KR20060101193A - Dye-containing negative-type curable composition, color filter and method of producing the same - Google Patents

Abstract

It is possible to form a fine pattern of rectangular cross section with high sensitivity and to improve the uniformity in the film of the coated film.

The negative curable composition using the organic solvent soluble dye contains at least 2 oxime compounds as a photoinitiator.

Description

Dye-containing negative curable composition, color filter and manufacturing method thereof {DYE-CONTAINING NEGATIVE-TYPE CURABLE COMPOSITION, COLOR FILTER AND METHOD OF PRODUCING THE SAME}

The present invention relates to a dye-containing negative curable composition suitable for forming a color filter for use in a liquid crystal display device or a solid state image pickup device, a dye-containing color filter, and a manufacturing method thereof.

As a method of manufacturing the color filter used for a liquid crystal display element (LCD) and a solid-state image sensor (CCD, CMOS, etc.), the dyeing method, the printing method, the electrodeposition method, and the pigment dispersion method are known.

Among these, the pigment dispersion method is a method of producing a color filter by a photolithography method using a colored radiation-sensitive composition in which a pigment is dispersed in various photosensitive compositions. Since the pigment is used, it is stable to light or heat. Has the advantage. Moreover, in order to pattern by the photolithographic method, it has been widely used as a method with high positional precision and suitable for manufacturing the color filter for a large screen and high definition color display.

When manufacturing a color filter by the pigment dispersion method, after forming a coating film by apply | coating and drying a radiation sensitive composition on a glass substrate with a spin coater or a roll coater, a colored pixel is formed by pattern exposure and development of this coating film. The color filter is obtained by repeating this operation for each desired number of colors. As such a pigment dispersion method, the example using the negative photosensitive composition which used together the photopolymerizable monomer and the photoinitiator for alkali-soluble resin may be described (for example, refer patent documents 1-4).

On the other hand, high precision refinement is anticipated also in the color filter for solid-state image sensors in recent years. However, in the conventional pigment dispersion system, it is difficult to further improve the resolution, and since there is a problem such as color staining caused by coarse particles of the pigment, it is not suitable for the application requiring a fine pattern such as a solid state imaging device.

In view of such a problem, the technique which uses dye instead of a pigment is conventionally proposed (for example, refer patent document 5). However, the curable composition using a dye generally has a problem that it is inferior to a pigment in various performances, such as light resistance, heat resistance, solubility, and coating uniformity. In addition, since the film thickness of 1.5 micrometers or less is required for the manufacture of the color filter for solid-state image sensors, a large amount of pigment | dye must be added to curable composition, and adhesiveness with a board | substrate or hardening degree becomes inadequate, or a filter There is also a problem that the pattern formability is remarkably lowered, such as dye is drawn out from the exposed portion forming the film.

[Patent Document 1] Japanese Patent Application Laid-Open No. 2-181704

[Patent Document 2] Japanese Patent Application Laid-Open No. 2-199403

[Patent Document 3] Japanese Patent Application Laid-Open No. 5-273411

[Patent Document 4] Japanese Patent Application Laid-Open No. 7-140654

[Patent Document 5] Japanese Patent Application Laid-Open No. 6-75375

[Patent Document 6] Japanese Patent Application Laid-Open No. 54-63903

The present invention has been made in view of the above, and is a curable composition suitable for constituting the dye system. Specifically, the composition is highly sensitive, capable of forming a fine pattern of cross-sectional square shape, and in-film uniformity of the coated film (film thickness). To provide a dye-containing negative curable composition having high uniformity, and the pattern is composed of sharp (highly rectangular in cross section) at high resolution and exhibits good color spectroscopic characteristics. An object of the present invention is to provide a color filter having a color filter and a method for producing a color filter which can produce the color filter at high productivity (high cost performance).

The specific means for achieving the said subject is as follows.

<1> In the dye-containing negative curable composition which contains at least (A) organic solvent soluble dye, (B) photoinitiator, and (C) radically polymerizable monomer, (B) photoinitiator is at least 2 type It is a dye-containing negative curable composition containing an oxime compound.

It is a dye-containing negative curable composition as described in said <1> which also contains <2> (D) binder resin.

<3> The said (C) radically polymerizable monomer is a dye-containing negative curable composition as described in said <1> or <2> which is a polyfunctional (meth) acryl compound.

<4> The said (D) binder resin is a dye-containing negative curable composition as described in said <2> or <3> which is alkali-soluble resin.

The <5> above-mentioned (A) organic solvent soluble dye is a dye-containing negative curable composition in any one of said <1>-<4> which consists of a mixture of 2 or more types of dyes of other absorption characteristics.

<6> It is a color filter formed using the dye-containing negative curable composition in any one of said <1>-<5>.

<7> Color characterized by having the process of apply | coating the dye-containing negative curable composition in any one of said <1>-<5> on a support body, exposing through a mask, developing, and forming a pattern shape. It is a manufacturing method of a filter.

In the manufacturing method of the said color filter, in manufacturing the color filter which consists of a desired color, the said process is repeated according to the desired number of colors, and if necessary, it has a process of hardening the said pattern shape by heating and / or exposure. The form is also appropriate.

The dye-containing negative curable composition of the present invention, a color filter, and a method for producing the same include, in a system containing an organic solvent-soluble dye as a colorant, two oxime compounds having different molecular structures as photopolymerization initiators. To do it. EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

[Dye-containing negative curable composition]

The dye-containing negative curable composition of this invention contains (A) organic solvent soluble dye, (B) photoinitiator, and (C) radically polymerizable monomer at least, Preferably it further contains (D) binder Generally, it can comprise using (E) organic solvent. Moreover, you may contain other components, such as a crosslinking agent, as needed.

(A) Organic solvent soluble dye

The dye-containing negative curable composition of this invention contains at least 1 sort (s) of organic solvent soluble dye. The organic solvent soluble dye can be used without particular limitation, and can be selected from known dyes and the like as a conventional color filter application.

For example, Japanese Patent Application Laid-Open No. 64-90403, Japanese Patent Application Laid-Open No. 64-91102, Japanese Patent Application Laid-Open No. Hei 1-94301, Japanese Patent Application Laid-Open No. 6-11614, Japanese Patent Registration 2592207, United States Patent 4,808,501, US 5,667,920, US 5,059,500, Japanese Patent Laid-Open No. 5-333207, Japanese Patent Laid-Open No. 6-35183, Japanese Patent Laid-Open No. 6-51115, The pigment | dye described in Unexamined-Japanese-Patent No. 6-194828, etc. are mentioned.

Examples of the chemical structure include azo, triphenylmethane, anthraquinone, anthrapyridone, benzylidene, oxonol, a pyrazole azo, anilinoazo, aryl azo, pyrazolotriazole azo and pyridone azo. Dyes such as cyanine series, phenothiazine series, pyrrolopyrazole azomethine series, xanthene series, phthalocyanine series, benzopyran series, indigo series and the like can be used. Especially preferably, they are dyes of a pyrazole azo system, an anilino azo system, a pyrazolotriazole azo system, a pyridone azo system, an anthraquinone system, and an anthrapyridone system.

In addition, when it is comprised by the resist system which develops in water or alkali, an acid dye and / or its derivative is suitable from a viewpoint of completely removing a binder and / or dye by image development. In addition, direct dyes, alkaline dyes, mordant dyes, acid mordant dyes, azoic dyes, disperse dyes, useful dyes, food dyes, and / or derivatives thereof may also be usefully used.

Hereinafter, the acid dyes and derivatives thereof will be described.

Acid dyes and derivatives thereof

The acid dye is not particularly limited as long as it is a dye having an acidic group such as sulfonic acid, carboxylic acid, or phenolic hydroxyl group, but it is soluble in an organic solvent or a developing solution to be used at the time of developing treatment, salt formability with basic compounds, and absorbance. It selects in consideration of all the performance which interaction with other components in a curable composition, light resistance, heat resistance, etc. are required.

Hereinafter, the specific example of acid dye is given. However, in this invention, it 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 chrome 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;

Mordant Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 50, 61, 62, 65;

Mordant Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47,48;

Mordant 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;

Mordant Violet 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58;

Mordant 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;

Mordant Green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53;

Food Yellow 3;

And dye derivatives thereof.

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:

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 dye derivatives thereof.

In addition, azo, xanthene and phthalocyanine acid dyes other than the above are also preferable, and CI Solvent Blue 44, 38, CI Solvent Orange 45, Rhodamine B, Rhodamine 110, 2,7-Naphthalenedisulfonic acid, 3-[( Acid dyes such as 5--chloro-2-phenoxyphenyl) hydrazono] -3,4-dihydro-4-oxo-5-[(phenylsulfonyl) amino]-, and derivatives of these dyes can also be suitably used.

As the derivative of the acid dye, inorganic salts of acid dyes having acid groups such as sulfonic acid and carboxylic acid, salts of acid dyes and nitrogen compounds, amide compounds such as sulfonamides of acid dyes, and the like can be used. There is no particular limitation so long as it is soluble when the type curable composition is prepared in solution, and solubility, absorbance, interaction with other components in the composition, light resistance, heat resistance, etc. It is selected considering all of the performances.

Said "salt of an acidic dye and a nitrogen compound" is demonstrated. The method of forming a salt of an acidic dye and a nitrogen compound may be effective in improving the solubility of the acidic dye (providing solubility in an organic solvent), or improving heat resistance and light resistance.

Nitrogen-containing compounds that form salts with acidic dyes, and nitrogen-containing compounds that form amide bonds with acidic dyes, are soluble in organic solvents or developing solutions of salts or amide compounds, salt-forming properties, absorbance of dyes, colors, and other compositions. It selects in consideration of all the interaction with a component, heat resistance as a coloring agent, light resistance, etc. When selecting only from the viewpoint of absorbance and color value, as a nitrogen-containing compound, it is preferable that molecular weight is as low as possible, Among these, a molecular weight of 300 or less is preferable, A molecular weight of 280 or less is more preferable, A molecular weight of 250 or less is especially preferable. Do.

The mol ratio (hereinafter abbreviated as n) of a nitrogen compound / acid dye in an "acid dye and a nitrogen compound salt" is demonstrated. n is a value which determines the mol ratio of an acid dye molecule and a nitrogen-containing compound (amine compound) which forms a counter ion, and can be selected freely according to the salt formation conditions of an acid dye-amine compound. Specifically, the numerical value between 0 <n≤5 of the functional group number of the acid in an acid dye is used practically, and it is a solubility, salt formation property, absorbance, and interaction with the other components in an organic solvent or a developing solution. It selects in consideration of all the required performances, such as light resistance and heat resistance. When selecting from the viewpoint of absorbance only, n preferably takes a value between 0 <n ≦ 4.5, more preferably takes a value between 0 <n ≦ 4, and a value between 0 <n ≦ 3.5 It is particularly desirable to take

Said acid dye is an acid dye by introducing an acidic group in the structure, and can be said to be a non acid dye by changing the substituent. That is, an acid dye may act suitably at the time of alkali image development, On the other hand, it may become overdevelopment, and a non-acid dye may be used suitably. As the non-acid dye, those which do not have an acid group of the above-mentioned acid dyes can be suitably used.

The above-mentioned dye can use monochromatic dye, respectively, when forming a complementary color system yellow, magenta, and cyan, However, when forming red, green, and blue which are primary colors, generally, it can use combining two or more types of dyes. . In this invention, it can use suitably as a mixed system (mixture) which combined at least 2 sort (s) of dye which differs in water absorption characteristic, and can configure the color of a primary color system suitably.

As content in the dye-containing negative curable composition of the organic-solvent-soluble dye, although it changes with dye, 05-80 mass% is preferable with respect to the total solid component of the said composition, and 10-60 mass% is more preferable. In addition, when mixing and coloring two or more types of dyes, it is preferable that it is at least 10% or more when the amount of all dyes is 100% as the amount of the dye to add the smallest amount.

(B) photoinitiator

The dye-containing negative curable composition of the present invention contains, as a photopolymerization initiator, at least two oxime compounds (hereinafter also referred to as "an oxime initiator or an oxime initiator"). will be. Moreover, you may contain the other initiator which has another structure by addition to the oxime compound containing at least 2 types.

A photoinitiator (containing an oxime compound and other initiators) is contained together with the radically polymerizable monomer described later, and is not particularly limited as long as it can polymerize the radically polymerizable monomer described later. It is preferable to select from a viewpoint of absorption wavelength, water availability, cost, etc.

Examples of the oxime initiator according to the present invention include oxime initiators disclosed in Japanese Patent Application Laid-Open No. 2000-80068, WO-02 / 100903A1, Japanese Patent Application Laid-Open No. 2001-233842, and the like. When selecting 2 types of oxime initiator which are the characteristics of this invention, the compound of 2 types of structures can be selected arbitrarily from these known compound groups.

For example, 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-heptanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 2- (O-benzoyl Oxime) -1- [4- (methylphenylthio) phenyl] -1,2-butanedione, 2- (O-benzoyloxime) -1- [4- (ethylphenylthio) phenyl] -1,2-butanedione , 2- (O-benzoyloxime) -1- [4- (butylphenylthio) phenyl] -1,2-butanedione, 1- (O-acetyl oxime) -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- (0-acetyloxime)- 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (0-acetyloxime) -1- [9-ethyl-6- (2-butyl Benzoyl) -9H-carba 3-yl] ethanone can be mentioned and the like. However, it is not limited to these.

In this invention, although using together the 2 or more types of oxime system initiator arbitrarily selected by these specific examples etc., it can comprise suitably, Especially, the form which uses a phenyl system and a carbazole system together is preferable. In particular, 2- (O-benzoyl oxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione (for example, Chiba Specialty Chemicals Co., Ltd.), 1- ( O-acetyloxime) -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone (e.g., Chiba Specialty Chemicals Co., Ltd.) is mixed The most preferred form is thus obtained.

In addition to the two kinds of oxime compounds according to the present invention described above, one or more other initiators may be mixed and used. Mixable materials Other initiators include at least one active halogen compound, a 3-aryl substituted coumarin compound, a tropine dimer, a benzophenone compound, and acetophenone selected from halomethyloxadiazole-based compounds and halomethyl-s-triazine-based compounds. A compound, its derivative (s), a cyclopentadiene benzene-complex, its salt, etc. are mentioned.

As an active halogen compound which is the said halomethyl oxadiazole type compound, the 2-halomethyl-5-vinyl-1,3,4-oxadiazole compound of Unexamined-Japanese-Patent No. 57-6096, etc., 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 etc. are mentioned.

As an active halogen compound which is the said halomethyl-s-triazine type compound, the vinyl-halomethyl-s-triazine compound of Unexamined-Japanese-Patent No. 59-1281, 2- (naph "of Unexamined-Japanese-Patent No. 53-133428 To-1-yl) -4,6-bis-halomethyl-s-triazine compound and 4- (p-aminophenyl) -2,6-di-halomethyl-s-triazine compound .

As another embodiment, 2,4-bis (trichloromethyl) -6-p-methoxystyryl-s-triazine, 2,6-bis (trichloromethyl) -4- (3,4-methylene Dioxyphenyl) -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-naphtho-1-yl) -4,6- Bis-trichloromethyl-s-triazine,

2- (4-ethoxy-naphtho-1-yl) 4,6-bis-trichloromethyl-s--triazine, 2- (4-butoxy-naphtho-1-yl) -4,6 -Bis-trichloromethyl-s-triazine, 2- [4- (2-methoxyethyl) -naphtho-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2-Ethoxyethyl) -naphtho-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2-butoxyethyl) -naphtho- 1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- (2-methoxy-naphtho-1-yl) -4,6-bis-trichloromethyl-s-triazine , 2- (6-methoxy-5-methyl-naphtho-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-methoxy-naphtho-2-yl ) -4,6-bis-trichloromethyl-s-triazine, 2- (5-methoxy-naphtho-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4,7-dimethoxy-naphtho-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-ethoxy-naphtho-2-yl) -4, 6 -Bis-trichloromethyl-s-triazine, 2- (4,5-dimethoxy-naphtho-1-yl) -4,6-bis-trichloro Tyl-s-triazine, 4- [pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2, 6-di (trichloromethyl) -s-triazine, 4- [o-methyl-pN , N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [pN, N-di (chloroethyl) aminophenyl] -2,6 -Di (trichloromethyl) -s-triazine, 4- [o-methyl-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4 -(pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- [pN, N-di (phenyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (pN-chloroethylcarbonylaminophenyl)- 2,6-di (trichloromethyl) -s-triazine, 4- [pN- (p-methoxyphenyl) carbonylaminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [mN, N-di (ethoxy carbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s- Liao Jin, 4- [m- bromo -p-N, 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) amino Phenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-chloro-pN, N-di (ethoxycarbonylmethyl) aminophenyl-2,6-di (trichloromethyl ) -s-triazine, 4- [o-fluoro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [ o-bromo-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-chloro-pN, N-di (chloroethyl) Aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-fluoro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl ) -s-triazine, 4- [m-bromo-pN, N-di (chloroethyl) amiminophenyl] -2,6-di (trichloromethyl) -s-tri Azine, 4- [m-chloro-p-N, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine,

4- [m-fluoro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (m-bromo-pN-ethoxycarb Bonylmethylaminophenyl) -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 ( Trichloromethyl) -s-triazine, 4- (o-fluoro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m- Bromo-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-chloro-pN-chloroethylaminophenyl) -2,6-di (trichloro Methyl) -s-triazine, 4- (m-fluoro-pN-chloroethyla Nophenyl) -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-chloroethylaminophenyl) -2,6 -Di (trichloromethyl) -s-triazine and the like.

In addition, TAZ series (for example, TAZ-107, TAZ-110, TAZ-104, TAZ-109, TAZ-140, TAZ-204, TAZ-113, TAZ-123, etc.) by Midori Chemical Co., Ltd., PANCHIM company make T series (e.g., T-OMS, T-BMP, TR, T-, B, etc.), Chiba Specialty Chemical Co., Ltd. first monocure series (e.g., monocure 651, monocure 184, Illucure 500, Illucure 1000, Illucure 149, Illucure 819, Illucure 261, etc.), Tarocure Series (e.g., Tarocure 1173, etc.),

4, 4'-bis (diethylamino) -benzophenone, 2-benzyl-2-dimethylamino-4-morpholinobutyllophenone, 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-diphenylimida Zolyl dimer, 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-methylmercaptophenyl) -4,5-diphenylimidazolyl dimer And benzoin isopropyl ether are also useful.

In the dye-containing negative curable composition of this invention, other well-known photoinitiators other than the said photoinitiator can also be used together. Specifically, the bisinal polyketolaldonyl compound described in US Pat. No. 2,367,660, the α-carbonyl compound described in US Pat. Nos. 2,367,661 and 2,367,670, and the acyl described in US Pat. No. 2,448,828. Inethers, aromatic acyloin compounds substituted with α-hydrocarbons described in US Pat. No. 2,722,512, polynuclear quinone compounds described in US Pat. Nos. 3,046,127 and 2,951,758, and triallyl described in US Pat. No. 3,549,367 The combination of midazole dimer / p-aminophenyl ketone and the benzothiazole type compound / trihalomethyl-s-triazine type compound of Unexamined-Japanese-Patent No. 51-48516 are mentioned.

Content in the dye-containing negative curable composition of the oxime initiator (and other initiator as needed, another well-known photoinitiator as needed) is solid content (mass) of the (C) radically polymerizable monomer mentioned later. , 0.01-50 mass% is preferable, 1-30 mass% is more preferable, 1-20 mass% is especially preferable. When the said content is in the said range, sufficient superposition | polymerization hardening will be performed and superposition | polymerization will become difficult to progress, a polymerization rate will become large, but molecular weight will become low and a film strength will not weaken.

Moreover, when comprised with two oxime system initiators, the mixing ratio of two oxime system initiators can be arbitrarily set in the range of 1/99-99/1, and it is preferable to set it as the range of 5/95-95/5. , More preferably 10/90 to 90/10.

In addition, a sensitizer and a light stabilizer can be used together for said photoinitiator.

Specific examples thereof include benzoin, benzoin methyl ether, 9-fluolinone, 2-chloro-9-fluolenonone, 2-methyl-9-fluolenonone, 9-anthrone, 2-bromo-9 -Antron, 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-diethyl thioxanthone, acridon, 10-butyl- 2-chloroacridone, benzyl, dibenzalacetone, p- (dimethylamino) phenylstyrylketone, p- (dimethylamino) phenyl-p-methylstyrylketone, benzophenone, p- (dimethylamino) benzophenone (Or Michler's ketone), p- (diethylamino) benzophenone, benzoanthrone and the like, and benzothiazole-based compounds described in Japanese Patent Publication No. 51-48516, such as tinubin 1130, copper 400, and the like. .

(C) radically polymerizable monomer

The dye-containing negative curable composition of this invention contains at least 1 sort (s) of a radically polymerizable monomer. As a radically polymerizable monomer, the compound which has a boiling point of 100 degreeC or more under normal pressure, and has at least 1 addition-polymerizable ethylenically unsaturated group is preferable. This radically polymerizable monomer can be comprised with the negative curable composition by containing with the said (B) photoinitiator.

As said ethylenically unsaturated group, a (meth) acryloyl group is especially preferable. In addition, the (meth) acryloyl group represents acryloyl or methacryloyl, and likewise shown below, (meth) acrylate represents acrylate or methacrylate.

Examples thereof include monofunctional acrylates and methacrylate polyethylene glycol di (meth) acrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate, Trimetholethane 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, trimetholpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, glycerin or trimeme (Meth) acrylated after adding ethylene oxide or propylene oxide to polyfunctional alcohols such as tyrolethane, Japanese Patent Urethane acrylate described in Japanese Patent Application Laid-Open No. 48-41708, Japanese Patent Publication No. 50-6034, and Japanese Patent Publication No. 51-37193, Japanese Patent Publication No. 48-64183, and Japanese Patent Publication No. 49-43191 Polyfunctional acrylates and methacrylates such as the polyester acrylates described in JP-A-52-30490 and epoxy acrylates which are reaction products of epoxy resins and (meth) acrylic acid; And these mixtures. Moreover, the thing introduce | transduced as a photocurable monomer and oligomer can be mentioned in Japanese adhesive association Vol.20, No, 7, pages 300-308.

Among the above, the polyfunctional (meth) acryl compound which has two or more (meth) acryloyl groups from a point of hardening degree improvement is preferable, and polyfunctional (meth) acrylate is preferable. As polyfunctional (meth) acrylate, dipentaerythrol hexaacrylate is especially preferable.

Among them, at least one kind of polyfunctional (meth) acrylate (preferably dipentaerythritol hexaacrylate), two kinds of the aforementioned phenyl oxime initiator and carbazole oxime initiator [particularly, two -(O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione and 1- (O-acetyloxime) -1- [9-ethyl-6- (2-methylbenzoyl ) -9H-carbazol-3-yl] ethanone] is particularly preferred.

As content in the dye-containing negative curable composition of a radically polymerizable monomer, 1-60 mass% is preferable with respect to the total solid of the said composition, and 10-50 mass% is more preferable. If the said content is the said range, sufficient hardening degree and the elution property of an unexposed part can be maintained, and the hardening degree of an exposed part may be insufficient, or the elution property of an unexposed part may fall remarkably.

(D) binder resin

The dye-containing negative curable composition of this invention can contain at least 1 sort (s) of binder resin as needed. The binder resin can be appropriately selected from known resin components as long as the organic solvent is soluble, and the organic polymer aggregate is suitably used. Especially, an alkali-soluble binder is preferable, and if an alkali-soluble binder has water solubility or alkali solubility, there will be no limitation in particular, It is preferable to select from a viewpoint of heat resistance, developability, water availability, etc.

As said alkali-soluble binder, it is preferable that it can develop in weak alkaline aqueous solution in the linear organic polymer aggregate in soluble to an organic solvent. Examples of such linear organic polymer aggregates include polymers having a carboxylic acid in the side chain, for example, Japanese Patent Application Laid-Open No. 59-44615, Japanese Patent Publication No. 54-34327, Japanese Patent Publication No. 58-12577, and Japanese Patent Publication Methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid, as described in Japanese Patent Application Laid-Open No. 54-25957, Japanese Patent Laid-Open No. 59-53836, Japanese Patent Laid-Open No. 59-71048, and the like. A copolymer, a maleic acid copolymer, a partially esterified maleic acid copolymer, etc. are mentioned, Especially the acidic cellulose derivative which has a carboxylic acid in a side chain is useful. In addition, an acid anhydride is added to the polymer which has a hydroxyl group, etc., polyhydroxy styrene resin, polysiloxane resin, poly (2-hydroxyethyl (meth) acrylate), polyvinylpyrrolidone, polyethylene oxide , Polyvinyl alcohol and the like are also useful.

Moreover, you may copolymerize the monomer which has a hydrophilic group, and as this example, alkoxyalkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, glycerol (meth) acrylate, (meth) acrylamide, N-metholacrylamide , Secondary and tertiary alkylacrylamides, dialkylaminoalkyl (meth) acrylates, morpholino (meth) acrylates, N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, vinyltriazole , Methyl (meth) acrylate, ethyl (meth) acrylate, branched or straight propyl (meth) acrylate, branched or straight butyl (meth) acrylate, phenoxyhydroxypropyl (meth) acrylate, etc. The copolymerization etc. are mentioned.

In addition to the above, as a monomer having a hydrophilic group, a monomer containing a tetrahydrofurfuryl group, a phosphate site, a phosphate ester site, a quaternary ammonium salt site, an ethyleneoxy chain, a propyleneoxy chain, a sulfonic acid or a site of the salt thereof, a morpholin ethyl group and the like It is also useful.

In addition, the polymer which may have a polymeric group in a side chain from a viewpoint of improving crosslinking efficiency, and the polymer etc. which have an allyl group, a (meth) acryl group, an allyloxyalkyl group, etc. in a side chain are also useful. As an example of the polymer which has these polymerizable groups, KS resist-106 (made by Osaka Organic Chemical Industry Co., Ltd.), a cyclomer P series (made by Daicel Chemical Industry Co., Ltd.), etc. are mentioned.

Moreover, from a viewpoint of raising the intensity | strength of a hardened film, alcohol soluble nylon, the polyether of 2, 2-bis (4-hydroxyphenyl) propane, and epichlorohydrin is also useful.

Among the various alkali-soluble binders described above, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins and acrylic / acrylamide copolymer resins are preferable from the viewpoint of heat resistance, and from the viewpoint of development control , Acrylic resins, acrylamide resins, and acryl / acrylamide copolymer resins are preferable. As said acrylic resin, the copolymer which consists of monomers chosen from benzyl (meth) acrylate, (meth) acrylic acid, hydroxyethyl (meth) acrylate, (meth) acrylamide, etc., and KS resist-106 (Osaka organic chemical industry) Co., Ltd., Cyclomer P series (made by Daicel Chemical Industries, Ltd.), etc. are preferable.

As for the said alkali-soluble binder, the aggregate whose mass mean molecular weight (polystyrene conversion value measured by the GPC method) is 100-2x10 <^5> is preferable, The aggregate of 20 <0> -100 * 10 <^5> is more preferable, and 50-100 <^5><10> Aggregate of ⁴ is particularly preferred.

Although binder resin is not necessarily an essential component in this invention, it may add it for the purpose of modifying a film surface shape. It is preferable that it is 1-40 mass% with respect to solid content of dye containing negative curable composition, and, as for the addition amount in that case, it is more preferable that it is 1-30 mass%. When binder resin is contained in the said range, coating film surface uniformity can be improved effectively and it is effective also at the point of the elution suppression of an exposure part. Moreover, when there is too much quantity of binder resin, the elution inhibitory property of an exposure part may remarkably deteriorate.

(E) Organic Solvent

At the time of preparation of the dye-containing negative curable composition of the present invention, at least one kind of organic solvent can be generally used. The organic solvent is not particularly limited as long as it satisfies the solubility of each component and the applicability of the dye-containing negative curable composition.

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 propylate, ethyl butyrate, butyl butyrate, Alkyl esters, methyl lactate, ethyl lactate, methyl oxyacetate, ether oxyacetate, butyl oxyacetate, methyl methoxy acetate, ethyl methoxy acetate, butyl butyl acetate, ethoxy acetate, ethyl ethoxy acetate, and the like;

3-oxypropionate alkyl esters, such as 3-oxymethylpropionate and 3-oxyethylpropionate, for example, 3-methoxypropionate, 3-methoxyethylpropionate, 3-ethoxypropionate and 3-ethoxy Ethyl propionate, etc .; 2-oxypropionate alkyl esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate and propyl 2-oxypropionate, for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-Methoxypropionate, 2-ethoxy propionate, 2-ethoxy propionate, 2-oxy-2-methylpropionate, 2-oxy-2-methylpropionate, 2-methoxy-2-methylpropionic acid Methyl, 2-ethoxy-2-methyl propionate, and the like; methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, methyl 2-oxobutyrate, ethyl 2-oxobutanoate, and the like;

Ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosol part acetate, ethyl cellosol part acetate, diethylene glycol monomethyl ether, diethylene Glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate and the like;

Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and the like; Aromatic hydrocarbons, for example, toluene, xylene and the like can be mentioned suitably.

(F) other ingredients

-Cross-linking system-

In the present invention, it is also possible to use a crosslinking agent to supplement and to obtain a highly cured film. In this case, it can comprise using at least one of the crosslinking agents shown below.

The crosslinking agent that can be used in the present invention is not particularly limited as long as the film can be cured by a crosslinking reaction. For example, from (a) an epoxy resin, (b) a methrol group, an alkoxymethyl group, and an acyloxymethyl group A phenol compound substituted in at least one group selected from a melamine compound, guanamine compound, glycoluril compound, or urea compound, (c) a methrol group, an alkoxymethyl group, and an acyloxymethyl group substituted in one group selected, A naphthol compound or a hydroxyanthracene compound is mentioned. Especially, polyfunctional epoxy resin is especially preferable.

As said (a) epoxy resin, as long as it has an epoxy group and has crosslinkability, any may be sufficient, For example, bisphenol A glycidyl ether, ethylene glycol diglycidyl ether, butanediol diglycidyl ether, Divalent glycidyl-group containing low molecular weight compounds, such as hexanediol diglycidyl ether, dihydroxy biphenyl diglycidyl ether, phthalic acid diglycidyl ester, and N, N- diglycidyl aniline, are similarly trimmed Trivalent glycidyl group-containing low molecular compounds represented by tyrol propane triglycidyl ether, trimetholphenol triglycidyl ether, TrisP-PA triglycidyl ether, and the like, pentaerythritol tetraglycidyl ether, tetramethol bisphenol Tetravalent glycidyl group-containing low-molecular weight compounds represented by A tetraglycidyl ether and the like; dipentaerythritol pentaglycidyl ether and dipentaerythritol 1,2-epoxy-4- (2) of polyhydric glycidyl group-containing low molecular weight compounds such as hexaglycidyl ether, polyglycidyl (meth) acrylate, and 2,2-bis (hydroxymethyl) -1-butanol A glycidyl group containing high molecular compound etc. represented by -oxyranyl) cyclohexane addition product etc. are mentioned.

As a number substituted by the metharol group, the alkoxy methyl group, and the acyloxy methyl group contained in the said crosslinking agent (b), it is 2-6 in the case of a melamine compound, 2-4 in the case of a glycoluril compound, a guanamine compound, and a urea compound. However, in the case of a melamine compound, it is preferably 5-6, 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 the above (b) are generally compounds related to (b) (metholol-containing compound, alkoxymethyl group-containing compound, or acyloxymethyl group-containing compound) I may say.

The metyrol group-containing compound according to (b) is obtained by heating the alkoxymethyl group-containing compound according to (b) in the presence of an acid catalyst such as hydrochloric acid, sulfuric acid, acetic acid, and methane sulfonic acid in alcohol. The acyloxymethyl group containing compound which concerns on said (b) is obtained by mixing and stirring the metyrol group containing compound which concerns on (b) with an acyl chloride in a basic catalyst presence.

Hereinafter, the specific example of the compound which concerns on (b) which has the said substituent is given.

As the melamine compound, for example, a compound or mixture thereof, hexamethoxyethylmelamine, hexaacyl, in which 1 to 5 of the methol groups of hexametholmelamine, hexamethoxymethylmelamine, and hexametholmelamine are methoxymethylated The compound which carried out acyloxymethylation of 1-5 of the methol groups of oxymethyl melamine and hexamethol melamine, or mixtures thereof, etc. are mentioned.

As said guanamine compound, the compound or its mixture, tetramethoxyethylguar which methoxymethylated 1-3 methyrol groups of tetrametholguanamine, tetramethoxymethylguanamine, and tetrametholguanamine, for example The compound which carried out acyloxymethylation of 1-3 methyrol groups, such as namin, tetraacyloxymethyl guanamine, and tetramethyrol guanamine, or its mixture, etc. are mentioned.

As said glycoluril compound, the compound in which methoxymethylated 1-3 of the methirol groups of tetrametholglycoluril, tetramethoxymethylglycoluril, and tetrametholglycoluril, or its mixture, tetramethylolglycol, for example is mentioned. The compound which carried out acyloxymethylation of 1-3 of the methyrol groups of usyl, or its mixture, etc. are mentioned.

As said urea compound, the compound which carried out the methoxymethylation of 1-3 methyrol groups of tetramethyrol urea, tetramethoxymethyl urea, tetramethyrrole urea, its mixture, tetramethoxyethylurea, etc. are mentioned, for example. have..

The compound concerning (b) may be used independently and may be used in combination.

The crosslinking agent (c), that is, a phenol compound, a naphthol compound, or a hydroxyanthracene compound substituted in at least one group selected from a methirol group, an alkoxymethyl group, and an acyloxymethyl group, is the same as in the case of the crosslinking agent (b). In addition, the intermixing with the top photoresist is suppressed by thermal crosslinking, and the film strength is also increased.

Hereinafter, these compounds are generally called the compound (metholol group containing compound, alkoxy methyl group containing compound, or acyloxymethyl group containing compound) which concerns on (c).

As the number of the metyrol group, the acyloxymethyl group, and the alkoxy methyl group contained in the crosslinking agent (c), at least two are required per molecule, and from the viewpoints of crosslinkability and storage stability, two positions and four of the phenol compounds serving as skeletons are used. Preferred are compounds in which all positions are substituted. Moreover, as for the naphthol compound and the hydroxyanthracene compound which become a frame | skeleton, the compound in which both the ortho-position and para position of an OH group are substituted is preferable. The 3 or 5 position of the phenol compound serving as the skeleton may be unsubstituted or may have a substituent. In addition, also in a naphthol compound, it may have an substituent other than the ortho position of an OH group, even if it is unsubstituted.

The methirol group-containing compound according to the above (c) uses a compound having a hydrogen atom at 2-position or 4-position (ortho position or para position) of the phenolic OH group as a raw material, which is sodium hydroxide, potassium hydroxide, ammonia, It is obtained by reacting with formalin in the presence of a basic catalyst such as tetraalkylammonium hydroxide.

The alkoxy methyl group-containing compound according to (c) is obtained by heating the metyrol group-containing compound according to (c) in the presence of an acid catalyst such as hydrochloric acid, sulfuric acid, acetic acid, and methane sulfonic acid in alcohol.

The acyloxymethyl group containing compound which concerns on said (c) is obtained by making the metyrol group containing compound which concerns on (c) react with an acyl chloride in presence of a basic catalyst.

As a skeletal compound in a crosslinking agent (c), the phenolic compound, a naphthol compound, the hydroxy anthracene compound, etc. which are unsubstituted in the ortho position or para position of a phenolic OH group are mentioned, for example, of phenol, cresol Bisphenols, such as each isomer, 2, 3- xylenol, 2, 5- xylenol, 3, 4- xylenol, 3.5- xylenol, and bisphenol A, 4,4'-bishydroxy biphenyl , TrisP-PA (manufactured by Honshu Chemical Co., Ltd.), naphthol, dihydroxynaphthalene, 2,7-dihydroxy anthracene, and the like are used.

As a specific example of the said crosslinking agent (c), the compound which methoxymethylated 1-2 methyrol groups of a trimethol phenol, a tri (methoxymethyl) phenol, and a trimethol phenol as a phenol compound, and trimethol-3- Dimethol cresols such as cresol, tri (methoxymethyl) -3-cresol, compounds obtained by methoxymethylation of 1 to 2 methrol groups such as trimethol-3-cresol, and 2,6-dimethylol-4-cresol; Tetramethylol bisphenol A, tetramethoxymethyl bisphenol A, the compound which methoxymethylated 1-3 methyrol groups of tetramethoxymethyl bisphenol A, tetramethyrol-4,4'-bishydroxybiphenyl, tetrameth 1-5 methirol groups of methoxymethyl-4,4'-bishydroxybiphenyl, hexametholol of TrisP-PA, hexamethoxymethyl body of TrisP-PA, and hexametholol of TrisP-PA A methoxymethylated compound etc. are bishydroxymethyl naphthalenediol etc. as a naphthol compound.

Moreover, as a hydroxy anthracene compound, 1, 6- dihydroxy methyl-2, 7- dihydroxy anthracene etc. are mentioned, for example.

Moreover, as an acyloxymethyl group containing compound, the compound etc. which carried out the partial or all acyloxymethylation of the metyrol group of the said metyrol group containing compound are mentioned, for example.

Among these compounds, preferred are trimetholphenol, bishydroxymethyl-p-cresol, tetramethyrol bisphenol A, and hexamethyrol bodies of TrisP-PA (manufactured by Honshu Chemical Co., Ltd.) or their methrol groups. The phenol compound substituted by both a methyl group and a metyrol group and the alkoxy methyl group is mentioned.

The compounds relating to these (c) may be used alone or in combination.

The total content in the dye-containing negative curable composition of the crosslinking agent when the crosslinking agent (a) to (c) is contained varies depending on the material, but is 1 to 70 based on the solid content (mass) of the composition. Mass% is preferable, 5-50 mass% is more preferable, 7-30 mass% is especially preferable.

Thermal polymerization inhibitor

In addition to the above, it is preferable to further add a thermal polymerization inhibitor. 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-t-butylphenol), 2-mercaptobenzoimidazole and the like are useful.

Various additives

In the dye-containing negative curable composition of the present invention, various additives, for example, fillers, polymer compounds other than those described above, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, anti-agglomerating agents, and the like can be blended as necessary.

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; Surfactants such as nonionic, cationic and anionic systems; 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-epoxycyclo Hexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane and the like accelerant; Antioxidants such as 2,2-thiobis (4-methyl-6-t-butylphenol) and 2,6-di-t-butylphenol; Ultraviolet absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenone; And aggregation inhibitors such as sodium polyacrylate.

In addition, in order to promote alkali solubility of the non-hardened portion and to further improve the developability of the dye-containing negative curable composition of the present invention, the composition may contain an organic carboxylic acid, preferably a low molecular weight organic carr having a molecular weight of 1000 or less. An acid can be added.

Specifically, For example, aliphatic monocarboxylic acids, such as formic acid, acetic acid, propionic acid, butyric acid, gil acetic acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid; oxalic acid, malonic acid, succinic acid, glu Aliphatic dicarboxes such as taric acid, azipine acid, pimeric acid, sublinic acid, azeline acid, sebacic acid, brassyl acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid, and the like. Acid; Aliphatic tricarboxylic acids such as tricarbaric acid, aconic acid and caporic acid; Aromatic mono carboxylic acids such as benzoic acid, toluic acid, cuminic acid, hemelic acid and mesitylene acid; Aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, telephthalic acid, trimellitic acid, trimesic acid, melanoic acid and pyromellitic acid; And other carboxylic acids such as phenylacetic acid, hydratropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropaic acid, cinnamon acid, methyl cinnamic acid, cinnamic acid benzyl, cinnamic acid, cumalic acid, and unberic acid. .

The exposure method of the dye-containing negative curable composition of the present invention is applicable to either of the proximity method, the mirror projection method, and the stepper method, but particularly in the stepper method (reduced projection exposure method using a reduced projection exposure machine). It is preferable to perform exposure. This stepper system forms a pattern by performing exposure while varying an exposure amount stepwise, and when stepper exposure is performed, especially the squareness of the pattern which is one of the effects of this invention can be made more favorable. As an exposure apparatus used for stepper exposure, i line | wire stepper (brand name: FPA-3000i5 +, cannon Corporation make) etc. can be used, for example.

The dye-containing negative curable composition of the present invention is for forming colored pixels such as color filters used in liquid crystal displays (LCDs), solid-state imaging devices (e.g., CCDs, CMOS, etc.), and also for printing inks and ink jet inks. It can be used suitably as manufacture uses, such as and a paint.

<< color filter and manufacturing method thereof >>

Next, the color filter of this invention is demonstrated in detail through the manufacturing method.

In the manufacturing method of the color filter of this invention, the dye-containing negative curable composition of this invention mentioned above is used. The color filter of the present invention can be most suitably produced using the above-described dye-containing negative curable composition of the present invention. Specifically, the dye-containing negative curable composition is rotated onto a support, a flexible coating roll coating, or the like. It can apply | coat by the coating method of this, forms a radiation sensitive composition layer, exposes the said layer through a predetermined mask pattern, and develops in a developing solution, and can form a negative coloring pattern (image forming process) . At this time, if necessary, a curing step of curing the formed colored pattern by heating and / or exposure can be performed.

In the production of a color filter, by repeating the above-described image forming step (and curing step if necessary) in accordance with the desired number of colors, it is possible to produce a color filter composed of a desired number of colors. As light or radiation used at this time, particularly ultraviolet rays such as g-rays, h-rays, and i-rays are preferably used.

Examples of the support include soda glass, pyrex (registered trademark) glass, quartz glass and a transparent conductive film attached thereto, or a photoelectric conversion substrate used for an imaging device, for example, a silicon substrate. Etc., complementary metal oxide film semiconductor (CM0S), etc. are mentioned. These supports may be provided with a black stripe that separates each pixel.

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

As a developing solution used for the manufacturing method of the color filter of this invention, as long as it melt | dissolves the uncured part of the dye-containing negative curable composition of this invention, and the hardening part which comprises a filter does not melt | dissolve, any can be used. Specifically, combinations of various organic solvents and alkaline aqueous solutions can be used. The organic solvent mentioned above is used for preparation of the dye-containing negative curable composition of this invention.

Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, and tetraethylammonium hydroxide. Alkaline compounds such as seed, corin, pyrrole, piperizine, and 1,8-diazabicyclo- [5.4,0] -7-undecene have a concentration of 0.01 to 10% by mass, preferably 0.01 to 1 The alkaline aqueous solution which melt | dissolved so that it may become mass% is preferable. In addition, when the developing solution which consists of such alkaline aqueous solution is used, it generally washes with water after image development.

The color filter of the present invention can be used for solid-state image pickup devices such as liquid crystal display devices and CCDs, and is particularly preferable for high resolution CCD devices and CMOS devices that exceed 10 million pixels. The color filter of this invention can be used as a color filter arrange | positioned, for example between the light receiving part of each pixel which comprises CCD, and the microlens for condensing.

EXAMPLE

Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited to a following example, unless the meaning is exceeded.

(Examples 1-8 and Comparative Examples 1-4)

1) Preparation of dye-containing negative curable composition

The compound of the composition shown in following Table 1 was mixed and dissolved, and the dye-containing negative curable composition of this invention and the comparative was prepared.

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: DPHA (brand name; main ingredient: dipentaerythritol hexaacrylate) made by Nippon Kayaku Co., Ltd.

* TAZ-107: Product of Midori Chemical Co., Ltd.

* TAZ-140: Midori Chemical Co., Ltd.

* Oxime A: Chiba, Specialty, Chemicals Co., Ltd.

        2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione

* Oxime B: Chiba, Specialty, Chemicals Co., Ltd.

       1- (O-acetyloxime) -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone

* Imidazolyl dimer A: 2- (o-crophenyl) -4,5-diphenylimidazolyl dimer

2) Production of glass substrate with underlay layer

Resist CT-200OL solution (manufactured by Fujifilm Electronics Co., Ltd.) was applied onto the silicon wafer substrate using a spin coater so as to have a thickness of 2 μm, and dried at 220 ° C. for 1 hour to form a cured film (undercoat layer). Formed.

3) Exposure and development of dye-containing negative curable compositions (image formation)

Each of the dye-containing negative curable compositions obtained in the above 1) was applied sequentially using a spin coater so as to have a film thickness of 1 占 퐉 on the underlying layers of the undercoat layered glass substrate obtained in the above 2). It prebaked at 120 degreeC for 120 second.

Subsequently, the exposure amount was changed and irradiated through the mask of a line width of 2 micrometers at the wavelength of 365 nm using the i line reduction projection exposure apparatus. After irradiation, the solution was developed under conditions of 23 ° C. for 60 seconds using a 60% CD-2000 (manufactured by FUJIFILM Materials). Subsequently, after rinsing for 20 seconds in running water, spray drying was performed to obtain a pattern shape (color filter). Formation of the image was confirmed by a general method by an optical microscope and SEM photograph observation.

4) Evaluation

The following evaluation was performed about each pattern shape obtained using the dye-containing negative curable composition obtained by each Example and the comparative example. The evaluation results are shown in Table 2 below.

-One. Uniformity in Coating Film

 The dye-containing negative curable composition obtained in said 1) was apply | coated using the spin coater on the silicon wafer with undercoat so that a film thickness might be set to 1 micrometer, and it prebaked at 100 degreeC for 120 second. And ten arbitrary places of the formed coating film surface were wound up to the wafer, and the film thickness [micrometer] was measured by the stylus-type film thickness gauge (Dektak6, Veeco make). Among these 10 points, an average value of 8 points obtained by excluding one point of maximum and minimum is obtained, and one point, which is the value that is farthest from the absolute value from the average value, is selected from eight points, and the difference (membrane thickness difference) is calculated. did. The value means that the smaller one has a higher in-plane uniformity.

-2. Sensitivity-

In the 12 micrometer wide pattern, the exposure amount which the width | variety of a dot and space becomes 1: 1 was made into the appropriate exposure amount, and the exposure amount was made into the sensitivity. The smaller the value is, the higher the sensitivity is, and the better the sensitivity is.

-3. profile-

The cross-sectional shape of a pattern shape is visually observed with the SEM image in said appropriate exposure amount of said 2. The thing whose profile is a rectangle is called "(circle)", and a slightly round top (rounded head) shape is "△". The round top (round head) shape was referred to as "x".

As shown in the said Table 2, in the Example using two types of oxime initiators from which a structure differs, high sensitivity was obtained and the cross-sectional shape of the formed pattern shape was a favorable rectangle. In addition, the formed coating film was formed very uniformly, and the resultant device was obtained at high yield as a result. On the other hand, in the comparative example which did not use 2 types of oxime system initiators, also in any of the examples which used 1 type individually and 2 types of non-oxime system initiators, not only the sensitivity and pattern shape cross-sectional rectangle formation was inferior significantly, but also in the film of a coating film. It was also insufficient in terms of uniformity.

In addition, in addition to the combination of the two oxime initiators used in the above examples, the oxime initiators according to the present invention listed above may be configured in any combination, and thus have the same effect as the combination employed in the examples. As described above, high sensitivity is obtained, and pattern formation having an angled rectangular cross section and uniformity in film is possible.

According to the present invention, it is possible to form a cross-sectional square micropattern at high sensitivity, and to have uniformity in the film (including uniformity in film thickness) of a coating film formed on a substrate (for example, a glass substrate or a silicon wafer). This high dye-containing negative curable composition can be provided. It is especially effective when patterning is performed by stepper exposure.

In addition, a color filter having a high resolution in a sharp pattern (especially a square having a good cross-sectional shape), having a spectral characteristic having good color, and a color filter capable of producing the color filter at high productivity (high cost performance) It can provide a manufacturing method of.

Claims (7)

In the dye-containing negative curable composition which contains at least (A) organic solvent soluble dye, (B) photoinitiator, and (C) radically polymerizable monomer, The dye-containing negative curable composition, wherein the photopolymerization initiator (B) contains two or more oxime compounds. 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 (C) radical polymerizable monomer is a polyfunctional (meth) acryl compound. The dye-containing negative curable composition according to claim 2 or 3, wherein the binder resin (D) is an alkali-soluble resin. The dye-containing negative curable composition according to any one of claims 1 to 4, wherein the (A) organic solvent soluble dye is composed of a mixture of two or more dyes having different absorption characteristics. The color filter formed using the dye-containing negative curable composition in any one of Claims 1-5. A method for producing a color filter comprising the step of applying the 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. .