TWI395061B - Dye-containing negative type curable composition, color filter and method of producing the same - Google Patents

Description

Negative hardening composition containing dye, color filter, and manufacturing method thereof

The present invention relates to a dye-containing negative-type hardenable composition, and a dye-containing color filter and a method for producing the same, which are suitable for use in a liquid crystal display element or a solid-state imaging element.

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

Among them, the pigment dispersion method is a method using a Lithography method in which a color filter is prepared by dispersing a pigment in a coloring photosensitive composition of various photosensitive compositions, and has a light for use of a pigment. Or heat is the advantage of stability. In addition, since patterning by photolithography is used, a suitable method for producing a large-screen, high-definition color filter for color display has been gradually used.

In the case where a color filter is produced by a pigment dispersion method, a photosensitive composition is applied onto a glass substrate by a spin coater or a roll coater, and dried to form a coating film, and then the coating film is formed. The pattern is exposed and developed to form the colored pixels so as to match the desired number of tones, and the color is repeated for each operation to obtain a color filter. In such a pigment dispersion method, an example of a negative photosensitive composition in which a photopolymerizable monomer and a photopolymerization initiator are combined with an alkali-soluble resin has been proposed (for example, refer to Patent Documents 1 to 4).

On the other hand, in recent years, it has been desired to further refine the color filter for solid-state imaging devices. However, in the conventional pigment dispersion system, it is difficult to further improve the resolution, and problems such as color unevenness due to coarse particles of the pigment occur, and it is not applicable to applications requiring a fine pattern such as a solid-state imaging element.

In view of such a problem, a technique of using a dye to replace a conventional pigment has been proposed (for example, refer to Patent Document 5). However, the curable composition using a dye has various problems in terms of, for example, light resistance, heat resistance, solubility, coating uniformity, and the like, and there is a problem of deterioration as compared with a general pigment. In the case of a color filter for a solid-state imaging device, since a film thickness of 1.5 μm or less is required, it is necessary to add a large amount of a dye to the curable composition, so that the adhesion to the substrate or the degree of hardening become Insufficient, or in the exposed portion of the filter, the dye will be removed, etc., and problems such as a marked decrease in pattern formation still occur.

[Patent Document 1] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei.

In view of the above problems, an object of the present invention is to provide a dye-containing negative-type hardenable composition which is suitable for a dye-based hardenable composition, specifically, high-sensitivity, and can be cross-sectionally rectangular. Forming the pattern, at the same time, making the film uniformity (including film thickness uniformity) of the coating film formed by coating high; and providing a method for manufacturing a color filter, the pattern of which is clear (in particular, horizontal The cross-sectional shape is a good rectangle and is composed of a high resolution, a color filter having a spectral characteristic of a good hue, and the color filter can be produced with high productivity (high cost performance). The object of the present invention is to achieve this object.

The specific technical means for achieving this problem is as follows: <1> A negative-type curable composition containing a dye containing at least (A) an organic solvent-soluble dye, (B) a photopolymerization initiator, and (C) a radical polymerizable monomer; and characterized in that the (B) photopolymerization initiator contains at least two hydrazine compounds.

<2> The negative-type hardenable composition containing the dye according to <1>, further comprising (D) an adhesive resin.

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

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

The dye-containing negative-type hardenable composition according to any one of <1> to <4> wherein the (A) organic solvent-soluble dye is a mixture of at least two dyes having different absorption characteristics. of.

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

<7> A method of producing a color filter, comprising: applying a dye-containing negative-type hardenable composition disclosed in any one of <1> to <5> on a carrier, and transmitting the mask The step of performing exposure and development to form a pattern.

In the method for producing a color filter, when a color filter having a desired color tone is produced, the step is repeated in accordance with the required number of tones, and if necessary, it is preferably morphologically preferable. There is a step of hardening by heating and/or exposing the pattern image.

According to the present invention, it is possible to provide a negative-type hardenable composition containing a dye which is highly sensitive and which can be formed into a rectangular thin pattern of a cross section, and is also formed on a substrate (for example, a glass substrate or a germanium wafer). The in-film uniformity (including film thickness uniformity) of the coating film formed by the upper coating is high. In particular, it is effective at the time of pattern formation by exposure by a stepper. In addition, it is possible to provide a color filter having a pattern in which the pattern is clear (in particular, the cross-sectional shape is a good rectangle) and is composed of high resolution, and has a color filter exhibiting a good color tone. The color filter can be fabricated using high productivity (high cost performance).

The present invention contains a negative-type curable composition of a dye, and the color filter and the method for producing the same are characterized in that a system containing an organic solvent-soluble dye as a colorant, in particular, a molecule as a photopolymerization initiator Construct two different bismuth compounds. Hereinafter, the present invention will be described in detail.

[negative hardenable composition containing dye]

The dye-containing negative-type hardenable composition of the present invention can contain at least: (A) an organic solvent-soluble dye, (B) a photopolymerization initiator, (C) a radical polymerizable monomer, and more preferably (D) adhesion. The agent is generally constituted by using (E) an organic solvent. Further, if necessary, other components such as a crosslinking agent may be further contained.

(A) organic solvent soluble dye

The dye-containing negative-type hardenable composition of the present invention contains at least one organic solvent-soluble dye. The organic solvent-soluble dye can be used without particular limitation, and the use of the conventional color filter can be selected from conventional dyes and the like.

For example, Japanese Laid-Open Patent Publication No. SHO-64-90403, Japanese Patent Laid-Open No. Hei-64-91102, Japanese Patent Laid-Open No. Hei No. Hei 1-94301, Japanese Patent Laid-Open No. Hei 6-11614, and Japan Patent No. 2,592, 207, U.S. Patent No. 4,808,501, U.S. Patent No. 5,679, 920, U.S. Patent No. 5,569, 920, U.S. Patent No. 5,059,500, U.S. Patent No. 5, 333, 207, and Japanese Patent Laid-Open No. Hei. A pigment such as Japanese Patent Laid-Open No. Hei 6-51115, and Japanese Patent Laid-Open No. Hei 6-194928.

As the chemical structure, an azo type such as a pyrazole azo type, an aniline azo type, an aryl azo type, a pyrazole triazole azo type, or a pyridone azo type, a triphenylmethane type, or an anthraquinone type can be used. Anthrapyridone, benzylidene, oxalican, phthalocyanine, phenothiazine, pyrrolopyrazole-imine, xanthene, phthalocyanine, benzopyran, indigo, etc. Dye. In particular, a pyrazole azo type, an aniline azo type, a pyrazole triazole azo type, a pyridone azo type, an anthraquinone type, an anthrapyridone type dye is especially preferable.

Further, in the case of constituting a photoresist system developed by water or an alkali solution, an acid dye and/or a derivative thereof is suitable from the viewpoint of completely removing the binder and/or the dye by development. In addition, direct dyes, salt-based dyes, mordant dyes, acid mord dyes, insoluble azo dyes, disperse dyes, oil-soluble dyes, food dyes, and/or derivatives thereof can also be effectively used.

Hereinafter, the acid dye and its derivative will be described.

~Acid dyes and their derivatives~

The acid dye is not particularly limited as long as it is an acid group having an acidic group such as a sulfonic acid, a carboxylic acid or a phenolic hydroxyl group, and all the solubility and the salt for the developing liquid used in the organic solvent or development treatment described later are considered. The salt formation property, the absorbance, the interaction with other components in the composition, the light resistance, the heat resistance, and the like of the basic compound are selected as necessary properties.

Specific examples of the acid dye are listed below. However, the invention is not limited by these specific examples. For example, acid glucosinolate 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 medium purple K; acid magenta; acid green 1,3,5,9,16,25,27,50,58, 63,65,80,104,105,106,109;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, 14,17,18,26,27,29,31,34,35,37,42,44,50,51,52,57,66,73,80,87,88,91,92,94,97,103,111,114,129,133,134,138,143,145,150,151,158,176,182,183,198,206,211,215,216,217,227,228,249,252,257,258,260,261,266,268,270,274,277,280,281,295,308,312,315,316,339,341,345,346,349,382,383,394,401,412,417,418,422,426; 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, 76,79,98,99,111,112,113,114,116,119,123,128,134,135,138,139,140,144,150,155,157,160,161,163,168,169,172,177,178,179,184,190,193,196,197,199,202,203,204,205,207,212,214,220,221,228,230,232,235,240,240,242,243,251; 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; 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, 93,94,95,97,98,99,100,101,106,107,108,109,113,114,115,117,119,137,149,150,153,155,156,158,159,160,161,162,163,164,166,167,170,171,172,173,188,189,190,192,193,194,196,198,199,200,207,209,210,212,213,214,222,228,229,237,238,242,243,244,245,247,275,293; direct green 25,27,31,32,34,37,63,65,66,67,68,69,72,77,79,82; mordant yellow 5, 8,10,16,20,26,30,31,33,42,43,45,56,60,61,62,65; 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 purple 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 derivatives of such dyes.

Among the acid dyes, it is preferably acid black 24; acid blue 23, 25, 29, 62, 80, 86, 87, 92, 138, 158, 182, 243, 324: 1; lime orange 8, 51, 56, 74, 63; acid red: 1, 4,8,34,37,42,52,57,80,80,97,114,143,145,151,183,217,249; 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 these dyes a derivative.

Further, an azo-based, xanthene-based or phthalocyanine-based acid dye other than the above is also suitable, and CI solvent blue 44, 38, CI solvent orange 45, rhodamine B, rhodamine 110, and the like can also be suitably used. 2,7-naphthalene disulfonic acid, 3-[(5-chloro-2-phenoxyphenyl) terpylene]-3,4-dichloro-4-carbonyl-5-[(phenylsulfonyl) Acid dyes such as amine groups and derivatives of such dyes.

As the derivative of the acid dye, an acid dye inorganic salt derived from an acidic group such as a sulfonic acid or a carboxylic acid, a salt of an acid dye and a nitrogen-containing compound, or a guanamine compound such as an acid dye sulfonamide can be used. When the negative-type hardening composition of the dye is prepared into a solution, it is not particularly limited as long as it is soluble, and all the solubility, absorbance, and the solubility of the developing liquid used in the organic solvent or development treatment described later are considered. The interaction, light resistance, heat resistance and the like of other components in the composition are selected as necessary properties.

The "salt of acid dye and nitrogen-containing compound" will be described. The method of forming a salt of an acid dye and a nitrogen-containing compound is often advantageous for improvement in solubility of an acid dye (to impart solubility to an organic solvent) or improvement in heat resistance and light resistance.

The nitrogen-containing compound forming an acid dye and a salt and the nitrogen-containing compound forming an acid dye and a guanamine bond are considered to have solubility, salt formability, dye absorbance of an organic solvent or a developing solution for a salt or a guanamine compound. The color price, the interaction with other components in the composition, the heat resistance and light resistance of the colorant, and the like are selected. In the case of selecting only the viewpoints of the absorbance and the color price, the nitrogen-containing compound is preferably as low as possible. Among them, those having a molecular weight of 300 or less are more preferably those having a molecular weight of 280 or less, and those having a molecular weight of 250 or less are particularly preferable. .

The molar ratio (hereinafter, abbreviated as n) of the nitrogen-containing compound/acid dye in the "salt of acid dye and nitrogen-containing compound" will be described. The n-series determines the value of the molar ratio of the acid dye molecule to the nitrogen-containing compound (amine compound) forming the counter ion, and can be freely selected depending on the salt formation conditions of the acid dye-amine compound. Specifically, most of the acid functional groups in acid dyes are practically used. The values of the five values are selected as the necessary properties for all the solubility in the organic solvent or the developing solution, the salt formability, the absorbance, the interaction with other components in the cured composition, the light resistance, the heat resistance, and the like. In the case of selecting only based on the viewpoint of absorbance, it is preferable to use 0<n. 4.5 values, more preferably 0<n 4 values, especially ideal for 0<n The value between 3.5.

Since the acid dye is an acid dye by introducing an acidic group in its structure, it is possible to form a non-acid dye in reverse by changing its substituent. That is, acid dyes are often suitable for the action of lye imaging, and on the other hand, may be over-developed, and may also be suitable for use with non-acid dyes. The non-acid dye can be applied to an acidic base without the acid dye or the like.

When the dye forms yellow, magenta, or navy in a complementary color system, each of the monochromatic dyes can be used. When the red, green, and blue colors of the primary color system are formed, generally, two or more dyes can be used in combination. . In the present invention, a mixed system (mixture) of at least two kinds of dyes having different absorption characteristics can be suitably used, and the color tone of the primary color system can be appropriately formed.

Although it is different depending on the dye, the content of the dye-containing negative-type hardening composition of the organic solvent-soluble dye is preferably from 0.5 to 80% by mass, more preferably from 10 to 60, based on all the solid components of the composition. quality%. Further, when two or more kinds of dyes are mixed and toned, the amount of the dye to be added in a minimum amount is preferably at least 10% or more when all the amounts of the dye are 100%.

(B) Photopolymerization initiator

The negative-type hardening composition containing a dye according to the present invention is characterized in that the photopolymerization initiator contains at least two kinds of hydrazine compounds (hereinafter also referred to as "the oxime-based initiator of the present invention" or "anthracene initiator" "). Further, in addition to at least two kinds of hydrazine compounds, other initiators of other structures may be contained.

The photopolymerization initiator (containing a ruthenium compound and other initiators) is contained in combination with a radical polymerizable monomer to be described later, and may be used as long as the radical polymerizable monomer described later can be polymerized. It is particularly limited, but it is preferably selected based on the characteristics, the initial efficiency, the absorption wavelength, the availability, the cost, and the like.

The oxime-based initiators of the present invention include those disclosed in JP-A-2000-80068, WO-02/100903A1, and JP-A-2001-233842. In the case of selecting two oxime-based initiators of the character of the present invention, a compound of any two configurations can be selected from a group of conventional compounds.

For example, 2-(O-phenylhydrazinyl)-1-[4-(phenylthio)phenyl]-1,2-butanedione, 2-(O-phenylhydrazinyl)-1 -[4-(phenylthio)phenyl]-1,2-pentanedione, 2-(O-phenylhydrazinyl)-1-[4-(phenylthio)phenyl]-1,2- Hexanedione, 2-(O-phenylhydrazinyl)-1-[4-(phenylthio)phenyl]-1,2-heptanedione, 2-(O-phenylhydrazinyl)-1- [4-(phenylthio)phenyl]-1,2-octanedione, 2-(O-phenylhydrazinyl)-1-[4-(methylphenylthio)phenyl]-1,2 -butanedione, 2-(O-phenylhydrazinyl)-1-[4-(ethylphenylthio)phenyl]-1,2-butanedione, 2-(O-benzoinhydrazinyl) 1-[4-(butylphenylthio)phenyl]-1,2-butanedione, 1-(O-ethylindenyl)-1-[9-ethyl-6-(2-A Benzophenyl)-9H-aminomethylmercapto-3-indenyl]ethanone, 1-(O-ethylindenyl)-1-[9-methyl-6-(2-methylphenylhydrazine) -9H-Aminomethylmercapto-3-indolyl]ethanone, 1-(O-ethylindenyl)-1-[9-propyl-6-(2-methylphenylindenyl)- 9H-Aminomethylmercapto-3-indenyl]ethanone, 1-(O-ethylindenyl)-1-[9- -6-(2-methylphenylhydrazino)-9H-aminocarbamidin-3-mercapto]ethanone, 1-(O-ethylindenyl)-1-[9-ethyl-6 -(2-butylphenylhydrazino)-9H-aminomethylmercapto-3-indenyl]ethanone. However, it is not limited by these specific examples.

In the present invention, two or more kinds of anthraquinone initiators arbitrarily selected from the above specific examples and the like can be used in combination, and it is preferred to use a combination of a phenyl group and an aminocarbamidine group. form. In particular, it is preferred to mix 2-(O-phenylhydrazinyl)-1-[4-(phenylthio)phenyl]-1,2-octanedione [for example, manufactured by Ciba Speciality Chemicals (stock)] and 1-(O-Ethylindole)-1-[9-ethyl-6-(2-methylphenylindenyl)-9H-aminomethylindolyl-3-indenyl]ethanone [eg, Ciba The form formed by the Speciality Chemicals system.

Further, in addition to the two anthraquinone compounds of the present invention, one or more other initiators may be used in combination. Other initiators which can be mixed include at least one active halide selected from a halomethyl oxadiazole compound and a halomethyl- s -triazole compound, a 3-aryl substituted coumarin compound, Lofin base dimer, benzophenone compound, acetophenone compound and its derivative, cyclopentadiene-benzene-iron coordination compound and salts thereof.

The active halide of the halomethyl oxadiazole compound may, for example, be a 2-halomethyl-5-vinyl-1,3,4-oxadiazole compound disclosed in Japanese Patent Publication No. Sho 57-6096; Or 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, and the like.

The active halide of the halomethyl- s -triazole-based compound is exemplified by the vinyl halomethyl- s -triazole compound disclosed in Japanese Patent Publication No. Sho 59-1281, which is disclosed in Japanese Patent Laid-Open No. 53 2-(Naphtho-1-indenyl)-4,6-dihalomethyl- s -triazole compound and 4-( p -aminophenyl)-2,6-dihalo-methyl A s -triazine compound or the like.

Other specific examples include 2,4-bis(trichloromethyl)-6- p -methoxystyryl- s -triazine and 2,6-bis(trichloromethyl)-4-( 3,4-methylenedihydroxyphenyl)-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-trichloro Methyl-4-amino-6- p -methoxystyryl- s -triazine, 2-(naphtho-1-indenyl)-4,6-bistrichloromethyl- s -triazine , 2-(4-methoxynaphtho-1-indenyl)-4,6-bistrichloromethyl- s -triazine, 2-(4-ethoxynaphthen-1-yl)- 4,6-bis-trichloromethyl- s -triazine, 2-(4-butoxynaphthalen-1-yl)-4,6-bistrichloromethyl- s -triazine, 2-[ 4-(2-methoxyethyl)naphtho-1-indenyl]-4,6-bistrichloromethyl- s -triazine, 2-[4-(2-ethoxyethyl)naphthalene And-1-mercapto]-4,6-bistrichloromethyl- s -triazine, 2-[4-(2-butoxyethyl)naphthacene-1-yl]-4,6- Double trichloro Base- s -triazine, 2-(2-methoxynaphtho-1-indenyl)-4,6-bistrichloromethyl- s -triazine, 2-(6-methoxy-5- Methylnaphtho-2-indenyl)-4,6-bistrichloromethyl- s -triazine, 2-(6-methoxynaphtho-2-indenyl)-4,6-ditrichloro Methyl- s -triazine, 2-(5-methoxynaphtho-1-indenyl)-4,6-bistrichloromethyl- s -triazine, 2-(4,7-dimethoxy (n-naphthalen-1-yl)-4,6-bistrichloromethyl- s -triazine, 2-(6-ethoxynaphthalen-2-yl)-4,6-bistrichloromethyl Base- s -triazine, 2-(4,5-dimethoxynaphtho-1-indenyl)-4,6-bistrichloromethyl- s -triazine, 4-[ p -N,N - bis(ethoxycarbonylmethyl)amine phenyl]-2,6-bis(trichloromethyl) -s -triazine, 4-[ o -methyl- p- N,N-di(ethoxycarbonyl) Methyl)amine phenyl]-2,6-bis(trichloromethyl) -s -triazine, 4-[ p- N,N-di(chloroethyl)amine phenyl]-2,6-di (trichloromethyl) -s -triazine, 4-[ o -methyl- p- N,N-bis(chloroethyl)aminephenyl]-2,6-di(trichloromethyl) -s -triazine, 4-( p -N-chloroethylamine phenyl)-2,6-bis(trichloromethyl) -s -triazine, 4-( p -N-ethoxycarbonylmethylamine phenyl)-2,6-di (trichloromethyl) -s -triazine, 4-[ p- N,N-di(phenyl)amine phenyl]-2,6-di(trichloromethyl) -s -triazine, 4- ( p -N-chloroethylcarbonylamine phenyl)-2,6-bis(trichloromethyl) -s -triazine, 4-[ p -N-( p -methoxyphenyl)carbonylamine phenyl -2,6-bis(trichloromethyl) -s -triazine, 4-[ m- N,N-bis(ethoxycarbonylmethyl)aminephenyl]-2,6-di(trichloromethane) -s -triazine, 4-[ m -bromo- p- N,N-bis(ethoxycarbonylmethyl)aminephenyl]-2,6-bis(trichloromethyl) -s -triazine 4-[ m -Chloro- p -N,N-bis(ethoxycarbonylmethyl)amine phenyl]-2,6-di(trichloromethyl) -s -triazine, 4-[ m -fluorine - p- N,N-bis(ethoxycarbonylmethyl)amine phenyl]-2,6-bis(trichloromethyl) -s -triazine, 4-[ o -bromo- p- N,N- Di(ethoxycarbonylmethyl)amine phenyl]-2,6-bis(trichloromethyl) -s -triazine, 4-[ o -chloro- p- N,N-bis(ethoxycarbonylmethyl Amine phenyl] 2,6-bis (trichloromethyl) - s - triazine, 4- [o - fluoro - p -N, N- bis (ethoxycarbonylmethyl) aminophenyl] -2,6-di (tri Chloromethyl) -s -triazine, 4-[ o -bromo- p- N,N-bis(chloroethyl)aminephenyl]-2,6-bis(trichloromethyl) -s -triazine 4-[ o -chloro- p- N,N-bis(chloroethyl)aminephenyl]-2,6-bis(trichloromethyl) -s -triazine, 4-[ o -fluoro- p -N,N-bis(chloroethyl)amine phenyl]-2,6-bis(trichloromethyl) -s -triazine, 4-[ m -bromo- p- N,N-di(chloroethane) Aminophenyl]-2,6-bis(trichloromethyl) -s -triazine, 4-[ m -chloro- p- N,N-bis(chloroethyl)aminephenyl]-2, 6-bis(trichloromethyl) -s -triazine, 4-[ m -fluoro- p- N,N-bis(chloroethyl)aminephenyl]-2,6-di(trichloromethyl) - s -triazine, 4-( m -bromo- p -N-ethoxycarbonylmethylamine phenyl)-2,6-bis(trichloromethyl) -s -triazine, 4-( m -chloro - p -N-ethoxycarbonylmethylamine phenyl)-2,6-bis(trichloromethyl) -s -triazine, 4-( m -fluoro- p -N-ethoxycarbonylmethylamine benzene Base)-2,6-two (three Methyl) - s - triazine, 4- (o - bromo - p -N- ethoxycarbonylmethyl aminophenyl) -2,6-bis (trichloromethyl) - s - triazine, 4- ( o -Chloro- p -N-ethoxycarbonylmethylamine phenyl)-2,6-bis(trichloromethyl) -s -triazine, 4-( o -fluoro- p -N-ethoxycarbonylmethyl Phenyl phenyl)-2,6-bis(trichloromethyl) -s -triazine, 4-( m -bromo- p -N-chloroethylamine phenyl)-2,6-di(trichloro) Methyl) -s -triazine, 4-( m -chloro- p -N-chloroethylaminephenyl)-2,6-bis(trichloromethyl) -s -triazine, 4-( m- Fluorine- p -N-chloroethylamine phenyl)-2,6-bis(trichloromethyl) -s -triazine, 4-( o -bromo- p -N-chloroethylamine phenyl)- 2,6-bis(trichloromethyl) -s -triazine, 4-( o -chloro- p -N-chloroethylaminephenyl)-2,6-di(trichloromethyl) -s - Triazine, 4-( o -fluoro- p -N-chloroethylamine phenyl)-2,6-di(trichloromethyl) -s -triazine, and the like.

Others, TAZ series manufactured by Midori Chemical Co., Ltd. (for example, TAZ-107, TAZ-110, TAZ-104, TAZ-109, TAZ-140, TAZ-204, TAZ-113, TAZ-123, etc.), manufactured by PANCHIM T series (for example, T-OMS, T-BMP, T-R, T-B, etc.), Irugacure series by Ciba Speciality Chemical (shares) (for example, Irugacure 651, Irugacure 184, Irugacure 500, Irugacure 1000, Irugacure 149) , Irugacure 819, Irugacure 261, etc.), Darocure series (eg, Darocure 1173, etc.), 4,4'-bis(diethylamino)benzophenone, 2-benzyl-2-dimethylamino-4 -morpholinobutene, 2,2-dimethoxy-2-phenylacetophenone, 2-( o -chlorophenyl)-4,5-diphenylimidazole dimer, 2-( O -fluorophenyl)-4,5-diphenylimidazole dimer, 2-( o -methoxyphenyl)-4,5-diphenylimidazole dimer, 2-( p -methoxy Phenyl)-4,5-diphenylimidazole dimer, 2-( p -dimethoxyphenyl)-4,5-diphenylimidazole dimer, 2-(2,4-di methoxyphenyl) -4,5-diphenyl imidazole dimer, 2- (p - mercapto methyl phenyl) 4,5-diphenyl imidazole dimer, benzoin isopropyl ether and the like are also useful.

In the dye-containing negative-type hardenable composition of the present invention, other conventional photopolymerization initiators other than the photopolymerization initiator can be further used in combination. Specifically, a vicinal polyketol-uronic acid compound disclosed in the specification of U.S. Patent No. 2,367,660, and an α-carbonyl compound disclosed in the specification of U.S. Patent Nos. 2,276,661 and 2,367,670, The benzoin ether disclosed in the specification of U.S. Patent No. 2,448,828, the aromatic enamel compound substituted by the α-hydrocarbon disclosed in the specification of U.S. Patent No. 2,722,512, and the patents of U.S. Patent Nos. 3,046,127 and 2,951,758. The polynuclear oxime compound of the specification, the combination of a triaryl imidazole dimer/ p -amino phenyl ketone disclosed in the specification of U.S. Patent No. 3,549,367, the benzothiazole compound disclosed in Japanese Patent Publication No. Sho 51-48516 /trihalomethyl- s -triazine-based compound and the like.

The dye-containing initiator of the present invention (and, if necessary, other initiators, other conventional photopolymerization initiators), relative to the solid content (mass) of the (C) radical polymerizable monomer described later. The content of the negative-type hardenable composition is preferably from 0.01 to 50% by mass, more preferably from 1 to 30% by mass, particularly preferably from 1 to 20% by mass. When the content is in this range, sufficient polymerization and hardening can be performed, and polymerization is not made difficult, or the polymerization rate is increased, but the molecular weight is not lowered and the film strength is weak.

In addition, in the case of using two kinds of lanthanide initiators, the mixing ratio of the two lanthanide initiators can be arbitrarily set in the range of 1/99 to 99/1, and is preferably set to 5/95 to 95/ The range of 5 is more preferably set to the range of 10/90 to 90/10.

Further, in the photopolymerization initiator, a sensitizer or a photosensitizer may be used in combination.

Specific examples thereof include benzoin, benzoin methyl ether, 9-fluorenone, 2-chloro-9-fluorenone, 2-methyl-9-fluorenone, 9-fluorenone, 2-bromo- 9-fluorenone, 2-ethyl-9-fluorenone, 9,10-fluorene, 2-ethyl-9,10-fluorene, 2- t -butyl-9,10-fluorene, 2, 6-Dichloro-9,10-fluorene, xanthone, 2-methylxanthone, 2-methoxyxanthone, thiazinone, 2,4-diethylxanthone, anthraquinone Pyridone, 10-butyl-2-chlorothioxanthone, benzoin, benzoin, p- (dimethylamino)phenylstyrylone, p- (dimethylamino)phenyl - p -methylstyryl ketone, benzophenone, p- (dimethylamino)benzophenone (or michelone), p- (diethylamino)benzophenone, benzene A benzothiazole compound or the like disclosed in Japanese Patent Publication No. Sho 51-48516, or Tinuvin 1130, Tinuvin 400, or the like.

(C) Radical polymerizable monomer

The negative-type curable composition containing a dye of the present invention contains at least one of a radical polymerizable monomer. The radical polymerizable monomer preferably has a boiling point of 100 ° C or more at normal pressure and contains at least one ethylenically unsaturated group compound which can undergo addition polymerization. By containing the (B) photopolymerization initiator together with the radical polymerizable monomer, a negative-type curable composition can be formed.

The ethylenically unsaturated group is particularly preferably a (meth) acrylonitrile group. Further, the (meth)acrylonitrile group means an acryloyl group or a methacryloyl group. Similarly, the following (meth)acrylate means an acrylate or a methacrylate.

Examples thereof include monofunctional acrylates or methacrylates such as poly(ethylene) methacrylate, poly(meth)acrylic acid propylene glycol ester, and (meth)acrylic acid phenoxyethyl ester; Polyethylene glycol di(meth)acrylate, trimethylolethyl tris(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, tetrakis(methyl) Pentaerythritol acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, hexanediol (meth)acrylate, trimethylolpropane tris(propylene oxypropyl)ether a (meth) acrylated tris(propylene oxy oxyethyl) isocyanate, which is obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol such as glycerin or trimethylolethane; The urethane acrylates disclosed in Japanese Patent Publication No. Sho 48-41708, Japanese Patent Publication No. Sho 50-6034, and JP-A-51-37193 are disclosed in Japanese Patent Laid-Open No. Sho 48-64183, No. Polyester acrylates of the publications No. 49-43191 and special public notice No. 52-30490; epoxy resins and (methyl) A polyfunctional ester of acrylic acid reaction product of a mixture of an epoxy acrylate or methacrylate esters of these, and the like. Further, examples thereof include photocurable monomers and oligomers disclosed in Japanese Patent Association Vol. 20, No. 7, pages 300-308.

Among them, from the viewpoint of improvement in the degree of hardening, a polyfunctional (meth) propylene compound having two or more (meth) acrylonitrile groups is more preferable, and a polyfunctional (meth) acrylate is more preferable. Polyfunctional (meth) acrylates are particularly suitable as dipentaerythritol hexaacrylate.

Wherein at least one of polyfunctional (meth) acrylates (preferably dipentaerythritol hexaacrylate) and the quinone initiator of the phenyl group and the oxime initiator of the aminomethanyl group Species [in particular, 2-(O-phenylhydrazinyl)-1-[4-(phenylthio)phenyl]-1,2-octanedione and 1-(O-ethylindenyl)-1- A combination of [9-ethyl-6-(2-methylphenylhydrazyl)-9H-aminomethylindolyl-3-indenyl]ethanone] is particularly preferred.

The content of the negative-type curable composition containing the dye in the radically polymerizable monomer is preferably from 1 to 60% by mass, more preferably from 10 to 50% by mass, based on the total solid content of the composition. When the content is in this range, the sufficient degree of hardening and the elution property of the unexposed portion can be maintained, and the degree of hardening of the exposed portion is not caused to be insufficient or the elution property of the unexposed portion is remarkably lowered.

(D) Adhesive resin

The present invention contains a negative-type curable composition of a dye, and if necessary, can contain at least one of binder resins. When the binder resin is soluble in an organic solvent, it can be appropriately selected from conventional resin components, and an organic polymer is preferably used. In particular, the alkali-soluble binder is not particularly limited as long as it is water-soluble or alkali-soluble, and is preferably selected from the viewpoints of heat resistance, developability, and availability.

The alkali-soluble binder is preferably a linear organic high molecular polymer, soluble in an organic solvent, and capable of being developed in a weak alkaline aqueous solution. Such a linear organic polymer is a polymer having a carboxylic acid in a side chain, and examples thereof include, for example, JP-A-59-44615, JP-A-54-34327, and JP-A-58-12577. Methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid disclosed in Japanese Patent Publication No. Sho 54-25957, JP-A-59-53836, and JP-A-59-71048 Copolymers, partially esterified maleic acid copolymers and the like are particularly useful as acidic cellulose derivatives having a carboxylic acid in a side chain. In addition, an acid anhydride is added to a polymer having a hydroxyl group, or a polyhydroxystyrene resin, a polyoxyalkylene resin, poly(2-hydroxyethyl (meth)acrylate), or polyethylene. Pyrrolidone or polyethylene oxide, polyvinyl alcohol and the like are also useful.

Further, copolymerization with a hydrophilic group monomer may be carried out, and examples thereof include alkoxyalkyl (meth)acrylate, hydroxyalkyl (meth)acrylate, and glyceryl (meth)acrylate. Base) acrylamide, acrylamide-N-hydroxymethyl ester, propylene amide alkyl esters of grades 2 and 3, dialkylaminoalkyl (meth)acrylate, morpholino (meth)acrylate, N-vinylpyrrolidone, N-vinyl caprolactam, vinylimidazole, vinyltriazole, methyl (meth)acrylate, ethyl (meth)acrylate, branched or linear (meth)acrylic acid Ester, branched or linear butyl (meth) acrylate, phenoxy hydroxypropyl (meth) acrylate, and the like.

In addition, a monomer having a hydrophilic group containing a tetrahydroindenyl group, a phosphoric acid moiety, a phosphate moiety, a 4-stage ammonium salt moiety, an ethylene oxide chain, a propylene oxide chain, a sulfonic acid or the like A monomer such as a moiety or a morpholinoethyl group is also useful.

Further, from the viewpoint of improving the crosslinking efficiency, a polymerizable group may be provided in the side chain, and a polymer having an allyl group, a (meth)acryl group or a propyleneoxyalkyl group in the side chain may also be used. useful. Examples of the polymer having such a polymerizable group include KS photoresist-106 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), and Cyclomer P series (manufactured by Daicel Chemical Industry Co., Ltd.).

Further, from the viewpoint of improving the strength of the cured film, alcohol-soluble nylon, a polyether of 2,2-bis(4-hydroxyphenyl)propane and epoxychloropropylpyrrolidone, and the like are also useful.

Among the various alkali-soluble binders, polyhydroxystyrene resin, polyoxyalkylene resin, propylene resin, acrylamide resin, acryl/acrylamide are preferred from the viewpoint of heat resistance. The copolymer resin is preferably a propylene-based resin, an acrylamide-based resin, or a propylene/acrylamide copolymer resin from the viewpoint of development control. The propylene-based resin is preferably copolymerized by a monomer selected from benzyl (meth)acrylate, (meth)acrylic acid, hydroxyethyl (meth)acrylate, (meth)acrylamide or the like. KS photoresist (106 manufactured by Osaka Organic Chemical Industry Co., Ltd.) and Cyclomer P series (made by Daicel Chemical Industry Co., Ltd.).

The mass average molecular weight of the alkali-soluble binder (polystyrene-converted value measured by GPC method) is preferably a polymer of 1000 to 2 × 10 ⁵ , more preferably a polymer of 2000 to 1 × 10 ⁵ , It is particularly desirable to be a polymer of 5000 to 5 x 10 ⁴ .

In the present invention, the binder resin is not a necessary component, and may be added for the purpose of modifying the surface of the film. The amount of the solid component in the case of the negative-type hardenable composition containing the dye is preferably from 1 to 40% by mass, more preferably from 1 to 30% by mass. When the binder resin is contained in this range, the uniformity of the coating film surface can be effectively improved, and it is effective from the viewpoint of suppressing the elution of the exposed portion. Further, when the amount of the binder resin is too large, the dissolution inhibiting property of the exposed portion is remarkably deteriorated.

(E) organic solvent

At least one of general organic solvents can be used in the preparation of the dye-containing negative-type hardenable composition of the present invention. The organic solvent is basically not particularly limited as long as it satisfies the solubility of each component or the coating property of the negative-type curable composition containing a dye, and in particular, the solubility, coatability, and safety of the alkali-soluble adhesive are considered. It is especially desirable to choose.

Specific examples of the organic solvent, for example, preferred examples of the ester include ethyl acetate, n -butyl acetate, isobutyl acetate, amyl amide, isoamyl acetate, isobutyl acetate, and butyl propionate. Isobutyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methoxy Methyl acetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.; methyl 3-oxypropionate, ethyl 3-oxypropionate Ethyl 3-oxopropionates, for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropane Ethyl acetate, etc.; 2-oxopropionic acid alkyl esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate, and propyl 2-oxypropionate, for example, 2-methoxyl Methyl propionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-oxy- Methyl 2-methylpropionate, ethyl 2-oxy-2-methylpropionate Methyl 2-methoxy-2-methylpropanoate, ethyl 2-ethoxy-2-methylpropionate, etc.; methyl pyruvate, ethyl pyruvate, propyl pyruvate, ethyl acetate Ester, ethyl acetate ethyl acetate, methyl 2-carbonylbutyrate, ethyl 2-carbonylbutyrate, etc.; for example, preferred ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol-methyl Ether, ethylene glycol monoethyl ether, methyl cellulose acetate, ethyl cellulose 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.; for example, preferred ketones can be mentioned: methyl ethyl ketone, cyclohexyl A ketone, 2-heptanone, 3-heptanone or the like; an aromatic hydrocarbon such as toluene or xylene.

(F) Other ingredients -crosslinker -

In the present invention, a film which is more highly hardened can be obtained by using a sufficient crosslinking agent. In this case, it can be configured using at least one of the crosslinking agents shown below.

The crosslinking agent which can be used in the present invention is not particularly limited as long as it can be cured by a crosslinking reaction, and examples thereof include (a) an epoxy resin and (b) a hydroxyl group. a melamine compound, a melamine compound, a glycoluril compound or a urea compound in which at least one functional group selected by a methyl group, an alkoxymethyl group and a decyloxymethyl group is substituted; (c) using a methylol group, A phenol compound, a naphthol compound or a hydroxy hydrazine compound in which at least one functional group selected from the alkoxymethyl group and the methoxymethyl group is substituted. Among them, a polyfunctional epoxy resin is particularly preferable.

The (a) epoxy resin may be, as long as it has an epoxy group and has crosslinkability, for example, bisphenol A epoxy propyl ether, ethylene glycol diepoxypropyl ether, and dibutyl Alcohol diglycidyl ether, hexanediol diepoxypropyl ether, dihydroxybiphenyl diglycidyl ether, diepoxypropyl phthalate, N,N-diepoxypropyl aniline, etc. a low molecular compound containing a divalent epoxy propyl group; similarly, trimethylolpropane triepoxypropyl ether, trimethylol phenol triepoxypropyl ether, TrisP-PA triepoxypropyl ether, etc. a low molecular compound containing a trivalent epoxy propyl group; similarly, a tetravalent epoxy propyl group represented by pentaerythritol tetraepoxypropyl ether, tetramethylol bisphenol A tetraepoxypropyl ether or the like Low molecular compound; similarly, low molecular compound containing polyvalent epoxy propyl group such as dipentaerythritol pentaethoxypropyl ether, dipentaerythritol hexa-epoxypropyl ether; polyepoxypropyl (meth) acrylate a 1,2-bis(hydroxymethyl)-1-butanol 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct, etc. Base height Sub compound.

The number of substitutions of the methylol group, the alkoxymethyl group, and the decyloxymethyl group contained in the crosslinking agent (b), the case of the melamine compound is 2 to 6; the glycoluril compound, the melamine diamine The case of the compound and the urea compound is 2 to 4; the case of the melamine compound is preferably 5 to 6; the case of the glycoluril compound, the melamine diamine compound, and the urea compound is preferably 3 to 4.

Hereinafter, the melamine compound, the melamine diamine compound, the glycoluril compound, and the urea compound of (b) are collectively referred to as a compound related to (b) (a compound containing a methylol group, a compound containing an alkoxymethyl group or containing a compound of a methoxymethyl group).

The compound containing a hydroxyl group in the above (b) is heated by the alkoxymethyl group-containing compound of (b) in the presence of an acid catalyst such as hydrochloric acid, sulfuric acid, nitric acid or methanesulfonic acid in an alcohol. owned. The oxiranylmethyl group-containing compound of the above (b) is obtained by mixing and stirring a compound containing a methylol group (b) and hydrazine chloride in the presence of a salt-based catalyst.

Specific examples of the compound (b) having the substituent are listed below.

For example, the melamine compound may be hexamethylol melamine, hexamethoxymethyl melamine, hexamethylol melamine, 1 to 5 methylol groups, methoxymethylated compounds or mixtures thereof, hexamethoxy A compound in which one to five methylol groups of ethyl melamine, hexamethoxymethyl melamine, and hexamethylol melamine are methoxyoxymethylated or a mixture thereof.

For example, the melamine compound can be exemplified by 1 to 3 hydroxyl groups of tetramethylol melamine, tetramethoxymethyl melamine, and tetramethylol melamine. a methoxymethylated compound or a mixture thereof, tetramethoxyethyl melamine, tetramethoxymethyl melamine, tetramethylol melamine A compound in which three methylol groups are methylated by methyloxy group or a mixture thereof.

For example, the glycoluril compound may be exemplified by a methoxymethylated compound of 1 to 3 methylol groups of tetramethylol glycoluril, tetramethoxymethyl glycoluril or tetramethylol glycoluril or A mixture or a mixture of 1 to 3 methylol groups of tetramethylol glycoluril, which is a methyloxymethylated group, or a mixture thereof.

For example, the urea compound may be exemplified by a compound of tetramethylol urea, tetramethoxymethyl urea, hydroxymethyl group of 1,4-hydroxymethyl urea, or a mixture thereof, or a mixture thereof. Oxyethyl urea and the like.

The compound of (b) may be used singly or in combination.

The crosslinking agent (c), that is, the phenol compound, the naphthol compound or the hydroxy hydrazine compound substituted with at least one substituent selected by a methylol group, an alkoxymethyl group and a fluorenyloxymethyl group is the same In the case of the crosslinking agent (b), the miscibility with the surface coating photoresist is suppressed by thermal crosslinking while further increasing the film strength.

Hereinafter, these compounds are collectively referred to as the compound (c) (a compound containing a methylol group, a compound containing an alkoxymethyl group or a compound containing a methoxymethyl group).

The number of hydroxymethyl, decyloxymethyl or alkoxymethyl groups contained in the crosslinking agent (c) must be at least 2 per molecule, based on the viewpoint of thermal crosslinkability and preservation stability. It is preferred to be a compound in which all of the 2-position and 4-position of the naphthol compound of the backbone are substituted. Further, the naphthol compound and the hydroxyquinone compound which are the backbone are preferably compounds which are substituted at all ortho and para positions of the OH group. The 3- or 5-position of the phenol compound which becomes the backbone may be unsubstituted or may have a substituent. Further, the naphthol compound may be unsubstituted or may have a substituent in addition to the ortho position of the OH group.

The compound containing a methylol group of (c) is used as a raw material by using a compound having a phenolic OH group at the 2- or 4-position (ortho or para) as a hydrogen atom, and is made to be sodium hydroxide or hydrogen. It is obtained by reacting with formalin in the presence of a salt-based catalyst such as potassium oxide, ammonia or tetraalkylammonium hydroxide.

The alkoxymethyl group-containing compound of the above (c) is subjected to a methylol group-containing compound according to (c) in the presence of an acid catalyst such as hydrochloric acid, sulfuric acid, nitric acid or methanesulfonic acid in an alcohol. Heated up.

The oxiranylmethyl group-containing compound of the above (c) is obtained by reacting a compound containing a methylol group (c) with ruthenium chloride in the presence of a salt-based catalyst.

The backbone compound of the crosslinking agent (c) may be an unsubstituted phenol compound, a naphthol, a hydroxy hydrazine compound or the like in the ortho or para position of the phenolic OH group. For example, each isomer of phenol or cresol may be used. , 2,3-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, bisphenol A, etc., bisphenols, 4,4'-dihydroxyl linkage Benzene, TrisP-PA (manufactured by Honshu Chemical Co., Ltd.), naphthol, dihydroxynaphthalene, 2,7-dihydroxyindole, and the like.

Specific examples of the crosslinking agent (c) include, for example, trishydroxymethylphenol, tris(methoxymethyl)phenol, and 1 to 2 methylol groups of trimethylolphenol. One or two hydroxymethyl groups of oxymethylated compound, trimethylol-3- cresol, tris(methoxymethyl)-3-cresol, and trishydroxymethyl-3-cresol a methoxymethylated compound, dimethylol cresol such as 2,6-dimethylol-4-cresol, tetramethylol bisphenol A, tetramethoxymethylbisphenol A, or the like a methoxymethylated compound of 1 to 3 hydroxymethyl groups of hydroxymethyl bisphenol A, tetramethylol-4,4'-bishydroxybiphenyl, tetramethoxymethyl-4,4' - bishydroxybiphenyl, hexamethylol of TrisP-PA, hexamethoxymethyl of TrisP-PA, 1-6 methylol of hexamethylol of TrisP-PA, methoxymethyl The naphthol compound may, for example, be a dimethylol naphthalenediol or the like.

Further, examples of the hydroxy hydrazine compound include 1,6-dihydroxymethyl-2,7-dihydroxyindole and the like.

In addition, examples of the compound containing a methoxymethyl group include a compound in which a part or all of a methylol group of a methylol group-containing compound is methoxyoxymethylated.

Among the compounds, preferred examples thereof include trishydroxymethylphenol, bishydroxymethyl- p -cresol, tetramethylol bisphenol A, and TrisP-PA (manufactured by Honshu Chemical Co., Ltd.). A hexamethylol or a phenolic compound in which the methylol group is replaced by an alkoxymethyl group and both a methylol group and an alkoxymethyl group.

The compounds of these (c) may be used singly or in combination.

Depending on the type of the raw material, the total amount of the negative-type hardenable composition containing the crosslinking agent dye in the case of the solid content (mass) of the composition containing the crosslinking agents (a) to (c) The content is preferably from 1 to 70% by mass, more preferably from 5 to 50% by mass, particularly preferably from 7 to 30% by mass.

- Thermal polymerization inhibitor -

In addition to the above, it is preferred to further carry out the addition of the thermal polymerization inhibitor. For example, hydroquinone, p -methoxyphenol, di- t -butyl- p -cresol, pyrogallol, t -butyl catechol, benzophenone, 4,4'-thiobis (3 -Methyl-6- t -butylphenol), 2,2'-methylenebis(4-methyl-6- t -butylphenol), 2-hydrothiobenzimidazole, and the like are useful.

- Various additives -

In the dye-containing negative-type hardenable composition of the present invention, if necessary, various additives such as a filler, a polymer compound other than the above, a surfactant, a adhesion promoter, an antioxidant, and an ultraviolet absorber may be blended. , anti-coagulant, etc.

Specific examples of the various additives include a filler such as glass or alumina; a polymer compound other than an adhesive resin such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether or polyfluoroalkyl acrylate; and nonionic Surfactants such as cations, cationics, and anionics; vinyl trimethoxy decane, vinyl triethoxy decane, vinyl tris(2-methoxyethoxy) decane, N-(2-amino B 3-aminopropylmethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyltrimethoxydecane, 3-aminopropyltriethoxylate Baseline, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethyl Oxydecane, 3-chloropropylmethyldimethoxydecane, 3-chloropropyltrimethoxydecane, 3-methylpropoxypropyltrimethoxydecane, 3-hydrothiopropyltrimethyl An adhesion promoter such as oxydecane; an antioxidant such as 2,2-thiobis(4-methyl-6- t -butylphenol) or 2,6-di- t -butylphenol; (3- t - butoxy 5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxy of benzophenone ultraviolet absorbers; sodium polyacrylate, etc. and an anti-coagulant.

Further, in order to promote the alkali solubility of the non-hardened portion, it is desirable that the developer of the negative-type curable composition containing the dye of the present invention is further improved, and it is preferred to add the organic carboxylic acid to the composition. A low molecular weight organic carboxylic acid having a molecular weight of 1,000 or less.

Specific examples thereof include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trimethylacetic acid, caproic acid, diethyl acetic acid, heptanoic acid, and octanoic acid; oxalic acid and propylene; Diacid, succinic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, malic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, A An aliphatic dicarboxylic acid such as succinic acid, tetramethyl succinic acid or citraconic acid; an aliphatic tricarboxylic acid such as tris-trimethylbenzene, propylene-1,2,3-tricarboxylic acid or camphoric acid ; aromatic monocarboxylic acid such as benzoic acid, toluic acid, p-isopropylbenzoic acid, dimethylphenyl acid, 3,5-dimethylbenzoic acid; phthalic acid, isophthalic acid, p-phenylene An aromatic polycarboxylic acid such as formic acid, trimellitic acid, trimesic acid, pyromellitic acid or pyromellitic acid; phenylacetic acid, α-methylphenylacetic acid, hydrogenated cinnamic acid, α-phenylglycolic acid, Phenyl succinic acid, α-phenylacrylic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamulinic acid, coumaric acid, 2,4-dihydroxycinnamic acid, etc. Acid.

For the exposure of the dye-containing negative-type hardenable composition of the present invention, any one of a proximity mode, a mirror projection mode and a stepper mode may be employed, in particular, using a stepping machine method (reduced projection exposure using a reduced projection exposure machine) Method) It is particularly desirable to perform exposure. In the stepping machine method, the pattern is changed in a stepwise manner, and the pattern is formed by exposure, and when the stepper is exposed, the pattern rectangle of one of the effects of the present invention can be formed more favorably. . For the exposure apparatus for stepper exposure, for example, an i-line stepping machine (trade name: FPA-3000i5+ manufactured by Canon) can be used.

The dye-containing negative-type hardenable composition of the present invention can be suitably used as a color image for use in a color filter such as a liquid crystal display device (LCD) or a solid-state imaging device (for example, CCD or CMOS), and also It can be applied to production applications such as printing inks, inkjet inks, and paints.

<<Color filter and its manufacturing method>>

Next, the color filter of the present invention will be described in detail based on the manufacturing method thereof.

In the method for producing a color filter of the present invention, a negative-type curable composition containing a dye of the present invention can be used. The color filter of the present invention is most suitably produced by using the dye-containing negative-type curable composition of the present invention, and specifically, by a coating method such as spin coating, flow coating, or roll coating. The dye-containing negative-type hardenable composition is applied onto a carrier to form a photosensitive composition layer, and after passing through a predetermined mask pattern, the thin layer is exposed to light, and then developed using a developing solution to form a negative colored pattern. (Image forming step). At this time, if necessary, a hardening step of curing the formed color pattern by heating and/or exposure may be provided.

In the production of a color filter, by repeating the image forming step (and the necessary hardening step) in accordance with the required number of tones, it is possible to produce a color filter comprising a desired number of tones. In this case, it is particularly preferable to use ultraviolet rays such as g-line, h-line, and i-line for the light or radiation to be used.

For example, the carrier may be a soda lime glass for a liquid crystal display element, a hard glass (Pyrex; registered trademark) glass, a quartz glass, or a transparent conductive film attached to the glass, or a photoelectric conversion for a photographic element or the like. The element substrate, for example, a germanium substrate or the like, or a complementary metal oxide film semiconductor (CMOS) or the like. These carriers can also form a black matrix driver that isolates each pixel.

Further, if necessary, an undercoat layer may be provided on the carrier in order to improve adhesion to the upper thin layer, prevent diffusion of the substance, or planarize the surface of the substrate.

The developing solution which is a method for producing a color filter of the present invention is a composition which dissolves the hardened portion of the negative-type curable composition containing the dye of the present invention, and the hardened portion of the filter is not dissolved. Any one of them can be used. Specifically, a combination of various organic solvents or an aqueous alkaline solution can be used. Examples of the organic solvent include the organic solvent used in the preparation of the negative-type curable composition containing the dye of the present invention.

For example, the alkaline aqueous solution is preferably sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide. , a basic compound such as tetraethylammonium hydroxide, choline, pyrrole, piperidine or 1,8-dibicyclobicyclo[5.4.0]-7-undecene is dissolved to make the concentration 0.001 to 10 mass. % is preferably an alkaline aqueous solution of 0.01 to 1% by mass. Further, in the case of using a developing solution obtained from such an alkaline aqueous solution, it is usually washed with water after development.

The color filter of the present invention can be used for a solid-state imaging element such as a liquid crystal display element or a CCD, and is particularly suitable for a CCD element or CMOS having a high resolution of more than 1,000,000 pixels. The color filter of the present invention can be used, for example, as a color filter disposed between each of the pixel light receiving portions constituting the CCD and the microlens for collecting light.

[Examples]

Hereinafter, the present invention will be more specifically described by the examples, and the present invention is not limited by the following examples as long as they do not.

[Examples 1 to 8 and Comparative Examples 1 to 4] 1) Modulation of a negative-type hardenable composition containing a dye

The compound of the composition shown in the following Table 1 was mixed and dissolved to prepare a dye-containing negative-type hardenable composition of the present invention and comparatively.

The details of the compositions (A) to (E) in Table 1 are as follows: * Resin A: benzyl methacrylate / methacrylic acid copolymer (= 80 / 20 [mr ratio]) * single Body A: DPHA (trade name; main component: dipentaerythritol hexaacrylate) manufactured by Nippon Kayaku Co., Ltd. * TAZ-107: Midori Chemical Co., Ltd. * TAZ-140: Midori Chemical Co., Ltd. *肟A : 2-(O-phenylhydrazinyl)-1-[4-(phenylthio)phenyl]-1,2-octanedione*肟B:Ciba Speciality Chemicals (shared by Ciba Speciality Chemicals) 1-(O-Ethylindole)-1-[9-ethyl-6-(2-methylphenylindenyl)-9H-aminomethylindolyl-3-indenyl]ethanone* Imidazole dimer A: 2-( o -chlorophenyl)-4,5-diphenylimidazole dimer

2) Fabrication of a glass substrate with an undercoat layer

On a wafer substrate, a photoresist CT-2000L solution (manufactured by Fujifilm Arch Co., Ltd., Japan) was applied to a film thickness of 2 μm by a spin coater, and heat-dried at 220 ° C for 1 hour to form a hardened film. Membrane (undercoat).

3) Exposure and development (image formation) of a negative-type hardenable composition containing a dye

The dye-containing negative-type hardenable composition obtained in each of the above 1) is sequentially applied to the glass substrate undercoat layer of the undercoat layer obtained in each of the above 2) by a spin coater to form a film. The thick coating was carried out in the same manner as 1 μm, and prebaking was carried out at 100 ° C for 120 seconds.

Next, the i-line reduction projection exposure apparatus was used to irradiate the coating film by changing the exposure amount by a 365 nm wavelength through a mask having a line width of 2 μm. After the irradiation, development was carried out using a 60% CD-2000 (manufactured by Fujifilm Electronics Materials Co., Ltd., Japan) at 23 ° C for 60 seconds. Subsequently, the mixture was rinsed for 20 seconds by a water flow method, and then spray-dried to obtain a pattern image (color filter). The image formation was confirmed by a general method by optical microscopy and SEM photographing.

4) Evaluation

The following evaluations were performed for each pattern image obtained by using the dye-containing negative-type curable composition obtained in each of the examples and the comparative examples. The results of the evaluation are shown in Table 2 below.

-1. Uniformity within the coating film -

The dye-containing negative-type curable composition obtained in the above 1) was applied onto a tantalum wafer to which an undercoat layer was applied by a spin coater to a film thickness of 1 μm, and was dried at 100 ° C for 120 seconds. Pre-baked. Then, a defect was placed at any ten positions of the formed coating film surface by a probe type film thickness meter (Dektak 6 manufactured by Veeco Co., Ltd.), and the film thickness [μm] was measured. Among the ten points, the eight-point average value after deducting the values from the maximum and the minimum is selected as the absolute value, and the point farthest from the average value is selected from the eight points to calculate the difference (film thickness). difference). It means that the smaller the value, the higher the in-plane uniformity.

-2. Sensitivity -

In the 2 μm width pattern, the exposure amount of the dot and the width of the gap is 1:1, and the exposure amount is set to an appropriate exposure amount, and the exposure amount is set as the sensitivity. The smaller the value, the higher the sensitivity and the better the sensitivity.

-3. Outline -

By visually observing the cross-sectional shape of the pattern image by the SEM image of the appropriate exposure amount of 2., the person whose outline is rectangular is evaluated as "○", and the person who is slightly dome-shaped (head is round) is evaluated. For "△", the shape of the dome (head is round) is evaluated as "X".

As shown in Table 2, in the examples in which two kinds of lanthanide initiators having different structures were used, high sensitivity was obtained, and the cross-sectional shape of the formed pattern image was a good rectangle. Further, the formed coating film is formed very uniformly, and as a result, the completed element can be obtained in a high yield. In contrast, in the comparative example in which the two oxime-based initiators were not combined, not only the single one and the two non-steroidal initiators were used, but not only the cross section of the sensitivity and the pattern image. The squareness is greatly deteriorated, and the uniformity of the film in the film is not sufficient.

Further, in addition to the combination of the two oxime initiators used in the examples, it can be used in combination with any of the examples in which the lanthanide initiators of the present invention are combined. The same effect of the combination, as described above, can be obtained with high sensitivity, and it is possible to form a pattern having a good rectangular cross section and uniformity within the film.

Claims (8)

A negative-type hardening composition containing a dye, comprising at least (A) an organic solvent-soluble dye, (B) a photopolymerization initiator, and (C) a radical polymerizable monomer; characterized in that: (A) Organic solvent soluble dyes are pyrazole azo, aniline azo, pyrazole triazole azo, pyridone azo, anthraquinone, anthrapyridone dyes; (B) photopolymerization initiator Containing at least a phenyl ruthenium starter and an aminomethionyl ruthenium starter; the (C) radically polymerizable single system having a polyfunctionality of two or more (meth) acrylonitrile groups (methyl) ) a propylene based compound. A dye-containing negative-type hardening composition according to claim 1, wherein the phenyl ruthenium initiator is 2-(O-phenylhydrazinyl)-1-[4-(phenylthio)benzene 1,1,2-octanedione, the aminomethanyl oxime initiator is 1-(O-ethylindenyl)-1-[9-ethyl-6-(2-methylbenzene Mercapto)-9H-aminomethylmercapto-3-indenyl]ethanone. A dye-containing negative-type hardening composition according to claim 1, wherein (D) an adhesive resin is further contained. The dye-containing negative-type hardenable composition according to any one of claims 1 to 3, wherein the (C) radical polymerizable monomer is a polyfunctional (meth)acryl-based compound. A dye-containing negative-type hardenable composition according to claim 3, wherein the (D) binder resin is an alkali-soluble resin. The dye-containing negative-type hardenable composition according to any one of claims 1 to 3, wherein the (A) organic solvent-soluble dye is composed of at least two dye mixtures having different absorption characteristics. A color filter comprising a negative-type curable composition containing a dye according to any one of claims 1 to 6. A method for producing a color filter, comprising: coating a negative-type hardening group containing a dye according to any one of claims 1 to 6 on a carrier; After the object is formed, the film is exposed and developed through a photomask to form a pattern.