TWI382279B - 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 suitable for forming a color filter of a liquid crystal display element or a solid-state imaging element, and a dye-containing color filter and a method of manufacturing the same.

A method of producing a color filter for a liquid crystal display element (LCD) or a solid-state imaging element (CCD, CMOS, etc.) is known as a dyeing method, a printing method, an electrode deposition 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 the colored pixels are formed by development, and the color tone is obtained by repeating this operation in accordance with the desired number of tones. 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, see Patent Document 1).

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 case of 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 suitable for use in applications requiring fine patterns such as solid-state imaging elements.

In view of such a problem, a technique of using a dye in place of a conventional pigment has been proposed (for example, refer to Patent Document 2). On the other hand, in recent years, in the case where a solid-state imaging element is used for a color filter, it is required to be further thinned. Further, in order to achieve a sufficient color concentration and film formation, a large amount of coloring agent is added to the composition, and at the same time, it is necessary to reduce the content of other raw materials.

In this manner, a photosensitive composition in which an organic solvent-soluble dye is increased and other raw materials are reduced is disclosed (for example, refer to Patent Document 3).

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

However, although a significant problem does not occur in a system using a conventional pigment as a coloring agent, in the case of using an organic solvent-soluble dye system, the organic solvent resistance of the formed coloring pattern becomes insufficient. When the next color is repeatedly applied, there is a problem that the dye in the colored pattern is eluted.

The present invention has been made in view of the above problems, and it is an object of the invention to provide a negative-type curable composition containing a dye, which can suppress formation of a cured product in which dye is eluted during repeated application, and proposes a color filter and a method for producing the same. In the case of a plurality of color patterns, it is possible to suppress the elution of the dye from the pattern in which the coating is repeated, and to form a good color tone without discoloration. This object is achieved as a subject of the present invention.

According to the present invention, when the dye is selected to form a hydrogen-containing dye in the presence of hydrogen, even when the dye concentration is made high, the pattern formed by temporarily hardening is further subjected to repeated coating or the like to further form. In the case of other coloring patterns, it is effective to suppress the dissolution of the dye from the existing pattern, and the present invention has been achieved based on such findings.

Specific technical means for achieving this problem are as follows: <1> A negative-type curable composition containing a dye, which is a dye-containing negative-type hardenable composition containing an organic solvent-soluble dye, which is characterized by: The content of the organic solvent-soluble dye is 50% by mass or more based on all the solid components, and at least one of the organic solvent-soluble dyes has two or more hydrogen bond donors.

<2> The negative-type hardenable composition containing the dye according to <1>, wherein the content of the organic solvent-soluble dye having two or more hydrogen bond donors is 50% by mass relative to the total amount of the organic solvent-soluble dye %the above.

<3> The negative photosensitive composition according to <1> or <2>, wherein the hydrogen bond donor is a carboxyl group, a hydroxyl group, an amine sulfonyl group, a monoalkylamine sulfonyl group, or an aryl group. The group selected by the sulfonyl group and the fluorenyl group.

The negative photosensitive composition of any one of <1> to <3>, wherein the hydrogen bond donor is a carboxyl group and/or a hydroxyl group.

(5) The negative photosensitive composition of any one of <1> to <4>, wherein the organic solvent-soluble dye having two or more hydrogen bond donors is represented by the following formula (I) dye.

In the above formula (I), A represents a residue of an aryl group or a 5- to 6-membered aromatic heterocyclic azo component A-NH ₂ . B ¹ represents -CR ¹ = or a nitrogen atom, B ² represents -CR ² = or a nitrogen atom, and B ¹ and B ² do not simultaneously represent a nitrogen atom. R ⁵ and R ⁶ represent a respective independently hydrogen atom, aliphatic group, aromatic group, heterocyclic group, fluorenyl group, alkoxycarbonyl group, aryloxycarbonyl group, aminomethyl fluorenyl group, alkyl sulfonyl group, aryl sulfonate. Indenyl or sulfonyl, R ⁵ and R ⁶ do not simultaneously represent a hydrogen atom. G, R ¹ and R ² represent a respective independently hydrogen atom, a halogen atom, an aliphatic group, an aromatic group, a heterocyclic group, a cyano group, a carboxyl group, an aminomethyl fluorenyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a fluorenyl group. , hydroxy, alkoxy, aryloxy, nonyloxy, decyloxy, aminomethyl methoxy, heterocyclic oxy, alkoxycarbonyloxy, aryloxycarbonyl, "alkyl", aryl Or a substituted amino group substituted by a heterocyclic group, a guanamine group, a ureido group, an amine sulfonamide group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, an alkylsulfonylamino group, an arylsulfonylamino group , nitro, alkylthio, arylthio, alkylsulfonyl, arylsulfonyl, alkylphosphonium, arylphosphonium, aminesulfonyl, sulfo, fluorenyl or heterocyclic thio . Among the groups represented by A, G, B ¹ , B ² , R ⁵ and R ⁶ , a group having at least two hydrogen bond donors, each group may have two or more independent hydrogen bond donors. Group. Further, R ¹ and R ⁵ and/or R ⁵ and R ⁶ may be bonded to each other to form a 5-member or 6-membered ring.

<6> The dye-containing negative-type curable composition according to any one of <1> to <5> further comprising a photosensitive compound, wherein the photosensitive compound is a photopolymerization initiator.

<7> The dye-containing negative-type curable composition according to any one of <1> to <5> further comprising a photosensitive compound, wherein the photosensitive compound is a photoacid generator.

<8> A color filter comprising the negative-type curable composition containing the dye according to any one of <1> to <7>.

<9> A method for producing a color filter, comprising applying a dye-containing negative-type curable composition disclosed in any one of <1> to <7> to a carrier, and then exposing through a reticle The step of forming a pattern image by imaging.

In the method of 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. Further, if necessary, it is preferred to have a form in which the step of hardening is performed by heating and/or exposure of the pattern image.

According to the present invention, it is possible to provide a negative-type curable composition containing a dye, which can suppress formation of a cured product in which dye is eluted during repeated application, and can provide a color filter and a method for producing the same, which are composed of several kinds. In the case of a color pattern, it is possible to suppress the elution of the dye from the pattern provided at the time of repeated application, and to form a good color tone without decoloring.

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

~ Negative hardening composition containing dye~

The negative-type curable composition containing a dye (hereinafter also referred to as "the composition of the present invention") contains at least (A) an organic solvent-soluble dye, more preferably (B) a photosensitive compound, (C) The alkali-soluble resin and the (D) curing agent can be generally used by using a solvent, and if necessary, various additives can be used.

(A) Organic solvent-soluble dye The negative-type hardening composition containing a dye of the present invention contains at least one organic solvent-soluble dye having two or more hydrogen bond donors (hereinafter, also referred to as "the organic solvent-soluble dye according to the present invention" ".) as a coloring agent. In particular, by using the organic solvent-soluble dye, even in the case where the dye concentration is high, in the process of forming a plurality of cured products (coloring patterns of several colors, etc.), for example, it is possible to prevent the pattern from being colored from the first color. Further, when the second coloring pattern is formed by repeated application or the like, the dye is eluted (organic solvent resistance), and the color density and the uniformity of color tone due to discoloration or the like are effectively suppressed.

Further, in the present invention, the case where the dye concentration is a high concentration with respect to all solid components of the dye-containing negative-type hardenable composition means 50% by mass or more.

The organic solvent-soluble dye of the present invention is a dye which is conventionally used as a color filter, and can be disclosed, for example, in Japanese Laid-Open Patent Publication No. SHO-64-90403, No. 64-91102, Japanese Patent Laid-Open No. Hei 1-94301, Japanese Patent Laid-Open No. Hei 6-11614, Japanese Patent No. 2,592,207, U.S. Patent No. 4,808,501, and U.S. Patent No. 5,676,920, and US Patent No. 5,059,500 Among the dyes such as Japanese Patent Publication No. Hei 5-333207, Japanese Patent Application Laid-Open No. Hei 6-35183, Japanese Patent Application Laid-Open No. Hei No. Hei 6-51115, and Japanese Patent Laid-Open No. Hei No. Hei. The above organic solvent soluble dye of the hydrogen bond donor.

As the chemical structure, a triphenylmethane type, an azo type, an anthrapyridone type, an anthraquinone type, a benzylidene type, an oxalican type, a cyanine type, a phenothiazine type, a pyrrolopyrazole type imine type can be used. , dyes such as xanthene, phthalocyanine, benzopyran, indigo. More preferably, it is a pyrazole azo type, an aniline azo type, a pyrazole triazole azo type, a pyridone azo type, an anthrapyridone type dye.

In the present invention, the hydrogen bond system refers to a substituent having a hydrogen bond capable of forming a hydrogen bond, and specific examples thereof include a hydroxyl group, a carboxyl group, an amine group, a monoalkylamine group, a monoarylamine group, a guanamine group, and a urea. Alkyloxycarbonylamino, sulfo, sulfonamide, amidoxime, monoalkylsulfonyl, monoarylsulfonyl, sulfonylamino, sulfonylaminomethyl Aminomethylmercaptosulfonyl, sulfonylsulfonyl, fluorenyl.

The dye can effectively use acid dyes and/or derivatives thereof, direct dyes, salt-based dyes, mordant dyes, acid mord dyes, insoluble azo dyes, disperse dyes, oil-soluble dyes, food dyes and/or derivatives thereof. Wait.

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 in a developing solution for use in an organic solvent or development treatment described later is considered. The salt formability of the salt-based compound, the absorbance, the interaction with other components in the composition, the light resistance, the heat resistance, and the like are selected as necessary properties.

In the present invention, the content of the organic solvent-soluble dye (the organic solvent-soluble dye of the present invention) having two or more hydrogen bond donors is made 50.0% by mass or more based on the total amount of the organic solvent-soluble dye. When the content of the organic solvent-soluble dye of the present invention is within this range, it is effective from the viewpoint of imparting organic solvent resistance, and when a plurality of color patterns are formed, it is possible to suppress further repeated coating from the existing pattern. The dye of the pattern is dissolved and does not decolorize to form a good color tone.

The content of the organic solvent-soluble dye having two or more hydrogen bond donors according to the present invention is preferably 60.0% by mass or more, and more preferably 70.0% by mass or more, based on the total amount of the organic solvent-soluble dye.

Among them, preferred examples of the hydrogen bond donor include a hydroxyl group, a carboxyl group, an amine sulfonyl group, a monoalkylamine sulfonyl group, a monoarylamine sulfonyl group, and an anthracenyl group. Among these groups, the most preferred hydrogen bond donor is a hydroxyl group or a carboxyl group.

Specific examples of the acid dye having two or more hydrogen bond donors are listed below. Can be mentioned: acid black 1,48; acid blue 18,23,25,27,29,40,42,45,51,62,70,74,80,92,96,129,138,147,150,158; acid green 25,27; lime 6 , 56; Acid Red 1,29,31,34,35,37,42,50,57,97,133,134,138,158,176,183,198,249,266,308; Acid Violet 6,7,19; Acid Yellow 25,29,42,54,73,99,134,172,199,220; Direct Yellow 2 , 33, 50, 69, 70, 86; direct orange 96; direct red 79, 83, 84, 98, 99, 173, 176, 181, 243, 250; direct purple 47, 66, 79, 80, 81, 103; direct blue 80, 81, 84, 93, 95 ,98,106,107,149,150,158,159,162,163,164,166,167,190,214; direct green 34; mordant yellow 5,16,26,30,33,45; mordant orange 3,4,14,29,35,37; mordant red 2,3,4,11,17,19,26 , 30, 39, 41, 45, 71, 74, 90, 94; mordant purple 1,4,5,30,40,44,58; mordant blue 7,9,13,23,24,31,32,44 48; mordant green 10, 15, 26, 34; solvent blue 25, 35, 37, 59; wherein, as having two or more hydrogen bond donors, the following acid dyes are particularly preferred.

Acid blue 42, 45, 70, 158; lime 6,56; acid red 29, 31, 97, 134, 158, 176, 183, 198, 308; acid purple 6; acid yellow 42, 54, 73, 99, 134, 220; direct yellow 2, 33, 69, 70; Direct red 79,83,98,99,173,176,181,243,250; direct violet 47,66,79,80,81,103; direct blue 80,81,84,93,95,98,150,158,159,162,163,164,166,167,214; mordant yellow 5,16,26,33,45; mordant orange 3,4,14,29,35,37; mordant red 2,3,4,11,17,19,26,30,39,41,45,71,90,94; mordant purple 1,4,5, 30, 40, 44, 58; mordant blue 7, 9, 13, 23, 24, 31, 32, 44; mordant green 10, 15, 26, 34; in addition, synthetic dyes can also be suitably used. Among them, an organic solvent-soluble dye having two or more hydrogen bond donors in one molecule is particularly preferable to contain an azo dye represented by the following formula (I).

In the above formula (I), A represents a residue of an aryl group or a 5- to 6-membered aromatic heterocyclic diazo component A-NH ₂ . Examples of the hetero atom of the 5- to 6-membered heterocyclic ring constituting the A of the A-NH ₂ include N, O and S. More preferably, it is a nitrogen-containing 5-membered heterocyclic ring, and the heterocyclic ring may be condensed with an aliphatic ring, an aromatic ring or other heterocyclic ring.

Examples of the preferred heterocyclic ring of A include a pyridine ring, a pyrimidine ring, a triazole ring, a pyrazole ring, an imidazole ring, a thiazole ring, an isothiazole ring, a thiadiazole ring, a benzothiazole ring, and a benzoxazole ring. Benzoisothiazole ring. Each heterocyclic ring may further have a substituent. Among them, a pyrazole ring, an imidazole ring, an isothiazole ring, a thiadiazole ring, and a benzothiazole ring represented by the following general formulae (a) to (f) are preferred.

R ⁷ to R ^{2 0 of} the general formulae (a) to (f) are synonymous with G, R ¹ and R ² described later, and preferred embodiments thereof are also the same. Among the general formulae (a) to (f), a pyrazole ring or an isothiazole ring represented by the formula (a) or (b) is preferred, and a pyrazole ring represented by the formula (a) is preferred.

The B ¹ represents -CR ¹ = or a nitrogen atom, and the B ² represents -CR ² = or a nitrogen atom, and B ¹ and B ² do not simultaneously represent a hydrogen atom. That is, -CR ¹ = or -CR ² = is indicated, or either B ¹ and B ² represent a nitrogen atom, and the other represents -CR ¹ = or -CR ² =. Among them, B ¹ represents -CR ¹ =, and B ² represents -CR ² = particularly desirable.

R ⁵ and R ⁶ represent a respective independently hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, a fluorenyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an aminomethyl fluorenyl group, an alkyl sulfonyl group, an aryl group. The sulfonyl group, the amine sulfonyl group, the monoalkylamine sulfonyl group or the monoarylamine sulfonyl group, each group may further have a substituent. Preferred groups represented by R ⁵ and R ⁶ include a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, a fluorenyl group, an alkylsulfonylamino group or an arylsulfonylamino group. Preferred is a hydrogen atom, an aromatic group, a heterocyclic group, a fluorenyl group, an alkylsulfonylamino group or an arylsulfonylamino group. It is preferably a hydrogen atom, an aryl group or a heterocyclic group. These preferred groups are preferably in the form of further substituents. However, R ⁵ and R ⁶ are not simultaneously a hydrogen atom.

The G, R ¹ and R ² represent a respective independently hydrogen atom, a halogen atom, an aliphatic group, an aromatic group, a heterocyclic group, a cyano group, a carboxyl group, an aminomethylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, or an anthracene group. Base, hydroxy, alkoxy, aryloxy, nonyloxy, decyloxy, aminomethyl methoxy, heterocyclic oxy, alkoxycarbonyloxy, aryloxycarbonyloxy, "alkyl" Substituted amine group substituted by a heterocyclic group or a heterocyclic group, a guanylamino group, a ureido group, an amine sulfonylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, an alkyl/aryl sulfonylamino group, a nitrate Base, alkyl/arylthio group, alkyl/aryl sulfonyl group, alkyl/aryl sulfinyl group, amine sulfonyl group, monoalkylamine sulfonyl group, monoarylamine sulfonate The thiol, sulfo, fluorenyl or heterocyclic thio group may also be further substituted.

Preferred groups represented by G include a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group, a hydroxyl group, an alkoxy group, an aryloxy group, a decyloxy group, a heterocyclic oxy group, and an alkyl group. a substituted amine group substituted with an aryl or heterocyclic group, a guanylamino group, a ureido group, an amine sulfonamide group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, an alkyl/aryl thio group or a heterocyclic group Sulfur group, more preferably hydrogen atom, halogen atom, alkyl group, hydroxyl group, alkoxy group, aryloxy group, decyloxy group, "substituted amino group substituted by alkyl group, aryl group or heterocyclic group" or decylamine base. Among them, a hydrogen atom, an arylamine group, and a decylamino group are preferable. Each group may further have a substituent.

Preferred groups represented by R ¹ and R ² include a hydrogen atom, an alkyl group, an alkoxycarbonyl group, a carboxyl group, an aminomethylguanidinyl group or a cyano group. Each group may further have a substituent.

Further, R ¹ and R ⁵ and/or R ⁵ and R ⁶ may be bonded to each other to form a 5-membered ring or a 6-membered ring.

The substituent in the case where each of the groups represented by A, R ¹ , R ² , R ⁵ , R ⁶ and G further has a substituent, and the substituents exemplified for the G, R ¹ and R ² may be mentioned.

However, it is suitable for the organic solvent-soluble dye having two or more hydrogen bond donors to have at least two hydrogen bond donors of the groups represented by A, G, R ¹ , R ² , R ⁵ and R ⁶ . The group, each group is more preferably a group having two or more independent hydrogen bond donors. The system for such hydrogen bonding is as described above.

Hereinafter, each group of the general formula will be described in detail.

In the present specification, the halogen atom may, for example, be a fluorine atom, a chlorine atom or a bromine atom. Preferred halogen atoms include a fluorine atom and a chlorine atom. A halogen atom is particularly preferred as a chlorine atom.

In the present specification, aliphatic radical means alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, aralkyl and substituted aralkyl, and may have a branch or a ring. .

The carbon number of the aliphatic group is preferably from 1 to 20, more preferably from 1 to 16. The aryl group of the aralkyl group and the substituted aralkyl group is preferably a phenyl group or a naphthyl group, and particularly preferably a phenyl group. Examples of the aliphatic group include methyl, ethyl, butyl, isopropyl, n -butyl, t -butyl, n -octyl, hydroxyethyl, methoxyethyl, cyanoethyl, Trifluoromethyl, 3-sulfopropyl, 4-sulfobutyl, cyclohexyl, benzyl, 2-phenylethyl, vinyl and allyl. Preferred aliphatic groups include methyl, ethyl, isopropyl, n -butyl, t -butyl and hydroxyethyl groups. Aliphatic groups are particularly preferred as methyl, ethyl and t -butyl groups.

In the present specification, an aromatic group means an aryl group which is unsubstituted or has a substituent. The aryl group is preferably a phenyl group or a naphthyl group, and particularly preferably a phenyl group. The carbon number of the aromatic group is preferably from 6 to 20, more preferably from 6 to 16. Examples of the aromatic group include: phenyl, p -tolyl, 1,3,5-trimethylphenyl, p -methoxyphenyl, o -chlorophenyl, m -nitrophenyl, p -nitrophenyl, p -carboxy- o -nitrophenyl, 2,4-dicarboxyphenyl and m- (3-sulfopropylamino)phenyl. Preferred examples of the aromatic group include a phenyl group, a p -tolyl group, a 1,3,5-trimethylphenyl group, a p -methoxyphenyl group, an m -nitrophenyl group, and a p -nitrophenyl group. P -carboxy- o -nitrophenyl and 2,4-dicarboxyphenyl. The aromatic group is particularly preferably a phenyl group, a 1,3,5-trimethylphenyl group, a p -carboxy- o -nitrophenyl group and a 2,4-dicarboxyphenyl group.

In the present specification, the heterocyclic group has a heterocyclic group having a substituent and a heterocyclic group having no substituent. The heterocyclic ring may also be condensed with an aliphatic ring, an aromatic ring or other heterocyclic ring. The heterocyclic group is preferably a heterocyclic group of 5 or 6 members. Examples of the substituent include: an aliphatic group, a halogen atom, a sulfonyl group of an alkyl group and an aryl group, a fluorenyl group, a decylamino group, an amine sulfonyl group, an N-alkylamine sulfonyl group, and an N-arylamine. A sulfonyl group, an aminomethyl fluorenyl group, an ionic hydrophilic group or the like, and preferred substituents include an anthracenyl group, a decylamino group, an amine sulfonyl group, a monoalkylamine sulfonyl group and an arylamine sulfonium sulfonate. base. Particularly preferred substitutions include an amine sulfonyl group, a monoalkylamine sulfonyl group and an arylamine sulfonyl group.

Examples of the unsubstituted heterocyclic group include 2-pyridyl, 2-thiol, 2-thiazolyl, 2-benzothiazolyl, 2-benzoxyl, 2-thiadiazolyl and 2- Furanyl. More preferably, it is 2-thiazolyl, 2-benzothiazolyl, 2-thiadiazolyl, and particularly preferably 2-benzoxanyl, 2-thiadiazolyl. These groups preferably contain a substituent.

In the present specification, the aminomethyl fluorenyl group having a substituent and an unsubstituted aminomethyl fluorenyl group are contained in the aminomethyl fluorenyl group. Examples of the substituent include an alkyl group, and specific examples are the same as the aliphatic group. The aminocarbamyl group is preferably an aminomethylcarbenyl group having 1 to 5 carbon atoms. Examples of the aminomethyl fluorenyl group include a methylaminomethyl fluorenyl group, an ethylaminomethyl fluorenyl group, and a dimethylaminomethyl fluorenyl group. Preferred examples of the methylaminocarbamyl group include a methylaminomethyl fluorenyl group and an ethylaminomethyl fluorenyl group. Particularly preferred aminomethylmercapto groups are exemplified by methylaminocarbamyl.

In the present specification, the alkoxycarbonyl group includes a substituted alkoxycarbonyl group and an unsubstituted alkoxycarbonyl group. The alkoxycarbonyl group is preferably an alkoxycarbonyl group having 2 to 12 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group and a butoxycarbonyl group. Preferred alkoxycarbonyl groups include methoxycarbonyl and ethoxycarbonyl. A particularly preferred alkoxycarbonyl group is exemplified by a methoxycarbonyl group.

In the present specification, the aryloxycarbonyl group includes a substituted aryloxycarbonyl group and an unsubstituted aryloxycarbonyl group. The aryloxycarbonyl group is preferably an aryloxycarbonyl group having 7 to 12 carbon atoms. The substituent includes an ionic hydrophilic group. Examples of the aryloxycarbonyl group include a phenoxycarbonyl group, a p -methoxyphenoxycarbonyl group and a p -methylphenoxycarbonyl group. Preferred aryloxycarbonyl groups include phenoxycarbonyl and p -methylphenoxycarbonyl. A particularly desirable aryloxycarbonyl group is exemplified by a phenoxycarbonyl group.

In the present specification, a fluorenyl group having a substituent and an unsubstituted fluorenyl group are contained in the fluorenyl group. The sulfhydryl group is preferably a fluorenyl group having a carbon number of 1 to 12. Examples of the substituent include an ionic hydrophilic group. Examples of the sulfhydryl group include: an ethyl fluorenyl group, a benzoinyl group, and an o -hydroxyphenyl fluorenyl group. Preferred examples of the fluorenyl group include an ethyl fluorenyl group and a phenyl fluorenyl group. A particularly desirable base is exemplified by an ethyl group.

In the present specification, alkoxy groups having a substituent and an unsubstituted alkoxy group are contained in the alkoxy group. The alkoxy group is preferably an alkoxy group having 1 to 12 carbon atoms. Examples of the substituent include an alkoxy group, a hydroxyl group, and an ionic hydrophilic group. Examples of the alkoxy group include a methoxy group, an ethoxy group, an isopropyl group, a methoxyethoxy group, a 2-hydroxyethoxy group, and a 3-carboxypropoxy group. Preferred alkoxy groups include methoxy, methoxyethoxy, 2-hydroxyethoxy and 3-carboxypropoxy. Particularly preferred alkoxy groups are exemplified by 2-hydroxyethoxy group and 3-carboxypropoxy group.

In the present specification, the aryloxy group includes a substituted aryloxy group and an unsubstituted aryloxy group. The aryloxy group is preferably an aryloxy group having 6 to 12 carbon atoms. Examples of the substituent include an alkoxy group and an ionic hydrophilic group. Examples of the aryloxy group include a phenoxy group, a p -methoxyphenoxy group, and an o -methoxyphenoxy group. Preferred aryloxy groups include phenoxy group and p -methoxyphenoxy group. A particularly desirable aryloxy group is exemplified by a phenoxy group.

In the present specification, a fluorenyloxy group having a substituent and an unsubstituted decyloxy group are contained in the fluorenyloxy group. The decyloxy group is preferably a decyloxy group having a carbon number of 1 to 12. Examples of the substituent include an ionic hydrophilic group. Examples of the fluorenyloxy group include an ethoxycarbonyl group, a benzoquinoneoxy group, and an o -hydroxyphenyl fluorenyl group. Preferred examples of the methoxy group include an ethoxy group and a phenyl hydroxy group. A particularly preferred methoxy group is exemplified by an ethoxy group.

In the present specification, the aminomethyl methoxy group includes a substituted aminomethyl methoxy group and an unsubstituted aminomethyl methoxy group. In the example of the substituent, it contains: an alkyl group. The aminomethyl methoxy group is preferably an aminomethyl methoxy group having 1 to 6 carbon atoms. Examples of the aminomethyl methoxy group include N-methylaminomethyl methoxy, N-ethylaminomethyl methoxy and N- n -butylaminomethyl methoxy. Preferred examples of the aminomethyl methoxy group include N-methylaminomethyl methoxy group and N-ethylaminomethyl methoxy group. A particularly desirable aminomethyl methoxy group is exemplified by N-methylaminomethyl methoxy group.

In the present specification, a heterocyclic oxy group having a substituent and an unsubstituted heterocyclic oxy group are contained in the heterocyclic oxy group. The heterocyclic ring is preferably a heterocyclic ring of 5 or 6 members, and the heterocyclic ring may be condensed with an aliphatic ring, an aromatic ring or other heterocyclic ring, and examples of the substituent are the same as the heterocyclic group. The preferred form is also the same. Examples of the unsubstituted heterocyclic oxy group include 3-isoxazolyloxy, 2-benzothiazolyloxy, 2-pyridyloxy and the like.

In the present specification, the alkoxycarbonyloxy group includes a substituted alkoxycarbonyloxy group and an unsubstituted alkoxycarbonyloxy group. The alkoxycarbonyloxy group is preferably an alkoxycarbonyloxy group having 1 to 5 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the alkoxycarbonyloxy group include a methoxycarbonyloxy group, an ethoxycarbonyloxy group, a propoxycarbonyloxy group and the like. A particularly preferred alkoxycarbonyloxy group is exemplified by a methoxycarbonyloxy group.

In the present specification, the aryloxycarbonyloxy group includes a substituted aryloxycarbonyloxy group and an unsubstituted aryloxycarbonyloxy group. The aryloxycarbonyloxy group is preferably an aryloxycarbonyloxy group having 6 to 15 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the aryloxycarbonyloxy group include a phenoxycarbonyloxy group, a p -methoxyphenoxycarbonyloxy group, a p -tolylphenoxycarbonyloxy group and the like. A particularly desirable aryloxycarbonyloxy group is exemplified by a phenoxycarbonyloxy group.

In the present specification, the "substituted amino group substituted with an alkyl group, an aryl group or a heterocyclic group" may further have a substituent. Does not contain unsubstituted amine groups. The alkylamine group is preferably an alkylamine group having 1 to 6 carbon atoms. Examples of the substituent in the case of further having a substituent include an ionic hydrophilic group. Examples of the alkylamino group include a methylamino group, a diethylamino group, a bis(2-hydroxyethyl)amino group, a bis(carbonylmethyl)amino group, and a 2-(1,3-dihydroxypropyl group). Amino, 2-(1,3-dihydroxy-2-methylpropyl)amino, 2-(hydroxypropyl-2-methyl)amino, 2,3-dihydroxypropylamino and 2-hydroxypropylamino group. Preferred alkylamino groups include methylamino, bis(2-hydroxyethyl)amino, bis(carbonylmethyl)amine, 2-(1,3-dihydroxypropyl)amino, 2,3. - Dihydroxypropylamino group and 2-hydroxypropylamino group. Particularly preferred alkylamine groups are bis(carbonylmethyl)amino group, 2-(1,3-dihydroxypropyl)amino group and 2-hydroxypropylamino group.

The arylamine group includes a substituted arylamine group and an unsubstituted arylamine group. The arylamine group is preferably an arylamine group having 6 to 12 carbon atoms. Examples of the substituent in the case of further having a substituent include a halogen atom and an ionic hydrophilic group. Examples of the arylamine group include an anilino group, a 1,3,5-trimethylanilino group, a p -methoxyanilino group, a 2-chloroanilino group, an m -carboxyanilino group and a 2,4-dicarboxyanilino group. . Preferred examples of the arylamine group include an anilino group, a 1,3,5-trimethylanilino group, an m -carboxyanilino group and a 2,4-dicarboxyanilino group. Particularly preferred aromatic amine groups are exemplified by 1,3,5-trimethylanilino and 2,4-dicarboxyanilino.

In the present specification, a guanamine group having a substituent is contained in the guanamine group. The guanamine group is preferably a guanamine group having a carbon number of 2 to 12. Examples of the substituent include an ionic hydrophilic group. Examples of the amidoxime group include an acetamino group, a propylamine group, a benzoguanamine group, an N-phenylethylammonium group, and a 3,5-disulfobenzoquinone group. Preferred examples of the guanamine group include an acetamino group, a propylamine group, a benzoguanamine group and an N-phenylethylammonium group. Particularly preferred amidino groups are acetamino groups and benzoguanamine groups.

In the present specification, a ureido group having a substituent and an unsubstituted ureido group are contained in the ureido group. The urea group is preferably a urea group having 1 to 12 carbon atoms. Examples of the substituent include an alkyl group and an aryl group. Examples of the urea group include 3-methylureido, 3,3'-dimethylureido and 3-phenylureido. Preferred ureido groups are exemplified by 3-methylureido groups and 3-phenylureido groups. Particularly preferred ureido groups are exemplified by 3-methylureido groups.

In the present specification, the aminocarbamamine group contains a substituted aminomethylamino group and an unsubstituted aminoformamido group. In the example of the substituent, it contains: an alkyl group. Examples of the aminocarbamide group include: aminocarbamamine, 1,3-dihydroxypropylaminocarbamamine, N,N'-dipropylaminocarbamamine and N, N'-dipropionylaminocarboxamide. Preferred aminocarbamamine groups are exemplified by an aminomethylamino group, a 1,3-dihydroxypropylaminocarbamamine group and an N,N'-dipropionylaminocarboxamide group. Particularly preferred aminocarbamamine groups are 1,3-dihydroxypropylaminocarbamamine and N,N'-dipropionylaminocarboxamide.

In the present specification, the alkoxycarbonylamino group includes a substituted alkoxycarbonylamino group and an unsubstituted alkoxycarbonylamino group. The alkoxycarbonylamino group is preferably an alkoxycarbonylamino group having 2 to 12 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the alkoxycarbonylamine group include an ethoxycarbonylamino group, a propoxycarbonylamino group and a butoxycarbonylamine group. Preferred alkoxycarbonylamino groups are exemplified by an ethoxycarbonylamino group and a propoxycarbonylamine group. A particularly preferred alkoxycarbonylamino group is exemplified by an ethoxycarbonylamino group.

In the present specification, the aryloxycarbonylamino group includes a substituted aryloxycarbonylamino group and an unsubstituted aryloxycarbonylamino group. The aryloxycarbonylamino group is preferably an aryloxycarbonylamino group having 7 to 12 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the aryloxycarbonylamino group include a phenoxycarbonylamino group, a p -methylphenoxycarbonylamino group and an o -hydroxyphenoxycarbonylamino group. Preferred examples of the aryloxycarbonylamino group include a phenoxycarbonylamino group and an o -hydroxyphenoxycarbonylamino group. Particularly preferred aryloxycarbonylamino groups are exemplified by o -hydroxyphenoxycarbonylamino group.

In the present specification, the alkylsulfonylamino group and the arylsulfonylamino group (alkyl/arylsulfonylamino group) include: a substituted alkyl/arylsulfonylamino group and Unsubstituted alkyl/arylsulfonylamino group. The alkyl/arylsulfonylamino group is preferably a sulfonylamino group having an alkyl group/aryl group having 1 to 12 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the alkyl/arylsulfonylamino group include a methanesulfonamide group, an N-phenylmethanesulfonylamino group, a benzenesulfonylamino group, and a 3-carboxybenzenesulfonylamino group. Preferred alkyl/arylsulfonylamino groups include methanesulfonylamino and 3-carboxybenzenesulfonylamino. A particularly desirable alkyl/arylsulfonylamino group is exemplified by 3-carboxybenzenesulfonylamino.

In the present specification, the alkylthio group, the arylthio group and the heterocyclic thio group include a substituted alkylthio group, an arylthio group and a heterocyclic thio group, and an unsubstituted alkylthio group and an arylthio group. Heterocyclic thio group. The alkylthio group, the arylthio group and the heterocyclic thio group are preferably those having a carbon number of 1 to 12. Examples of the substituent include an ionic hydrophilic group. Examples of the alkylthio group, the arylthio group and the heterocyclic thio group include a methylthio group, a phenylthio group, and a 2-pyridylthio group.

In the present specification, examples of the alkylsulfonyl group and the arylsulfonyl group include various methanesulfonyl groups and phenylsulfonyl groups.

Examples of the alkylsulfinyl group and the arylsulfinyl group include various methanesulfinylene groups and phenylsulfinylene groups.

In the present specification, the aminesulfonyl group includes a substituted aminesulfonyl group and an unsubstituted aminesulfonyl group. Examples of the substituent include an alkyl group and an aryl group. Examples of the aminesulfonyl group include: an unsubstituted aminoximino group, a dimethylaminesulfonyl group, a bis(carboxymethyl)aminesulfonyl group, a bis(2-hydroxyethyl)aminesulfonyl group, 2 , 4-dicarboxyphenylamine sulfonyl, 2-(1,3-dihydroxypropyl)amine sulfonyl, 2-(hydroxypropyl)amine sulfonyl, 2-(hydroxy-2-methyl Propyl) sulfonamide, 2-(1,3-dihydroxy-2-methylpropyl)amine sulfonyl and acesulfonyl dipropionate. Preferred amine sulfonyl groups include unsubstituted sulfonyl, bis(carboxymethyl)amine sulfonyl, bis(2-hydroxyethyl)amine sulfonyl, 2,4-dicarboxyphenylamine. Sulfosyl, 2-(1,3-dihydroxypropyl)aminesulfonyl and acesulfonyl dipropionate. Particularly preferred amine sulfonyl groups are exemplified by bis(carboxymethyl)amine sulfonyl, bis(2-hydroxyethyl)amine sulfonyl and 2-(1,3-dihydroxypropyl)amine sulfonyl .

Particularly preferred azo dyes are those represented by the following formula (II).

In the formula (II), Z ¹ represents an electron withdrawing group having a Hammett substituent constant σ _p value of 0.20 or more, and is preferably an electron withdrawing group having a σ _p value of 0.30 to 1.0. Specific examples of preferred groups include the electron-withdrawing substituents described later. Among them, it is preferably a fluorenyl group having 2 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 12 carbon atoms, a nitro group, a cyano group, an alkylsulfonyl group having 1 to 12 carbon atoms, and an aryl group having 6 to 18 carbon atoms. A sulfonyl group, an amine carbenyl group having 1 to 12 carbon atoms, or a halogenated alkyl group having 1 to 12 carbon atoms. Particularly preferred groups are a cyano group, an alkylsulfonyl group having 1 to 12 carbon atoms, and an arylsulfonyl group having 6 to 18 carbon atoms. The most preferred group is a cyano group.

In the general formula (II), Z ² represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group, and the aliphatic group, the aromatic group or the heterocyclic group is as follows.

Further, in the general formula (II), R ¹ , R ² , R ⁵ and R ⁶ are synonymous with R ¹ , R ² , R ⁵ and R ⁶ of the general formula (I), and preferred forms are also the same. of.

In the formula (II), R ³ and R ⁴ each independently represent a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, a cyano group, an alkoxycarbonyl group, an aryloxycarbonyl group or an aminomethyl fluorenyl group. An alkylsulfonyl group, an arylsulfonyl group or an aminesulfonyl group. Among them, a hydrogen atom, an aromatic group, a heterocyclic group, a fluorenyl group, an alkylsulfonyl group and an arylsulfonyl group are preferable, and a hydrogen atom, an aromatic group or a heterocyclic group is particularly preferable. The details of each group are as described above.

In the formula (II), Q represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group. Wherein, Q is preferably a group formed by a non-metal atomic group necessary for forming a 5-8 member ring, and the formed 5-8 member ring may be substituted, and may be a saturated ring or may be unsaturated. A bond in which an aromatic group or a heterocyclic group of a 5- to 8-membered ring is particularly preferable. Preferred examples of the non-metal atom include a nitrogen atom, an oxygen atom, a sulfur atom and a carbon atom; and specific examples of the 5- to 8-membered ring include a benzene ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, and a ring. Octane ring, cyclohexene ring, pyridine ring, pyrimidine ring, pyrazine ring, pyridazine ring, triazine ring, imidazole ring, benzimidazole ring, oxazole ring, benzoxazole ring, thiazole ring, benzo Thiazole ring, oxyalkyl ring, cyclobutyl ring and sulfane ring, and the like.

Each of the groups of the formula (II) may further have a substituent, and examples of the substituent in the case where the group further has a substituent include the substituent described in the formula (I), G, a group exemplified by R ¹ or R ² or an ionic hydrophilic group.

Among them, in relation to the substituent Z ¹ , the Hammett substituent constant σ _p value used in the present specification will be described.

Since Hammett's law is a quantitative description of the reaction of benzene derivatives or the influence of substituents affecting equilibrium, in 1935, the rule of thumb advocated by P. Hammett, the validity of this rule is still widely accepted. The substituent constants σ _p and σ _m values obtained according to Hammett's law can be found in many general published books, for example, in the "Lange's and book of Chemistry", edited by JADean, 12th edition, 1979. Year (McGraw-Hill) or "Chemical Fields" Supplement, 122, 96-103, 1979 (Nippon Nanko). Further, in the present invention, although each substituent is defined or described based on the Hammett substituent constant σ _p value, it is not intended to be limited only to the substituents of the document's established value found in the published book, and even The values are unknown to the literature and include substituents within the range as determined by Hammett's law. Further, in the above formulas (I) and (II), a substituent of a non-benzene derivative is also contained, and as a standard for exhibiting the electron effect of the substituent, a value of σ _p irrespective of the position of substitution is used. In the present invention, the σ _p value in this sense is used.

Examples of the electron-donating group having a Hammett σ _p value of 0.60 or more may be exemplified by a cyano group, a nitro group, an alkylsulfonyl group (for example, a methanesulfonyl group), or an arylsulfonyl group (for example, a benzenesulfonyl group). ).

In addition to the above, the electron-donating group having a Hammett substituent constant σ _p value of 0.45 or more may be exemplified by a mercapto group (for example, an ethyl fluorenyl group), an alkoxycarbonyl group (for example, a dodecyloxycarbonyl group), or an aryloxycarbonyl group. (for example, m -chlorophenoxycarbonyl), alkylsulfinyl (for example, n -propylsulfinyl), arylsulfinyl (for example, phenylsulfinyl), amidoxime A group (for example, N-ethylaminesulfonyl, N,N'-dimethylaminesulfonyl), a halogenated alkyl group (for example, trifluoromethyl).

In addition to the above, the electron withdrawing group having a Hammett substituent constant σ _p value of 0.30 or more may be exemplified by a decyloxy group (for example, an ethoxylated group) or an aminomethyl fluorenyl group (for example, an N-ethylamino group). Mercapto, N,N'-dibutylaminocarbamyl), halogenated alkoxy (eg, trifluoromethoxy), halogenated aryloxy (eg, pentafluorophenoxy), sulfonyloxy a group (for example, a methylsulfonyloxy group), a halogenated alkylthio group (for example, a difluoromethylthio group), an aryl group substituted with two or more electron withdrawing groups having a σ _p value of 0.15 or more (for example, 2,4-Dinitrophenyl, pentachlorophenyl) and a heterocyclic group (for example, 2-benzoxazolyl, 2-benzothiazolyl, 1-phenyl-2-benzimidazolyl).

In addition to the above, specific examples of the electron withdrawing group having a Hammett σ _p value of 0.20 or more include a halogen atom and the like.

The azo dye represented by the formula (I) is particularly preferably a combination of the forms shown by the following formulas (1) to (4).

(1) R ⁵ and R ⁶ are preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkylsulfonyl group, an arylsulfonyl group or a fluorenyl group, preferably a hydrogen atom, an aryl group and a hetero group. Ring base. However, R ⁵ and R ^{6 do} not simultaneously represent a hydrogen atom.

(2) G is preferably a hydrogen atom, a halogen atom, an alkyl group, a hydroxyl group, a "substituted amino group substituted by an alkyl group, an aryl group or a heterocyclic group" or a guanamine group, more preferably a hydrogen atom or a halogen atom. The "substituted amino group substituted by an alkyl group, an aryl group or a heterocyclic group" or a decylamino group is preferably a hydrogen atom, a "substituted amino group substituted by an alkyl group, an aryl group or a heterocyclic group" or a decylamine. base.

(3) A is preferably a pyrazole ring, an imidazole ring, an isothiazole ring, a thiadiazole ring or a benzothiazole ring, more preferably a pyrazole ring or an isothiazole ring, and most preferably a pyrazole ring.

(4) B ¹ and B ² are -CR ¹ =, -CR ² = respectively, and R ¹ and R ² are preferably a hydrogen atom, a halogen atom, a cyano group, an aminomethyl fluorenyl group, a carboxyl group, an alkyl group or a hydroxyl group. Or an alkoxy group, more preferably a hydrogen atom, a cyano group, an aminomethyl fluorenyl group or an alkyl group.

In the compound of the formula (I), each group is preferably a combination, and a suitable compound - at least one of each group has a preferred group shown in the above (1) to (4); more preferably The compound-for each of the groups has a preferred group shown in the above (1) to (4); the most preferred compound - all of the groups are preferably shown in the above (1) to (4). Group.

Hereinafter, preferred examples of the organic solvent-soluble dye represented by the above formula (I) or (II) are exemplified (exemplary compounds (1) to (39)). However, in the present invention, it is not limited by these specific examples.

The preferred form of the curable composition containing a dye according to the present invention is particularly soluble in an organic solvent having one or more kinds of hydrogen bond donors represented by the formula (I) or the formula (II). The dye is particularly desirable.

In the present invention, it is possible to simultaneously use an organic solvent-soluble dye having two or more hydrogen bond donors (the organic solvent-soluble dye of the present invention), and other conventional organic substances other than the organic solvent-soluble dye of the present invention. Solvent soluble dye.

For example, as described above, among dyes well known for the use of conventional color filters, dyes having the chemical structure can be selected, and acid dyes and/or derivatives thereof are suitable. In addition, direct dyes, salt-based dyes, mordant dyes, acid mord dyes, insoluble azo dyes, disperse dyes, oil-soluble dyes, food dyes, and/or such derivatives can also be effectively used.

Hereinafter, an acid dye which can be used in combination with other conventional organic solvent-soluble dyes will be listed.

Acid acid purple N; acid black 1,2,24,48; acid blue 1,7,9,15,83,86,87,90,103,108,112,113,120,171,182,192,210,242,243,256,259,267,278,280,285,290,296,315,324:1,335,340; acid medium purple K; acid magenta; acid green 1,3 ,5,9,16,50,58,63,65,80,104,105,106,109;orange 7,8,10,12,26,50,51,52,62,63,64,74,75,94,95,107,108,169,173;acidic Red 4,8,14,17,18,26,27,44,51,52,66,73,80,87,88,91,92,94,103,111,114,129,143,145,150,151,182,206,211,215,216,217,227,228,252,257,258,260,261,268,270,274,277,280,281,312,315, 316, 341,345,346,349, 382, 383, 394,401, 412,417, 418, 422, 426; acid violet 6B, 9, 17, 49; acid yellow 1 , 3,7,9,11,17,23,34,36,38,40,65,72,76,79,98,111,112,113,114,116,119,123,128,135,138,139,140,144,150,155,157,160,161,163,168,169,177,178,179,184,190,193,196,197,202,203,204,205,207,212,214,221,228,230,232,235,238,240,242,243, 251; direct yellow 34,35,38,39,43,47,54,58,68 , 71, 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, 97, 106, 107; direct red 82, 91, 92, 96 ,97,105,106,107,172,177,179,182,184,2 04,207,211,213,218,220,221,222,232,233,234,241,246; Direct Violet 52,54,59,60,65,82,84,89,90,93,95,96,104; Direct Blue 57,77,85,86,90,94,97,99,100,101,108,109,113,114,115,117,119,137,153,155,156,160,161,170,171,172,173,188,189,192,193,194,196,198,199,200,207,209,210,212,213,222,228,229,237,238,242,243,244,245,247,248,250,251,252,256,257,259,260,268,274,275,293; Direct Green 25, 27,31,32,37,63,65,66,67,68,69,72,77,79,82; mordant yellow 8,10,20,31,42,43,56,61,62,65; Mordant orange 5,8,12,13,20,21,23,24,28,32,34,36,42,43,47,48; mordant red 1,9,12,14,18,22,23, 24,25,32,33,36,37,38,43,46,48,53,56,63,85,86,88,95; mordant violet 1,2,7,14,22,24,31, 32,37,41,45,47,48,53; mordant blue 1,2,3,8,12,15,16,19,20,21,22,26,30,39,40,41,43, 49,53,61,74,77,83,84; mordant green 1,3,4,5,19,26,29,33,35,41,43,53; food yellow 14.82,94,162; solvent yellow 3; Solvent orange 2, 7, 11, 15, 26, 56; solvent blue 38, 55, 67; solvent red 49; and derivatives of such dyes.

In addition, azo, xanthene, and phthalocyanine acid dyes are also suitable, CI Solvent Blue 44, 38, CI Solvent Orange 45, Rhodamine B, Rhodamine 110, 2, 7-naphthalene disulfonic acid, 3-[(5-chloro-2-phenoxyphenyl) terpylene]-3,4-dichloro-4-carbonyl-5-[(phenylsulfonyl)amine Acid dyes such as ketones and derivatives of such dyes are also suitable.

As the derivative of the acid dye, an acid dye inorganic salt derived from an acid group such as a sulfonic acid or a carboxylic acid, a salt of an acid dye and a nitrogen-containing compound, a sulfonamide of an acid dye, or the like can be used, except that the present invention is desired. The composition is not soluble except when it is soluble in a solution, and all the solubility, absorbance, and interaction with other components in the composition for the developing solution for organic solvent or development are considered. Light resistance, heat resistance and the like are selected as necessary properties.

The "salt of acid dye and nitrogen-containing compound" will be described. The salt of the acid dye and the nitrogen-containing compound is often effective for improving the solubility of the acid dye (providing solubility in an organic solvent) or improving heat resistance and light resistance.

The "nitrogen-containing compound" forming the acid dye and the salt is considered to have solubility in all organic solvents or imaging solutions for salts or guanamine compounds, salt formability, absorbance and color valence of dyes, and hardenable compositions. The interaction of the other components is selected as the heat resistance and light resistance of the colorant. When it is selected from the viewpoints of only the absorbance and the color price, the nitrogen-containing compound is preferably as low as possible, and more preferably has a molecular weight of 300 or less, more preferably 280 or less, and particularly preferably has a molecular weight of 250 or less.

Further, the "nitrogen-containing compound" which forms the sulfaamine bond of the "acid dye sulfonamide" is also the same.

Specific examples of the nitrogen-containing compound are listed below. However, in the present invention, it is not limited to these specific examples. Further, among the following nitrogen-containing compounds, those having no -NH- group are not suitable for forming a guanamine bond.

The molar ratio (n) of the "nitrogen-containing compound/acid dye" in the salt of the acid dye and the nitrogen-containing compound determines the molar ratio of the acid dye molecule to the amine compound of the counter ion, and can be based on the acid dye-amine compound. The salt is freely selected by forming conditions. Specifically, the number of acid groups in the acid dye is mostly 0<n 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 composition, the light resistance, the heat resistance, and the like. In the case of selecting only based on the viewpoint of absorbance, n is preferably satisfied to satisfy 0<n The value of 4.5 is better to satisfy 0<n The value of 4 is particularly desirable to satisfy 0<n The value of 3.5.

From the viewpoint of obtaining sufficient coloring concentration and hardenability even when thinned, it is preferable that the organic solvent-soluble dye of the present invention contains a negative-type hardenable composition of the dye with respect to all solid components of the composition. It is 50.0 to 80.0% by mass, more preferably 52.5 to 75.0% by mass, particularly preferably 55.0 to 70.0% by mass. In addition, the organic solvent-soluble dye content ratio having two or more hydrogen bond donors according to the present invention is 50.0% by mass or more based on the total amount (mass) of the organic solvent-soluble dye contained in the composition as described above.

(B) Photosensitive compound The negative-type curable composition containing a dye of the present invention can be suitably configured by containing at least one of photosensitive compounds. a compound capable of undergoing a chemical reaction such as radical generation, acid generation, or salt generation with respect to radiation such as UV, Deep UV, visible light, infrared light, or electron beam, based on the alkali-soluble resin The reaction such as cross-linking, polymerization, or acidic group decomposition does not melt, or the coating film is relatively caused by polymerization of a polymerizable monomer or oligomer coexisting in the coating film, cross-linking of a crosslinking agent, and the like. It is used for the purpose of not dissolving the alkali imaging solution. Among them, a photopolymerization initiator or a photoacid generator is suitable.

Hereinafter, a photopolymerization initiator and a photoacid generator suitable for the present invention will be mainly described.

-Photopolymerization initiator -

The photopolymerization initiator is not particularly limited as long as it can be polymerized with a polymerizable monomer (polymerizable monomer), and is preferably added based on characteristics, initial efficiency, absorption wavelength, availability, cost, and the like. select.

The photopolymerization initiator may, for example, be at least one active halide selected from a halomethyl oxadiazole compound and a halomethyl-s-triazole compound, a 3-aryl-substituted coumarin compound, and Luo A phenanthrene dimer, a benzophenone compound, an acetophenone compound and a derivative thereof, a cyclopentadiene-benzene-iron coordination compound, a salt thereof, a quinone compound, and the like.

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 Is 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5-( p -cyanostyryl)-1,3,4-oxa Diazole, 2-trichloromethyl-5-( p -methoxystyryl)-1,3,4-oxadiazole, and the like.

The photopolymerization initiator of the active halide of the halomethyl- s -triazole compound is exemplified by the vinyl halomethyl- s -triazole compound disclosed in Japanese Patent Publication No. Sho 59-1281, which is disclosed in Japan. 2-(Naphtho-1-indenyl)-4,6-dihalomethyl- s -triazole compound and 4-( p -aminophenyl)-2, as disclosed in Japanese Patent Laid-Open No. 53-133428, 6-Dihalomethyl- s -triazine compounds and 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- Ditrichloromethyl s - triazine, 2- (2-methoxy-naphtho -1- acyl) -4,6-bis-trichloro-methyl - s - triazine, 2- (6-methoxy-5-methyl Naphtho-2-indenyl)-4,6-bistrichloromethyl- s -triazine, 2-(6-methoxynaphtho-2-indenyl)-4,6-bistrichloromethyl - s -triazine, 2-(5-methoxynaphtho-1-indenyl)-4,6-bistrichloromethyl- s -triazine, 2-(4,7-dimethoxynaphthalene And-1-indenyl)-4,6-bistrichloromethyl- s -triazine, 2-(6-ethoxynaphthalen-2-yl)-4,6-bistrichloromethyl- 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'-bis(chloroethyl)amine phenyl]-2,6- Bis(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 benzene -2,6-bis(trichloromethyl)-s-triazine, 4-[ m -N,N'-bis(ethoxycarbonylmethyl)amine phenyl]-2,6-di(three Chloromethyl) -s -triazine, 4-[ m -bromo- p- N,N'-bis(ethoxycarbonylmethyl)aminephenyl]-2,6-di(trichloromethyl) -s -Triazine, 4-[ m -chloro-p-N,N'-bis(ethoxycarbonylmethyl)amine phenyl]-2,6-di(trichloromethyl) -s -triazine, 4- [ m -Fluoro- p -N,N'-bis(ethoxycarbonylmethyl)amine phenyl]-2,6-bis(trichloromethyl) -s -triazine, 4-[ o -bromo- p -N,N'-bis(ethoxycarbonylmethyl)amine phenyl]-2,6-bis(trichloromethyl) -s -triazine, 4-[ o -chloro- p- N,N'- Di(ethoxycarbonylmethyl)amine phenyl]-2 ,6-bis(trichloromethyl) -s -triazine, 4-[ o -fluoro- p- N,N'-bis(ethoxycarbonylmethyl)aminephenyl]-2,6-di(three Chloromethyl) -s -triazine, 4-[ o -bromo- p- N,N'-bis(chloroethyl)aminephenyl]-2,6-di(trichloromethyl) -s -three Pyrazine, 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'- Bis(chloroethyl)amine phenyl]-2,6-bis(trichloromethyl) -s -triazine, 4-[ m -chloro- p- N,N'-bis(chloroethyl)amine benzene -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-B Oxycarbonylmethylamine phenyl)-2,6-di ( Chloromethyl) - 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-ethoxycarbonyl Methylamine phenyl)-2,6-bis(trichloromethyl) -s -triazine, 4-( m -bromo- p -N-chloroethylamine phenyl)-2,6-di (three Chloromethyl) -s -triazine, 4-( m -chloro- p -N-chloroethylaminephenyl)-2,6-bis(trichloromethyl) -s -triazine, 4-( m -fluoro- 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-bis(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 Specialty Chemical (share) (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-(O-phenylhydrazinyl)-1-[ 4-(phenylthio)phenyl]-1,2-octanedione, 2-benzyl-2-dimethylamino-4-morpholinobutanyl, 2,2'-dimethoxy 2-phenylacetophenone, 2-( o -chlorophenyl)-4,5-diphenylimidazole dimer, 2-( o -fluorophenyl)-4,5-diphenylimidazole Polymer, 2-( o -methoxyphenyl)-4,5-diphenylimidazole dimer, 2-( p -methoxyphenyl)-4,5-diphenylimidazole dimer , 2-( p -dimethoxyphenyl)-4,5-diphenylimidazole dimer, 2-(2,4-dimethoxy Phenyl)-4,5-diphenylimidazole dimer, 2-( p -methylphenylphenyl)-4,5-diphenylimidazole dimer, benzoin isopropyl ether, etc. Useful.

Among the starting agents, a lanthanide compound is preferred, and 2-(O-phenylhydrazinyl)-1-[4-(phenylthio)phenyl]-1,2-octanedione is preferred. 1-(0-Ethylindole)-1-[9-ethyl-6-(2-methylphenylindenyl)-9H-aminomethylindolyl-3-indenyl]ethanone.

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 hydrazine compound of the specification, the combination of triallyl imidazole dimer/ p -aminophenyl ketone disclosed in the specification of U.S. Patent No. 3,549,367, and the benzothiazole disclosed in Japanese Patent Publication No. Sho 51-48516 A compound/trihalomethyl-s-triazine compound or the like.

The content of the photopolymerization initiator containing the dye in the negative-type hardenable composition is preferably 1.0 to 40.0% by mass, more preferably 2.5 to 30.0% by mass, particularly preferably 5.0 to 20.0% by mass, based on the total solid content. . When the amount of the photopolymerization initiator is in this range, the polymerization reactivity is good, and at the same time, the polymerization rate is increased although the content is too large, but the film strength is not weakened by lowering the molecular weight.

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-anthracene, xanthone, 2-methylxanthone, 2-methoxyxanthone, 2-ethoxyxanthone, thioxanthone, 2,4 - diethyl thiaxanthone, acridone, 10-butyl-2-chloroacridone, benzoin, benzoin, p- (dimethylamino)phenylstyrylone, p -(dimethylamino)phenyl- p -methylstyryl ketone, benzophenone, p- (dimethylamino)benzophenone (or michelone), p- (diethyl Amino)benzophenone, benzoxanthone or the like, or a benzothiazole-based compound disclosed in Japanese Patent Publication No. Sho 51-48516, or Tinuvin 1130, Tinuvin 400 or the like.

Further, in addition to the above, it is preferred to carry out the addition of the thermal polymerization inhibitor in advance. 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-mercaptobenzimidazole, and the like are useful.

- Photoacid generator -

The photoacid generator is decomposed by irradiation with active light or radiation to generate an acid, and is not particularly limited as long as it is a photoacid generator having a polymerizable monomer (polymerizable monomer), and conventionally used. Photoacid generator.

For example, didiazepine salts disclosed in SISchlesinger, Photogr. Sci. Eng., 18, 387 (1974), TS Balal et al., Polymer, 21, 423 (1980), and the like are disclosed in U.S. Patent No. 4,609,905, Ammonium salts of various patent specifications, such as Japanese Patent Publication No. 4069056, Japanese Patent Application Laid-Open No. Hei No. Hei No. Hei No. Hei No. Hei No. 3-140140; disclosed in DCNecker et al., Macromolecules, 17, 2468 (1984), CWen et al., Teh. Proc. Conf. Rad. ASIA, p. 478, Tokyo, Oct (1988), U.S. Patent No. 4,609, 905, and No. 4,609, 056, each of which is incorporated herein by reference in its entirety by reference to J. s. s., J., vol. .& Eng.News, Nov. 28, p31 (1988), European Patent No. 104143, and US Patent No. 339,049, 410,201, and Japanese Patent Laid-Open No. 2-150848, Japanese Patent Laid-Open No. 2- Iodine salt, et al., 296514; disclosed in JVCrivello et al., Polymer J. 17, 73 (1985), JVCrivello et al., J. Org. Chem., 43, 3055 (1978), WWRatt et al., J. Polymer Sci., Polymer Chem. Ed., 22, 1789 (1984), JVCrivello et al., Polymer Bull., 14, 279 (1985), JVCrivello et al., Macr Omolecules, 14(5), 1141 (1981), JVCrivello et al., J. Polymer Sci., Polymer Chem. Ed., 17, 2877 (1979), European Patent No. 370693, US Patent No. 3902114, Europe Patent Nos. 233, 567, 297, 443, 297, 442, U.S. Patent No. 4,933,377, No. 4,201,201, 339,049, No. 4,760,013, No. 4,734,444, No. 2,833,827, German Patent No. 2,904,626, No. 3,604,580, No. 3,604,581鎏 salt of each patent specification; disclosed in JVCrivello et al., Macromolecules, 10 (6), 1307 (1977), JVCrivello et al., J. Polymer Sci., Polymer Chem. Ed., 17, 1047 (1979) Selenium salt; etc.; disclosed in CWen et al., Teh. Proc. Conf. Rad. Curing ASIA, p. 478, Tokyo, Oct (1988) and the like arsenic salts; and disclosed in U.S. Patent No. 3,905,815 Japanese Patent Publication No. Sho 46-4605, Japanese Patent Laid-Open No. Sho 48-36281, JP-A-55-32070, JP-A-60-239736, JP-A-61-169835, JP-A-61-169837 Organic halides of various patent specifications, such as JP-A-62-58241, JP-A-62-212401, JP-A-6-70243, JP-A-63-298339, etc. In K. Meier et al., J. Rad. Curing, 13 (4), 26 (1986), TPGill et al., Inorg. Chem., 19, 3007 (1980), D. Astruc, Acc. Chem. Res. , 19(12), 377 (1896), Japanese Patent Laid-Open No. 2-161445, etc., organometallic/organic halides, S. Hayase et al., J. Polymer Sci., 25, 753 (1987), E. Reichmanis etal J. Polymer Sci., Polymer Chem. Ed., 23, 1 (1985), QQ Zhu et al., J. Photochem., 36, 85, 39, 317 (1987), B. Amit et al., Tetrahedron Lett., (24), 2205 (1973), DHR Barton et al., J. Chem. Soc., 3571 (1965), PM Collins et al., J. Chem. Soc., Perkin I, 1695 (1975), M. Rudinstein etal Tetrahedron Lett., (17), 1445 (1975), JW Walker et al., J. Am. Chem. Soc., 110, 7170 (1988), SC Busman et al., J. Imaging Technol., 11 (4) ), 191 (1985), HM Houlihan et al., Macromolecules, 21, 2001 (1988), PM Collinsetal, J. Chem. Soc., Chem. Commun., 532 (1972), S. Hayase et al., Macromolecules, 18 , 1799 (1985), E. Reichmanis et al., J. Electrochem. Soc., Solid State Sci. Technol., 130 (6), FM Houlihan et al., Macromolecules, 21, 2001 (1988), European Patent No. 0290750 , No. 046083, No. 156535, 271851, No. 0388343, U.S. Patent No. 3,901,710, No. 4,181,531, Japanese Patent Application Laid-Open No. Sho 60-198538, JP-A-53-133022, etc., having o-nitrobenzyl type A photoacid generator for protecting groups; disclosed in M. Tunooka et al., Polymer Preprints Japan, 35(8), G. Berner et al., J. Rad. Curing, 13(4), wJMijs et al., Coating Technol. , 55 (697), 45 (1983), Akzo H. Adachi et al., Polymer Preprints Japan, 37 (3), European Patent No. 0199672, No. 84515, No. 199672, No. 044115, No. 0101122, USA Patent Nos. 4,618, 564, 4, 371, 605, 4, 443, 774, Japanese Patent Laid-Open No. 64-18143, and JP-A No. 2-245756, etc., and Japanese Patent Laid-Open No. Hei-4-365048, etc., represent imiline sulfonic acid. A compound which is photolyzed by a salt or the like to produce a sulfonic acid, and a diterpene compound disclosed in JP-A-61-166544.

In addition, the compounds represented by the following formula (III) can be further appropriately enumerated.

In the formula (III), Q ¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and Q ² represents a phenyl group which is unsubstituted or substituted with an alkyl group having 1 to 3 carbon atoms, or is unsubstituted or A phenyl group substituted with an alkoxy group having 1 to 3 carbon atoms.

The alkyl group having 1 to 3 carbon atoms represented by Q ¹ may, for example, be a methyl group, an ethyl group or a propyl group. The phenyl group substituted by the alkyl group having 1 to 3 carbon atoms represented by Q ² may, for example, be o -isopropylphenyl group or the like; and the phenyl group substituted with an alkoxy group having 1 to 3 carbon atoms may be exemplified by p : -methoxyphenyl, p -ethoxyphenyl, p -propoxyphenyl and the like.

The content of the negative-type curable composition containing the dye in the photoacid generator is usually in the range of 0.001 to 40% by mass, preferably 0.01 to 20% by mass, based on the total mass of the composition (excluding the solvent). The range is more preferably in the range of 0.1 to 15% by mass.

From the viewpoint of sensitivity, a photopolymerization initiator is preferred as the photosensitive compound of the present invention as compared with a photoacid generator.

(C) Alkali-soluble resin The negative-type curable composition containing a dye of the present invention can be formed locally by containing at least one of an alkali-soluble resin (hereinafter also referred to as "adhesive"). The binder of the present invention is not particularly limited as long as it is alkali-soluble, and is preferably selected from the viewpoints of heat resistance, developability, and availability.

The alkali-soluble binder is preferably a linear organic polymer, the organic solvent is soluble, and the developer can be imaged by using a weak alkali aqueous solution. Such a linear organic polymer is a polymer having a carboxylic acid in a side chain, and examples thereof include, for example, Japanese Patent Laid-Open No. Sho 59-44615, Japanese Patent Publication No. Sho 54-34327, and No. Sho 58-12577. Japanese Patent Publication No. 54-25957, JP-A-59-53836, JP-A-59-71048, etc., methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid 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, a poly(2-hydroxyethyl (meth)acrylate), or a polyethylene. Pyrrolidone, polyethylene oxide, polyvinyl alcohol and the like are also useful.

Further, copolymerization of a monomer having a hydrophilic group may be carried out, and examples thereof include alkoxyalkyl (meth)acrylate, hydroxyalkyl (meth)acrylate, and glyceryl (meth)acrylate. Methyl) acrylamide, N-methylol acrylamide, alkyl propylene amide of grade 2 and 3, dialkylaminoalkyl (meth) acrylate, morpholino (meth) acrylate, N-vinylpyrrolidone, N-vinyl caprolactam, vinylimidazole, ethylene triazole, methyl (meth)acrylate, ethyl (meth)acrylate, branched or linear propyl (meth)acrylate, It is obtained by copolymerizing a branched or linear butyl (meth)acrylate or phenoxyhydroxypropyl (meth)acrylate.

In addition to the above, as a monomer having a hydrophilic group, it contains 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 a salt thereof. A monomer such as a moiety or a morpholinethyl group is also useful.

In addition, from the viewpoint of improving the crosslinking efficiency, a polymerizable group may be provided in the side chain, and a polymer such as an allyl group, a (meth)acryl group or an allyloxyalkyl group may be added to the side chain. Useful.

Hereinafter, an example of a polymer containing such a polymerizable group is shown, and is not limited by such a polymerizable group as long as it contains an alkali-soluble group and a carbon-carbon unsaturated bond such as a COOH group, an OH group, or an ammonium group. .

Specific examples thereof include, for example, 2-hydroxyethyl acrylate having an OH group, methacrylic acid containing a COOH group, and a monomer such as a propylene group or a vinyl compound which can be copolymerized. The copolymer is obtained by reacting an epoxy ring reactive with an OH group with a compound having a carbon-carbon unsaturated bond group (for example, a compound such as glycidyl acrylate).

In addition to the epoxy ring, a compound having an acid anhydride, an isocyanate group or an acrylonitrile group can also be used. In addition, it is also possible to use a compound obtained by reacting an unsaturated carboxylic acid such as an acrylic acid with a compound having an epoxy ring disclosed in Japanese Laid-Open Patent Publication No. Hei 6-102669, No. 6-1938, and The reactant obtained by reacting with a saturated or unsaturated polybasic acid anhydride.

A compound having a base solubilizing group and a carbon-carbon-unsaturated group such as a COOH group is exemplified, for example, Dianaol NR series (manufactured by Mitsubishi Rayon Co., Ltd.); Photomer 6173 (polyamine group containing COOH group) Acetylene-based oligomer, manufactured by Diamond Shamrock Co., Ltd.; Biscoat R-264, KS photoresist-106 (both manufactured by Osaka Organic Chemical Industry Co., Ltd.); Cyclomer P series, Praxel CF200 series (both It is a Daicel Chemical Industry (stock) system; Ebecryl 3800 (Daicel UCB (stock) system).

Among the various alkali-soluble resins, a propylene-based resin is preferred, and the propylene-based resin is preferably benzyl (meth)acrylate, (meth)acrylic acid, or hydroxyethyl (meth)acrylate, a copolymer of selected monomers such as methyl acrylamide; and KS photoresist - 106 (both manufactured by Osaka Organic Chemical Industry Co., Ltd.); Cyclomer P series (Daicel Chemical Industry Co., Ltd.) )Wait.

The weight average molecular weight of the alkali-soluble resin (polystyrene equivalent value measured by a GPC method) is preferably a polymer of 1000 to 2 × 10 ⁵ , more preferably a polymer of 2000 to 1 × 10 ⁵ , particularly preferably 5000~5×10 ⁴ polymer.

The content of the dye-containing negative-type hardenable composition of the alkali-soluble resin is preferably 0.0 to 25.0% by mass, more preferably 0.0 to 15.0% by mass, particularly preferably 0.0%, based on the total solid content of the composition. 10.0% by mass.

In the case of using a photoacid generator as the photosensitive compound, a suitable alkali-soluble resin may, for example, be a phenol-formaldehyde resin, a cresol-formaldehyde resin, a phenol-cresol-formaldehyde co-condensation resin, or a phenol-modified resin. Toluene resin, polyhydroxystyrene, polyhalogenated hydroxystyrene, copolymer of N-(4-hydroxyphenyl)methacrylamide, hydroquinone-methacrylate copolymer and phenolic resin; and, disclosed in Japan A sulfonyl quinone imine-based polymer of JP-A-7-28244, and a carboxyl group-containing polymer disclosed in Japanese Laid-Open Patent Publication No. Hei 7-36184. In addition, a propylene-based resin having a sulfonylamino group, which is disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. Various alkali-soluble polymer compounds such as urethane resins.

Among them, a phenol resin is preferable, and a phenol resin which is particularly preferable is exemplified by a phenol resin of p -cresol, a phenol resin of p -cresol and m-cresol, and a phenol resin represented by the following formula (IV) ( n represents a value in which the molecular weight satisfies the range of 5000 to 10000.).

The content of the alkali-soluble resin containing the dye in the negative-type hardening composition is preferably from 0.0 to 30.0% by mass, more preferably from 5.0 to 25.0% by mass, particularly preferably from 10.0 to 20.0, based on the total solid content of the composition. %.

(D) Hardener The negative-type hardenable composition containing a dye of the present invention can be suitably configured by containing at least one of a curing agent. This hardener is effective for further accelerating the degree of pattern hardening formed. Hereinafter, the curing agent will be described.

In the case of using a photopolymerization initiator, the photosensitive compound is preferably selected from at least one of the following radical polymerizable monomers; in the case of using a photoacid generator, the photosensitive compound is preferably selected from the following crosslinks. It is composed of at least one of the agents.

- Radical polymerizable monomer -

The radical polymerizable monomer is preferably a compound having a boiling point of 100 ° C or higher at normal pressure and containing at least one ethylenically unsaturated group capable of undergoing addition polymerization. The ethylenically unsaturated group is particularly preferably a (meth) acrylonitrile group.

Further, the (meth)acrylonitrile group means an acryloyl group or a methacryloyl group, and in the following, a (meth)acrylate means an acrylate or a methacrylate.

Examples of the radically polymerizable monomer having a (meth)acryl fluorenyl group include poly(ethylene) methacrylate, poly(meth)acrylic acid propylene glycol, and (meth)acrylic phenoxy group. Monofunctional acrylate or methacrylate such as ethyl ester; polyethylene glycol di(meth)acrylate, trimethylolethyl tris(meth)acrylate, neopentyl glycol di(meth)acrylate An ester, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, hexanediol (meth)acrylate, Trimethylolpropane tris(propylene oxypropyl)ether, tris(propylene decyloxyethyl)isocyanate, addition of ethylene oxide or propylene oxide to polyfunctionals such as glycerol or trimethylolethane The (meth) acrylated monomer after the alcohol; the urethane of each publication disclosed in Japanese Patent Publication No. Sho 48-41708, Japanese Patent Publication No. Sho-50-6034, and JP-A-51-37193 Acrylates; disclosed in Japanese Patent Laid-Open No. 48-64183, Japanese Patent No. 49-43191, and Special Public Show No. 52-30490 Publication of polyester acrylates; is a polyfunctional acrylic ester of a mixture of an epoxy resin with (meth) acrylic acid reaction product 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, a polyfunctional (meth) acryl-based compound having two or more (meth) acrylonitrile groups is preferable, and a polyfunctional (meth) acrylate is particularly preferable from the viewpoint of improvement in the degree of curing.

The content of the solid-state component of the composition is preferably from 1 to 45% by mass, more preferably from 5 to 43% by mass, based on the total amount of the negative-type curable composition of the radical polymerizable monomer. It is 10 to 40% by mass. 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.

-crosslinker -

The crosslinking agent is not particularly limited as long as it is subjected to film curing by a crosslinking reaction, and examples thereof include (a) an epoxy resin; and (b) use of a methylol group or an alkoxymethyl group. a melamine compound, a melamine compound, a glycoluril compound or a urea compound substituted with at least one selected from a methoxymethyl group; (c) utilizing a methylol group, an alkoxymethyl group and a hydrazine group A phenol compound, a naphthol compound or a hydroxy oxime compound in which at least one group selected by the methyl group is substituted. Among them, a polyfunctional epoxy resin is particularly preferred.

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 A low molecular compound containing a divalent epoxy propyl group; similarly, trimethylolpropane triepoxypropyl ether, trishydroxymethylphenol triepoxypropyl ether, TrisP-PA triepoxypropyl ether a low molecular compound containing a trivalent epoxy propyl group; similarly, pentaerythritol tetraepoxypropyl ether, tetramethylol bisphenol A tetraepoxypropyl ether, etc. a low molecular weight compound; a low molecular compound containing a polyvalent epoxy propyl group such as dipentaerythritol pentaepoxypropyl ether or dipentaerythritol hexa-epoxypropyl ether; polyepoxypropyl (meth)acrylic acid a ring containing an ester, 2,2'-bis(hydroxymethyl)-1-butanol, 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct, etc. Oxypropyl Molecular compounds.

The number of the melamine compound substituted by the methylol group, the alkoxymethyl group or the decyloxymethyl group contained in the crosslinking agent (b) is 2 to 6; the glycoluril compound, the cyanuric acid compound The case of the amine 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 (b) is heated by the alkoxymethyl group-containing compound (b) in the presence of an acid catalyst such as hydrochloric acid, sulfuric acid, nitric acid or methanesulfonic acid in an alcohol. The one obtained. The oxiranylmethyl group-containing compound of the above (b) is obtained by mixing and stirring the hydroxymethyl group-containing compound (b) and ruthenium 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 and 4 positions of the phenolic compound of the backbone are substituted. Further, the naphthol compound and the hydroxyquinone compound which are the backbone are also preferably compounds which are substituted at the ortho and para positions of all the OH groups. 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 in which the ortho or para (position 2 or 4) of the phenolic OH group is a hydrogen atom, and is made into sodium hydroxide and hydrogen. It is obtained by reacting with formaldehyde water 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 the methylol compound (c) in the presence of an acid catalyst such as hydrochloric acid, sulfuric acid, nitric acid or methanesulfonic acid. It is obtained by heating.

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.

Examples of the backbone compound of the crosslinking agent (c) include an unsubstituted phenol compound, a naphthol compound, a hydroxy hydrazine compound, and the like in the ortho or para position of the phenolic OH group. For example, various isomeric forms of phenol and cresol can be used. Bisphenol, 4,4'-dihydroxyl, 2,3-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, bisphenol A, etc. Biphenyl, TrisP-PA (manufactured by Honshu Chemical Co., Ltd.), naphthol, dihydroxynaphthalene, 2,7-dihydroxyindole, and the like.

Specific examples of the crosslinking agent (c) include trishydroxymethylphenol, tris(methoxymethyl)phenol, and methoxymethyl group of 1 to 2 methylol groups of trimethylolphenol. a compound, trimethylol-3-methylphenol, tris(methoxymethyl)-3-cresol, trimethylol-3-methylphenol, 1~2 hydroxymethyl group, methoxy group a compound such as dimethylol cresol such as 2,6-dimethylol-4-cresol, tetramethylol bisphenol A, tetramethoxymethyl bisphenol A or tetramethylol double a methoxymethylated compound of 1 to 3 hydroxymethyl groups of phenol A, tetramethylol-4,4'-bishydroxybiphenyl, tetramethoxymethyl-4,4'-dihydroxyl linkage a methoxymethylated compound of benzene, TrisP-PA hexamethylol, TrisP-PA hexamethoxymethyl, TrisP-PA hexamethylol, 1 to 5 hydroxymethyl groups, Dihydroxymethylnaphthalenediol and 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 methylol group containing a methylol compound is partially or wholly methylated by a methoxy group.

Among these compounds, preferred are: trimethylol phenol, bishydroxymethyl-p-cresol, tetramethylol bisphenol A, and TrisP-PA (manufactured by Honshu Chemical Co., Ltd.). A hexamethylol group or such a hydroxymethyl group is alkoxymethyl group and a phenol compound substituted with both a methylol group and an alkoxymethyl group.

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

In the case of containing a crosslinking agent in the present invention, the content of the dye-containing negative-type hardening composition containing the crosslinking agents (a) to (c) varies depending on the kind of the raw material, and the composition is different from the composition. The solid content (mass) of the substance is preferably from 1 to 40% by mass, more preferably from 10 to 30% by mass. 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 or the dissolution of the unexposed portion is not significantly lowered.

- solvent -

When the negative-type curable composition containing a dye of the present invention is prepared, it is generally possible to contain a solvent. The solvent is basically not particularly limited as long as it satisfies the solubility of each component or the coating property of the negative-type hardenable composition containing a dye, and is particularly limited in consideration of the solubility, coatability, and safety of the binder. ideal.

Specific examples of the solvent, for example, preferred esters include ethyl acetate, n -butyl acetate, isobutyl acetate, amyl amide, isoamyl acetate, isobutyl acetate, butyl propionate, and butyl. Isopropyl acrylate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, ethyl lactate, methyl hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, methyl methoxyacetate, Ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.; 3-hydroxypropionate such as methyl 3-hydroxypropionate or ethyl 3-hydroxypropionate Acid alkyl esters, for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.; An alkyl 2-hydroxypropionate such as methyl hydroxypropionate, ethyl 2-hydroxypropionate or propyl 2-hydroxypropionate, for example, methyl 2-methoxypropionate or 2-methoxypropene Ethyl acetate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-hydroxy-2-methylpropanoate, 2-hydroxyl Ethyl 2-methylpropionate, 2- Methyl oxy-2-methylpropanoate, ethyl 2-ethoxy-2-methylpropionate, etc.; methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate Ethyl acetate, methyl 2-carbonylbutyrate, ethyl 2-carbonylbutyrate, etc.; for example, preferred ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl 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 Methyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, etc.; for example, preferred ketones include methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone or the like; for example, preferred aromatic hydrocarbons include toluene, xylene, and the like.

Among these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellulose acetate, ethyl lactate, diethylene glycol dimethyl ether, and butyl acetate are more preferred. Ester, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, propylene glycol methyl ether acetate, and the like. Among them, ethyl lactate, cyclohexanone, propylene glycol methyl ether acetate and the like are preferable.

- 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-mercaptopropyltrimethoxy a adhesion promoter such as decane; an antioxidant such as 2,2'-thiobis(4-methyl-6- t -butylphenol) or 2,6-di- t -butylphenol; 2-( 3- t -butyl An ultraviolet absorber such as 5-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole or alkoxybenzophenone; and an anti-coagulant such as sodium polyacrylate.

Further, in order to promote the alkali solubility of the non-hardened portion, it is desirable to further improve the developability of the dye-containing negative-type hardenable composition of the present invention, and it is preferable to add an 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, Other carboxylic acids such as phenylsuccinic acid, α-phenylacrylic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamyl acetic acid, coumaric acid, and umbrella acid.

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, the negative-type curable composition containing the dye of the present invention described above can be used. The color filter of the present invention is obtained by using the negative-type curable composition containing the dye of the present invention, and can be hardened by a negative method containing a dye by a coating method such as spin coating, flow coating, or roll coating. The 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 by a developing solution to form a colored pattern to be optimally configured (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 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.

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.

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 glass to which a transparent conductive film is attached; or a photovoltaic for a photographic element or the like. The element substrate is changed, 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 used in the method for producing a color filter of the present invention is an unhardened portion which dissolves the negative-type curable composition containing the dye of the present invention, and on the other hand, the hardened portion is composed of an insoluble portion. Any of the developing solutions can be used. Specifically, a combination of various organic solvents or an aqueous alkaline solution can be used. The organic solvent may, for example, be a 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 a CMOS element 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, but the present invention is not limited by the following examples as long as they do not. Also, as long as there is no special statement, "parts" are quality benchmarks.

(Example 1)

1) Preparation of photoresist solution ● Propylene glycol monomethyl ether acetate (PGMEA)...19.20 parts ●Ethyl lactate...36.67 parts ●Adhesive agent...30.51 parts [Benzyl methacrylate/methacrylic acid/methacrylic acid- 2-Hydroxyethyl copolymer (copolymerization ratio [Mole ratio] = 41% EL solution of 60/20/20] ● Dipentaerythritol hexaacrylate (radical polymerizable monomer)...12.20 parts ● Polymerization inhibitor ( P -methoxyphenol)...0.0061 parts ●Fluorine-based surfactant...0.83 parts (F-475, manufactured by Dainippon Ink Chemicals Co., Ltd.) ●TAZ-107...0.586 parts (trihalomethyltriazine) Photopolymerization initiator; manufactured by Midori Chemical Co., Ltd.) These components were mixed and dissolved to prepare a photoresist solution.

2) Preparation of a glass substrate to which an undercoat layer was applied Ultrasonic cleaning of a glass substrate (Corning 1737) was carried out using a 1% aqueous NaOH solution, followed by washing with water and dehydration (200 ° C / 30 minutes). Then, the photoresist solution obtained in the above 1) was applied onto the cleaned glass substrate by a spin coater to have a film thickness of 2 μm, and then dried at 220 ° C for 1 hour to form a cured film ( Undercoat).

3) Preparation and coloring of the coloring curable composition (negative type) A-1 The compound of the following composition was dissolved and dissolved to prepare a color hardening composition A-1 of the present invention.

[Composition of Colored Curable Composition A-1]

●cyclohexanone...80 parts ●adhesive (alkali-soluble resin)...1.0 parts [benzyl methacrylate/methacrylic acid (=70/30 [mole ratio])] ●Solvent dyes related to the organic solvent of the present invention A...7.2 parts (exemplified compound (1)) ● 4.8 parts of the organic solvent-soluble dye B of the present invention (exemplified compound (38)) ● polymerization inhibitor ( p -methoxyphenol) ... 0.01 parts ● hexaacrylic acid II Pentaerythritol ester (radical polymerizable monomer)...4.9 parts ● Photopolymerization initiator CGI-124...2.1 parts (manufactured by Ciba Specialty Chemicals Co., Ltd.)

4) Exposure and development (image formation) of the colored curable composition on the undercoat layer of the undercoat layer obtained in the above 2), and applying the color hardening obtained by applying the 3) by a spin coater The composition A-1 was adjusted to have a film thickness of 0.8 μm and pre-baked at 100 ° C for 120 seconds.

Next, the coating film was irradiated with an exposure amount of 2000 mJ/cm ² using a wavelength of 365 nm using an exposure apparatus. After the irradiation, development was carried out using a 60% CD-2000 (manufactured by Fujifilm Electronics Materials Co., Ltd., Japan) at 23 ° C for 120 seconds. Thereafter, the mixture was washed with water for 10 seconds and then spray dried. Thereafter, it was baked at 200 ° C for 45 minutes to obtain a coating film.

(Examples 2 to 10 and Comparative Examples 1 to 2)

In Example 1, except that the organic solvent-soluble dyes A and B used for coloring the curable composition A-1 were replaced by the following Table 1, respectively, the same manner as in Example 1 was carried out to obtain color hardening. The composition A-2~A-12 was obtained at the same time.

(assessment)

The coating film obtained in each of the examples and the comparative examples was evaluated for the decolorization resistance in the following manner. The results are shown in Table 1 below.

The spectroscopic (spectral A) of each of the coated films after the baking was measured. Next, this coating film was immersed in cyclohexanone for 1 minute, and the spectroscopic (spectral B) was measured again. From the obtained spectral beams A and B, the dye residual ratio (%; B/A × 100) was calculated and evaluated. The closer the value is to 100%, the more excellent the decolorization resistance is.

* The exemplary compounds (1) to (39) disclosed in the organic solvent-soluble dyes A and B, and the direct red 181, the solvent blue 25, and the mordant blue 13 are organic solvent-soluble dyes having two or more hydrogen bond donors.

As shown in Table 1, in the examples, regardless of whether or not the dye concentration is high, discoloration due to dye elution during repeated application can be suppressed, and a coating film having a desired color density and color tone can be obtained. On the other hand, in the comparative example, the discoloration at the time of repeated coating was remarkable.

(Example 11)

In the first embodiment, the "composition of the colored curable composition A-1" for the preparation of the "3) coloring curable composition (negative type) A-1 is replaced by the following coloring hardening. The composition of the composition B-1 was prepared, and after heating and heating at 120 ° C for 60 seconds before the development, the same procedure as in Example 1 was carried out to prepare the colored curable composition B-1. A coating film was obtained, and at the same time, evaluation of decolorization resistance was performed.

[Composition of Colored Curable Composition B-1]

Cyclohexanone...80 parts ●Adhesive agent [ p -cresol novolac resin (Mw: 5000)] 6.0 parts ● Related organic solvent soluble dye A...6.6 parts (exemplary compound (1)) ● Related to the present invention Organic solvent soluble dye B...4.4 parts (exemplified compound (39)) ●hexamethoxymethyl melamine...2.5 parts ●The following compound (38) [photoacid generator] 0.5 parts

(Examples 12 to 15 and Comparative Examples 3 to 4)

In the same manner as in Example 11, except that the organic solvent-soluble dyes A and B used for coloring the curable composition B-1 were replaced by the following Table 2, respectively, the color hardening was carried out. After the composition B-2 to B-7, a coating film was obtained, and at the same time, evaluation of decolorization resistance was performed.

* The exemplary compounds (1) to (39) disclosed in the organic solvent-soluble dyes A and B, and the direct red 181 and the solvent blue 25-based organic solvent-soluble dyes having two or more hydrogen bond donors.

As shown in Table 2, in the examples, regardless of whether or not the dye concentration is high, discoloration due to elution of the dye during repeated application can be suppressed, and a coating film having a desired color density and color tone can be obtained. On the other hand, in the comparative example, the discoloration at the time of repeated coating was remarkable.

Further, in addition to the organic solvent-soluble dyes of the present invention used in the examples, since the exemplary compounds relating to the above-mentioned organic solvent-soluble dyes of the present invention also have hydrogen which can form hydrogen bonds, since they can be used in the same manner as used. The action of the exemplified compound (the organic solvent-soluble dye of the present invention) can suppress the discoloration due to the elution of the dye, and can obtain a coating film having a desired color density and color tone.

Claims (5)

A negative-type curable composition containing a dye, comprising an organic solvent-soluble dye, characterized in that the content of the organic solvent-soluble dye is 50% by mass or more based on all solid components, and at least one of the organic solvent-soluble dyes has Two or more hydrogen bond donors, and is a dye represented by the following formula (I); In the formula (I), A represents an aryl group or a 5- to 6-membered aromatic heterocyclic ring; B ¹ represents -CR ¹ = or a nitrogen atom, and B ² represents -CR ² = or a nitrogen atom, and B ¹ and B ² Does not simultaneously represent a nitrogen atom; R ⁵ and R ⁶ represent a respective independent hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, a fluorenyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an aminomethylcarbonyl group, an alkyl group. Sulfhydryl, arylsulfonyl or sulfonyl, R ⁵ and R ⁶ do not simultaneously represent a hydrogen atom; G, R ¹ and R ² represent a respective independent hydrogen atom, a halogen atom, an aliphatic group, or an aromatic group. Base, heterocyclic group, cyano group, carboxyl group, aminomethyl sulfonyl group, alkoxycarbonyl group, aryloxycarbonyl group, fluorenyl group, hydroxy group, alkoxy group, aryloxy group, decyloxy group, decyloxy group, aminomethicone Oxyl, heterocyclic oxy, alkoxycarbonyloxy, aryloxycarbonyloxy, "substituted amino group substituted by alkyl, aryl or heterocyclic group", decylamino, ureido, sulfonamide Alkyl, alkoxycarbonylamino, aryloxycarbonylamino, alkylsulfonylamino, arylsulfonylamino, nitro, alkylthio, arylthio, alkylsulfonyl, arylsulfonyl , alkylphosphonium, arylphosphonium, amine sulfonyl a sulfo group, a fluorenyl group or a heterocyclic thio group; a group having at least two hydrogen bond donor groups in the groups represented by A, G, B ¹ , B ² , R ⁵ and R ⁶ , each group The group may have two or more independent hydrogen bond donors; in addition, R ¹ and R ⁵ and/or R ⁵ and R ⁶ may be bonded to each other to form a 5- or 6-membered ring. The negative-type hardening composition containing a dye according to the first aspect of the invention, wherein the content of the organic solvent-soluble dye having two or more hydrogen bond donors is 50% by mass or more based on the total amount of the organic solvent-soluble dye . The dye-containing negative-type hardening composition according to claim 1, wherein the hydrogen bonding system is derived from a hydroxyl group, a carboxyl group, an amine sulfonyl group, a monoalkylamine sulfonyl group, or an arylamine sulfonyl group. The group selected with a thiol group. A color filter comprising a dye-containing negative-type hardenable composition according to any one of claims 1 to 3. A method for producing a color filter, comprising applying a dye-containing negative-type hardenable composition according to any one of claims 1 to 3 to a carrier, exposing through a photomask, and developing the image. The step of forming a pattern image.