prevent the molecular weight from being lowered and the film strength from being lowered.
As content of an oxime compound with respect to the total content of 2 or more types of photoinitiators, 10-90 mass% is preferable, and 30-70 mass% is still more preferable.

<(C) Radical polymerizable monomer>
Next, the radical polymerizable monomer will be described. As the radical polymerizable monomer, a compound having at least one addition-polymerizable ethylenic double bond and having a boiling point of 100 ° C. or higher under normal pressure is preferable. The ethylenic double bond is preferably (meth) acrylate, and the radical polymerizable monomer in the present invention is preferably a polyfunctional (meth) acrylic compound. By containing both the radically polymerizable monomer and the above-described photopolymerization initiator, the dye-containing negative curable composition of the present invention can be formed into a negative type.

  Examples of the radical polymerizable monomer 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 , Trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) ) Acrylate, hexanediol (meth) acrylate,

Trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, polyfunctional alcohols such as glycerin and trimethylolethane, and then (meth) acrylated after addition of ethylene oxide or propylene oxide; Urethane acrylates as described in JP-B-48-41708, JP-B-50-6034, JP-A-51-37193; JP-A-48-64183, JP-B-49-43191, Polyester acrylates described in JP-B-52-30490; polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid, and mixtures thereof be able to. Furthermore, the Japan Adhesion Association Vol. 20, no. 7, pages 300 to 308 are introduced as photocurable monomers and oligomers.

  In the dye-containing negative curable composition of the present invention, the radical polymerizable monomer is preferably 1% by mass to 60% by mass, and more preferably 10% by mass to 50% by mass with respect to the total solid content. . When the usage-amount of a radically polymerizable monomer exists in the range of 1 mass%-60 mass%, the sclerosis | hardenability of an exposure part can fully be improved and it can prevent that an exposure part elutes.

<(D) Organic solvent>
The organic solvent that can be used in the present invention is not particularly limited as long as the solubility of each component and the coating property of the dye-containing negative curable composition are satisfied, but in particular, the solubility and coating property of the dye and binder. In view of safety, it is preferably selected. Moreover, when preparing the dye-containing negative curable composition of this invention, it is preferable that at least 2 type of organic solvent is included.

  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, alkyl esters, and lactic acid. Methyl, 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.

  As described above, these organic solvents may be used in combination of two or more from the viewpoints of solubility of the dye and the alkali-soluble binder, improvement of the coated surface, and the like. In particular, the above-mentioned methyl 3-ethoxypropionate, 3- Ethyl 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, and propylene glycol methyl A mixed solution composed of two or more selected from ether acetate is preferably used.

  The amount of the organic solvent used in the present invention is preferably such that the total solid concentration of the dye-containing negative curable composition of the present invention is 5 to 80% by mass from the viewpoint of coatability, and 5 to 60. More preferably, it is more preferably 10 to 50% by weight.

<(E) Binder>
Next, the binder will be described. The binder in the present invention may be any as long as it is soluble in an organic solvent, and an organic high molecular polymer is preferably used. Among these, alkali-soluble resins are preferably used. The alkali-soluble resin is not particularly limited as long as it is water-soluble or alkali-soluble, but is preferably selected from the viewpoints of heat resistance, developability, availability, and the like.

  The alkali-soluble resin 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 polymers, maleic acid copolymers, partially esterified maleic acid copolymers, and acidic cellulose derivatives having a carboxylic acid in the side chain are also 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 and the like are also useful as the alkali-soluble resin.
The alkali-soluble resin may be a resin copolymerized with a hydrophilic monomer. Examples of this resin include alkoxyalkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, glycerol (meth) acrylate, ( (Meth) acrylamide, N-methylolacrylamide, secondary or tertiary alkylacrylamide, dialkylaminoalkyl (meth) acrylate, morpholine (meth) acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, vinyltriazole, methyl ( (Meth) acrylate, ethyl (meth) acrylate, branched or linear propyl (meth) acrylate, branched or linear butyl (meth) acrylate, phenoxyhydroxypropyl (meth) acrylate Theft, and the like.

  In addition, examples of the hydrophilic monomer include tetrahydrofurfuryl group, phosphoric acid, phosphate ester, quaternary ammonium salt, ethyleneoxy chain, propyleneoxy chain, sulfonic acid and its salt, morpholinoethyl group and the like Is also useful.

  In addition, the alkali-soluble resin may have a polymerizable group in the side chain in order to improve the crosslinking efficiency. For example, the alkali-soluble resin contains an allyl group, a (meth) acryl group, an allyloxyalkyl group or the like in the side chain. Also useful are polymers and the like. 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 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.

  Among these various alkali-soluble resins, from the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferable, and from the viewpoint of development control. Are preferably acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins.

  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, KS resist-106 (Osaka Organic Chemical Industry). And Cyclomer P series (manufactured by Daicel Chemical Industries, Ltd.).

As the alkali-soluble resin, a polymer having a weight average molecular weight (polystyrene conversion value measured by GPC method) of 1000 to 2 × 10 ⁵ is preferable, a polymer of 2000 to 1 × 10 ⁵ is more preferable, and 5000 to ⁵ is preferable. A polymer of × 10 ⁴ is particularly preferred.

  The binder is not always essential 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% by mass to 40% by mass and more preferably 1% by mass to 30% by mass with respect to the total solid content of the composition. When the usage-amount of the said binder exists in the range of 1 mass%-40 mass%, the coating-film surface uniformity and the elution suppression property of an exposure part are favorable.

<Crosslinking agent>
In the present invention, it is also possible to obtain a film that has been further cured by using a crosslinking agent. Hereinafter, the crosslinking agent will be described.
The crosslinking agent usable in the present invention is not particularly limited as long as the film can be cured by a crosslinking reaction. For example, (a) an epoxy resin, (b) a methylol group, an alkoxymethyl group, and an acyloxymethyl group. At least one substituent selected from a melamine compound, a guanamine compound, a glycoluril compound or a urea compound, (c) a methylol group, an alkoxymethyl group, and an acyloxymethyl group, which is substituted with at least one substituent selected from Substituted phenolic compounds, naphthol compounds or hydroxyanthracene compounds. Among these, as the crosslinking agent, a polyfunctional epoxy resin is preferable.

  The epoxy resin (a) may be any epoxy resin as long as it has an epoxy group and has crosslinkability, for example, bisphenol A diglycidyl ether, ethylene glycol diglycidyl ether, butanediol diglycidyl ether. , Hexanediol diglycidyl ether, dihydroxybiphenyl diglycidyl ether, diphthalic acid diglycidyl ester, N, N-diglycidyl aniline and other divalent glycidyl group-containing low molecular weight compounds, as well as trimethylolpropane triglycidyl ether, Trivalent glycidyl group-containing low molecular weight compounds represented by methylolphenol triglycidyl ether, TrisP-PA triglycidyl ether, etc., as well as pentaerythritol tetraglycidyl ether, tetramethylol vinyl Tetravalent glycidyl group-containing low molecular weight compounds typified by phenol A tetraglycidyl ether, polyvalent glycidyl group-containing low molecular weight compounds such as dipentaerythritol pentaglycidyl ether, dipentaerythritol hexaglycidyl ether, polyglycidyl ( And glycidyl group-containing polymer compounds represented by 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol and the like. .

The number of methylol groups, alkoxymethyl groups, and acyloxymethyl groups substituted in the crosslinking agent (b) is 2 to 6 for melamine compounds, 2 for glycoluril compounds, guanamine compounds, and urea compounds. Although it is -4, Preferably it is 5-6 in the case of a melamine compound, and is 3-4 in the case of a glycoluril compound, a guanamine compound, and a urea compound.
Hereinafter, the melamine compound, guanamine compound, glycoluril compound and urea compound of (b) may be collectively referred to as a compound (containing a methylol group, an alkoxymethyl group or an acyloxymethyl group) in (b).

  The methylol group-containing compound in (b) can be obtained by heating the alkoxymethyl group-containing compound in (b) in an alcohol in the presence of an acid catalyst such as hydrochloric acid, sulfuric acid, nitric acid, methanesulfonic acid or the like. The acyloxymethyl group-containing compound in (b) can be obtained by mixing and stirring the methylol group-containing compound in (b) with acyl chloride in the presence of a basic catalyst.

Hereinafter, specific examples of the compound in (b) having the substituent will be given.
Examples of the melamine compound include hexamethylol melamine, hexamethoxymethyl melamine, a compound in which 1 to 5 methylol groups of hexamethylol melamine are methoxymethylated, or a mixture thereof, hexamethoxyethyl melamine, hexaacyloxymethyl melamine, hexamethylol. Examples thereof include compounds in which 1 to 5 methylol groups of melamine are acyloxymethylated, or mixtures thereof.

  Examples of the guanamine compound include tetramethylol guanamine, tetramethoxymethyl guanamine, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylol guanamine or a mixture thereof, tetramethoxyethyl guanamine, tetraacyloxymethyl guanamine, tetramethylol. Examples thereof include compounds in which 1 to 3 methylol groups of guanamine are acyloxymethylated or a mixture thereof.

  Examples of the glycoluril compound include tetramethylol glycoluril, tetramethoxymethylglycoluril, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylolglycoluril, or a mixture thereof, or a methylol group of tetramethylolglycoluril. Examples thereof include compounds obtained by acylating 1 to 3 or a mixture thereof.

Examples of the urea compound include tetramethylol urea, tetramethoxymethyl urea, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylol urea, a mixture thereof, and tetramethoxyethyl urea.
These compounds in (b) may be used alone or in combination.

  The crosslinking agent (c), that is, a phenol compound, a naphthol compound or a hydroxyanthracene compound substituted with at least one group selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group is the crosslinking agent (b As in the case of), intermixing with the overcoated photoresist is suppressed by thermal crosslinking, and the film strength is further increased. Hereinafter, these compounds may be collectively referred to as a compound (containing a methylol group, an alkoxymethyl group or an acyloxymethyl group) in (c).

The number of methylol groups, acyloxymethyl groups or alkoxymethyl groups contained in the crosslinking agent (c) is at least 2 per molecule, and from the viewpoint of thermal crosslinkability and storage stability, phenol as a skeleton Compounds in which the 2nd and 4th positions of the compound are all substituted are preferred. In addition, the naphthol compound and hydroxyanthracene compound as the skeleton are preferably compounds in which all of the ortho-position and para-position of the OH group are substituted. The 3-position or 5-position of the phenol compound may be unsubstituted or may have a substituent.
The naphthol compound may be unsubstituted or substituted except for the ortho position of the OH group.

  The methylol group-containing compound in (c) is a compound in which the 2- or 4-position of the phenolic OH group is a hydrogen atom, and this is used as sodium hydroxide, potassium hydroxide, ammonia, tetraalkylammonium hydroxide, etc. Obtained by reacting with formalin in the presence of a basic catalyst. The alkoxymethyl group-containing compound in (c) can be obtained by heating the methylol group-containing compound in (c) in an alcohol in the presence of an acid catalyst such as hydrochloric acid, sulfuric acid, nitric acid, methanesulfonic acid or the like. The acyloxymethyl group-containing compound in (c) can be obtained by reacting the methylol group-containing compound in (c) with an acyl chloride in the presence of a basic catalyst.

  Examples of the skeletal compound in the crosslinking agent (c) include phenolic compounds, naphthols, hydroxyanthracene compounds in which the ortho-position or para-position of the phenolic OH group is unsubstituted, and examples thereof include phenol and cresol isomers, 2 , 3-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, bisphenols such as bisphenol A, 4,4'-bishydroxybiphenyl, TrisP-PA (Honshu Chemical Industry) Naphthol, dihydroxynaphthalene, 2,7-dihydroxyanthracene, etc. are used.

  Specific examples of the crosslinking agent (c) include, as a phenol compound, for example, trimethylolphenol, tri (methoxymethyl) phenol, a compound obtained by methoxymethylating one or two methylol groups of trimethylolphenol, trimethylol- Compounds obtained by methoxymethylating one or two methylol groups of 3-cresol, tri (methoxymethyl) -3-cresol, trimethylol-3-cresol, dimethylol cresol such as 2,6-dimethylol-4-cresol, Compounds obtained by methoxymethylating 1 to 3 methylol groups of tetramethylol bisphenol A, tetramethoxymethyl bisphenol A, tetramethylol bisphenol A, tetramethylol-4,4′-bishydroxybiphenyl, tetramethoxymethyl-4,4 ′ − Suhydroxybiphenyl, TrisP-PA hexamethylol, TrisP-PA hexamethoxymethyl, TrisP-PA hexamethylol compound methoxymethylated from 1 to 5 methylol groups, Bishydroxymethylnaphthalenediol, etc. Is mentioned.

  In addition, examples of the hydroxyanthracene compound include 1,6-dihydroxymethyl-2,7-dihydroxyanthracene, and examples of the acyloxymethyl group-containing compound include, for example, a part of the methylol group of the methylol group-containing compound or Examples include compounds that are all acyloxymethylated.

Among these compounds, trimethylolphenol, bishydroxymethyl-p-cresol, tetramethylolbisphenol A, trisP-PA (manufactured by Honshu Chemical Industry Co., Ltd.) or a methylol group thereof is preferable. Examples thereof include an alkoxymethyl group and a phenol compound substituted with both a methylol group and an alkoxymethyl group.
These compounds in (c) may be used alone or in combination.

  The total content of the crosslinking agent in the dye-containing negative curable composition of the present invention varies depending on the material, but is preferably 1 to 70% by mass, and 5 to 50% by mass based on the total solid content of the composition. % Is more preferable, and 7 to 30% by mass is particularly preferable.

<Thermal polymerization inhibitor>
It is preferable to add a thermal polymerization inhibitor to the dye-containing negative curable composition of the present invention. Examples of the thermal polymerization inhibitor 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), 2-mercaptobenzimidazole and the like are useful.

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

<< 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.
The dye-containing negative curable composition of the present invention is coated on a support by a coating method such as spin coating, cast coating, roll coating, etc. to form a radiation-sensitive composition layer, and the layer is formed into a predetermined mask pattern. And a negative coloring pattern is formed by developing with a developer (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 the 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 (substrate) include soda glass, Pyrex (registered trademark), glass, quartz glass and the like in which a transparent conductive film is attached thereto, an image sensor, and the like used for liquid crystal display elements. Examples of the photoelectric conversion element substrate include a silicon substrate and a complementary metal oxide semiconductor (CMOS). These supports may be formed with black stripes that separate pixels.
In addition, an undercoat layer may be provided on these supports, if necessary, for improving adhesion with the upper layer, preventing diffusion of substances, or flattening the support surface.

  Any developer can be used as long as it has a composition that dissolves the uncured portion of the dye-containing negative curable composition of the present invention but does not dissolve the irradiated portion. Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used. As said organic solvent, the above-mentioned 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. Unless otherwise specified, “part” is based on mass.

[Examples 1-8, Comparative Examples 1-4]
1) Preparation of dye-containing negative curable composition The compounds shown in Table 1 were mixed and dissolved to prepare the dye-containing negative curable composition of the present invention.

・樹脂Ａ：ベンジルメタクリレート／メタクリル酸共重合体（＝８０／２０〔モル比〕）
・モノマーＡ：日本化薬（株）製「ＤＰＨＡ」（主成分：ジペンタエリスリトールヘキサアクリレート）
・ＴＡＺ−１０７：みどり化学（株）製
・ＴＡＺ−１４０：みどり化学（株）製
・オキシムＡ：チバ・スペシャルティ・ケミカルズ（株）製
２−（Ｏ−ベンゾイルオキシム）−１−［４−（フェニルチオ）フェニル］−１，２−オクタンジオン）
・オキシムＢ：チバ・スペシャルティ・ケミカルズ（株）製
１−（Ｏ−アセチルオキシム）−１−［９−エチル−６−（２−メチルベンゾイル）−９Ｈ−カルバゾール−３−イル］エタノン
・イミダゾリル二量体Ａ：２−（ｏ−クロルフェニル）−４，５−ジフェニルイミダゾリル二量体

Resin A: benzyl methacrylate / methacrylic acid copolymer (= 80/20 [molar ratio])
Monomer A: “DPHA” manufactured by Nippon Kayaku Co., Ltd. (main component: dipentaerythritol hexaacrylate)
TAZ-107: Midori Chemical Co., Ltd. TAZ-140: Midori Chemical Co., Ltd. Oxime A: Ciba Specialty Chemicals Co., Ltd. 2- (O-benzoyloxime) -1- [4- ( Phenylthio) phenyl] -1,2-octanedione)
Oxime B: Ciba Specialty Chemicals 1- (O-acetyloxime) -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone imidazolyl 2 Monomer A: 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer

2) Production of silicon wafer substrate with undercoat layer A resist CT-2000L solution (manufactured by FUJIFILM Electronics Materials Co., Ltd.) was applied onto the silicon wafer substrate using a spin coater so as to have a film thickness of 2 μm. Heat-dried at 1 ° C. for 1 hour to form a cured film (undercoat layer).

3) Exposure and development of dye-containing negative curable composition (image forming process)
The dye-containing negative curable composition obtained in 1) above was applied on the silicon wafer with an undercoat layer obtained in 2) so as to have a film thickness of 1 μm using a spin coater at 100 ° C. Pre-baked 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 of 2 μm length × 2 μm width while changing the exposure amount. After irradiation, development was performed at 23 ° C. for 60 seconds using a developer (trade name: CD-2000, 60%, manufactured by Fuji Film Arch Co., Ltd.). Subsequently, after rinsing with running water for 20 seconds, spin drying was performed to obtain a pattern image. The image formation was confirmed by an ordinary method using an optical microscope and SEM photograph observation.

4) Evaluation (1) Sensitivity The exposure amount at which the width of the dot and space of the 2 μm pattern was 1: 1 was defined as the appropriate exposure amount, and the exposure amount was defined as the sensitivity. At this time, a smaller numerical value is preferable because of higher sensitivity.

(2) Profile In the above (2), the cross section of the pattern was observed on the SEM image for the pixel pattern formed at the appropriate exposure amount. At this time, a good rectangular profile was evaluated as “◯”, and a round top (rounded head) shape was evaluated as “X”. The results are shown in Table 2 below.

(3) In-plane uniformity of coating film The dye-containing negative curable composition obtained in 1) above was applied onto a silicon wafer with an undercoat layer using a spin coater so that the film thickness became 1 μm. Pre-baked at 120 ° C. for 120 seconds. The film was scratched to the substrate at 10 locations within the wafer surface, and the film thickness was measured with a stylus type film thickness meter (Dektak 6M, manufactured by Veeco).
Out of these 10 points, the average value is calculated at 8 points excluding the upper and lower points, and one point that is the most distant from the average value is selected from 8 points, the difference is calculated, and the value is calculated. The in-plane uniformity of the coating film was evaluated. At this time, a smaller numerical value means higher in-plane uniformity.

  As can be seen from Table 2, it is possible to provide a dye-containing negative curable composition capable of forming a highly sensitive and rectangular profile. Furthermore, since the applied film is produced very uniformly, the resulting device is obtained in high yield. Further, when the dye-containing negative curable composition of the present invention is used, it is possible to provide a color filter having high transmittance, wide development latitude, high resolution and particularly excellent light resistance. For this reason, by using the dye-containing negative curable composition of the present invention, a color filter excellent in resolution and heat resistance can be produced, and a method for producing a color filter with high cost performance can be provided.

Claims (7)

A dye-containing negative curable composition comprising at least (A) an organic solvent-soluble dye, (B) a photopolymerization initiator, (C) a radical polymerizable monomer, and (D) an organic solvent,
A dye-containing negative curable composition comprising two or more (B) photopolymerization initiators and at least one oxime compound as the (B) photopolymerization initiator.   The dye-containing negative curable composition according to claim 1, further comprising (E) a binder.   The dye-containing negative curable composition according to claim 1 or 2, wherein the (C) radical polymerizable monomer is a polyfunctional (meth) acrylic compound.   The dye-containing negative curable composition according to claim 2 or 3, wherein the binder (E) is an alkali-soluble resin.   The dye-containing negative curable composition according to any one of claims 1 to 4, wherein the organic solvent-soluble dye (A) comprises a mixture of two or more dyes having different absorption characteristics.   A color filter comprising the dye-containing negative curable composition according to any one of claims 1 to 5.   A color comprising a step of applying a dye-containing negative curable composition according to any one of claims 1 to 5 on a support, exposing through a mask, and developing to form a pattern. A method for manufacturing a filter.