JP2007147784A - Colored curable composition, color filter and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymer dye-containing colored curable composition having high lightfastness and heat fastness, as well as proper hues and high transmissivity characteristics, superior in temporal stability and solvent resistance, and which is suitable for a color filter. <P>SOLUTION: The colored curable composition contains a polymer dye, wherein the polymer dye is a copolymer of one kind of dye monomer represented by Formula (P) and one kind of colorless monomer having one ethylenic double bond. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a colored curable composition suitable for forming a color filter used for a liquid crystal display element (LCD) or a solid-state imaging element (for example, CCD, CMOS, etc.), and a color using the colored curable composition The present invention relates to a filter and a manufacturing method thereof.

As a color filter formed on the element for colorizing a solid-state image sensor or a liquid crystal display element, it is composed of a yellow filter layer, a magenta filter layer, and a cyan filter layer formed adjacent to each other on the same plane on the substrate. In addition, a color filter including a color filter, a red filter layer, a green filter layer, and a blue filter layer is known. In these filter layers, a band-like pattern or a mosaic pattern is formed.
Various methods have been proposed as a method for manufacturing the color filter as described above. In particular, a so-called color resist method in which a photosensitive resin composition containing a dye is exposed and developed to repeatedly perform patterning a required number of times is widely put into practical use.

  The color resist method is a method for producing a color filter by a photolithographic method using a colored radiation-sensitive composition in which pigments are dispersed in various photosensitive compositions. This method uses pigments. It is stable to light, heat, etc., and has sufficient positional accuracy for patterning by photolithography, and is a suitable method for producing a color filter for large screens and high-definition color displays.

  When a color filter is produced by a pigment dispersion method in which a pigment is dispersed as described above, a coating film is formed by applying a radiation sensitive composition on a glass substrate using a spin coater or a roll coater. A colored pixel is obtained by pattern exposure and development, and a color filter is obtained by performing this operation in accordance with the desired number of hues. As a pigment dispersion method, a negative photosensitive composition using a photopolymerizable monomer and a photopolymerization initiator in an alkali-soluble resin has been disclosed (see, for example, Patent Documents 1 to 8, 12, and 13).

  On the other hand, in recent years, there has been a demand for higher definition in color filters for solid-state imaging devices. However, in the conventional pigment dispersion system as described above, the resolution is not improved, and color unevenness due to the coarse particles of the pigment occurs. It was not suitable for applications where a pattern was required. In order to solve such problems, the use of dyes has been conventionally proposed (for example, see Patent Documents 9 to 10). A positive photosensitive composition is also disclosed (for example, see Patent Documents 11 to 12).

However, dye-containing colored curable compositions have the following problems, and further improvements have been demanded. That is,
(1) Dyes are generally inferior in heat fastness, light fastness and the like as compared with pigments.
(2) When the molar extinction coefficient of the dye is low, a large amount of dye must be added, and other components such as a polymerizable compound, a binder and a photopolymerization initiator in the colored curable composition are relatively It must be reduced to. As a result, the heat fastness of the cured part which has been cured and the solvent resistance at the time of coating the next layer are insufficient.
(3) Even if the dye has a high molar extinction coefficient, a dye having poor solubility needs to have a large molecular weight in order to improve the solubility in the liquid preparation or to improve the stability of the liquid preparation. As a result, a large amount (by weight) of a dye must be added, and other components such as a polymerizable compound, a binder, and a photopolymerization initiator in the colored curable composition must be relatively reduced. Therefore, the heat fastness of the cured part which has been cured and the solvent resistance when the next layer is applied are insufficient.

  Then, in order to improve the said subject, especially the subject of (2) and (3), although examination regarding what has a specific substituent is made | formed, it was not enough (for example, refer patent document 13). .

  On the other hand, yellow dyes and magenta dyes are used for red filter arrays of color filters, yellow dyes and cyan dyes are used for green filter arrays, and long wave magenta dyes and cyan dyes are used for blue filter arrays (for example, (See Patent Document 10).

Japanese Patent Laid-Open No. 1-102469 Japanese Patent Laid-Open No. 1-152499 JP-A-2-181704 JP-A-2-199403 Japanese Patent Laid-Open No. 4-76062 Japanese Patent Laid-Open No. 5-273411 JP-A-6-184482 JP-A-7-140654 JP-A-6-75375 JP 2002-14221 A Japanese Patent Publication No.7-111485 JP 2002-14223 A JP-A-7-72323

  However, no dye has been found that satisfies light and heat fastness, has good solubility, has excellent temporal stability when a colored curable composition is prepared, and sufficiently satisfies the solvent resistance after curing. However, further improvements are desired.

  In addition, dye-containing colored curable compositions are useful in applications such as solid-state imaging devices that require particularly high definition and uniform color, but they are fast against light and heat and stable over time when used as liquid preparations. There was a need to improve sex. Furthermore, when an organic solvent soluble dye is used, since the organic solvent resistance of the colored pattern is insufficient, the solvent in which the dye in the existing colored pattern elutes when the next color is overcoated on the existing pattern. Improvements in sex were also desired.

  The present invention has been made in view of the above, and has a good hue and high transmittance characteristics, and has high color fastness, high light fastness, high temporal stability, and excellent solvent resistance after curing. An object of the present invention is to provide a color composition excellent in light fastness, heat fastness, and solvent resistance, and a method for producing the same, and to achieve the object. This is the subject of the present invention.

As a result of intensive studies, the present inventors have obtained the knowledge that by using a specific polymer in a polymer dye, light fastness and heat fastness are high and stability over time is improved and solvent resistance is improved. The present invention has been achieved based on such findings.
Specific means for achieving the above object are as follows.

(1) A polymer dye is contained, and the polymer dye is at least one of a colorless monomer having at least one dye monomer represented by the following general formula (P) and at least one ethylenic double bond. One or more selected from the group consisting of a copolymer with a seed and a polymer derived from at least one dye monomer represented by the following general formula (P): It is a colored curable composition.

In general formula (P), R ^a1 and R ^a2 each independently represent a hydrogen atom, an aliphatic group, an aryl group or a heterocyclic group, and L ¹ represents the following (L-1), (L-2), (L -3) and any one of (L-4), i represents 0 or 1. Q represents a pigment residue obtained by removing a hydrogen atom from any possible position of the dye represented by the following general formula (1).

In (L-1) to (L-4), R ^a3 and R ^a4 each independently represent a hydrogen atom, an aliphatic group, an aryl group, or a heterocyclic group. In (L-1) to (L-4), the dye residue and the group having an ethylenic double bond may be bonded to either side.

In general formula (1), R ^{301 to} R ³⁰⁶ each independently represent a hydrogen atom or a substituent. When at least two of R ^{301 to} R ³⁰⁶ are adjacent to each other, they may be bonded to each other to form a 5- to 6-membered ring, and the ring may further have a substituent.

(2) A polymer dye is contained, and the polymer dye is at least one of a colorless monomer having at least one dye monomer represented by the following general formula (P) and at least one ethylenic double bond. One or more selected from the group consisting of a copolymer with a seed and a polymer derived from at least one dye monomer represented by the following general formula (P): It is a color filter.

In general formula (P), R ^a1 and R ^a2 each independently represent a hydrogen atom, an aliphatic group, an aryl group or a heterocyclic group, and L ¹ represents the following (L-1), (L-2), (L -3) and any one of (L-4), i represents 0 or 1. Q represents a pigment residue obtained by removing a hydrogen atom from any possible position of the dye represented by the following general formula (1).

In (L-1) to (L-4), R ^a3 and R ^a4 each independently represent a hydrogen atom, an aliphatic group, an aryl group, or a heterocyclic group. In (L-1) to (L-4), the dye residue and the group having an ethylenic double bond may be bonded to either side.

In general formula (1), R ^{301 to} R ³⁰⁶ each independently represent a hydrogen atom or a substituent. When at least two of R ^{301 to} R ³⁰⁶ are adjacent to each other, they may be bonded to each other to form a 5- to 6-membered ring, and the ring may further have a substituent.

(3) A method for producing a color filter, comprising: applying a colored curable composition as described in (1) above onto a support, exposing through a mask, developing, and forming a pattern image. It is.

  According to the present invention, a colored curable composition having good hue and high transmittance characteristics, high light fastness and heat fastness, excellent temporal stability and solvent resistance after curing, and good hue. And a color filter excellent in light fastness, heat fastness and solvent resistance and a method for producing the same can be provided.

  Below, the colored curable composition of this invention, a color filter, and its manufacturing method are demonstrated in detail.

<Colored curable composition>
The colored curable composition of the present invention contains a polymer dye, and the polymer dye is a colorless single dye having at least one dye monomer represented by the following general formula (P) and at least one ethylene double bond. Copolymer with at least one monomer or polymer derived from at least one dye monomer represented by the following general formula (P) (hereinafter collectively referred to as “the dye according to the present invention”) It is said that). This may be any one that can be cured by light or heat, and preferably contains a radiation-sensitive compound and a polymerizable monomer. Moreover, generally it can comprise using a solvent further and can comprise using other components, such as a binder and a crosslinking agent, as needed.
Moreover, a resist solution is synonymous with a curable composition.

[Aliphatic, aryl, heterocyclic ring in the present invention]
In the present invention, aliphatic means that the aliphatic moiety is linear, branched or cyclic and may be saturated or unsaturated. For example, an alkyl group, alkenyl group, cycloalkyl group, cycloalkenyl group may be substituted. Including, these may be unsubstituted or substituted with a substituent. In addition, the aryl in this specification may be either a single ring or a condensed ring, and may be unsubstituted or substituted with a substituent. In addition, the term “heterocycle” in the present specification means that the heterocycle moiety has a heteroatom (for example, a nitrogen atom, a sulfur atom, or an oxygen atom) in the ring. These may be either a single ring or a condensed ring, which may be unsubstituted or substituted with a substituent.

[Substituent in the Present Invention]
In the present specification, the substituent may be any group that can be substituted, for example, an aliphatic group, an aryl group, a heterocyclic group, an acyl group, an imide group, an azo group, an acyloxy group, an acylamino group, an aliphatic oxy group, Aryloxy group, heterocyclic oxy group, aliphatic oxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, carbamoyl group, aliphatic sulfonyl group, arylsulfonyl group, heterocyclic sulfonyl group, aliphatic sulfonyloxy group, aryl Sulfonyloxy group, heterocyclic sulfonyloxy group, sulfamoyl group, aliphatic sulfonylamino group, arylsulfonylamino group, heterocyclic sulfonylamino group, amino group, aliphatic amino group, arylamino group, heterocyclic amino group, aliphatic oxy Carbonylamino group, aryloxycarboni Amino group, heterocyclic oxycarbonylamino group, aliphatic sulfinyl group, arylsulfinyl group, aliphatic thio group, arylthio group, heterocyclic thio, hydroxy group, cyano group, sulfo group, carboxyl group, aliphatic oxyamino group, aryl Oxyamino group, carbamoylamino group, sulfamoylamino group, halogen atom, sulfamoylcarbamoyl group, carbamoylsulfamoyl group, dialiphatic oxyphosphinyl group, diaryloxyphosphinyl group, nitro group, carbamoyloxy Group and the like.

[Dye monomer represented by general formula (P)]
The dye monomer represented by the general formula (P) of the present invention is described in detail below.

In general formula (P), R ^a1 and R ^a2 each independently represent a hydrogen atom, an aliphatic group, an aryl group or a heterocyclic group, and L ¹ represents the following (L-1), (L-2), (L -3) and any one of (L-4), i represents 0 or 1. Q represents a pigment residue obtained by removing a hydrogen atom from any possible position of the dye represented by the following general formula (1).

In (L-1) to (L-4), R ^a3 and R ^a4 each independently represent a hydrogen atom, an aliphatic group, an aryl group, or a heterocyclic group. In (L-1) to (L-4), the dye residue and the group having an ethylenic double bond may be bonded to either side.

The aliphatic group represented by R ^a1 or R ^a2 and the aliphatic group represented by R ^a3 or R ^a4 in L ¹ are linear, branched or cyclic, saturated groups or unsaturated groups It may be unsubstituted or may have a substituent, preferably an aliphatic group having 1 to 15 carbon atoms, and more preferably an alkyl group. Examples thereof include a methyl group, an ethyl group, an isopropyl group, a 2-ethylhexyl group, an allyl group, a cyclohexyl group, and a 2-cyclohexenyl group.
The aryl group represented by R ^a1 or R ^a2 and the aryl group represented by R ^a3 or R ^a4 in L ¹ may be unsubstituted or substituted, and the aryl having 6 to 16 carbon atoms in total Groups are preferred. For example, a phenyl group, 2-chlorophenyl group, 4-methylphenyl group, 4-methoxyphenyl group, etc. are mentioned.
The heterocyclic group represented by R ^a1 or R ^a2 and the heterocyclic group represented by R ^a3 or R ^a4 in L ¹ may be unsubstituted or substituted, and may be saturated or unsaturated. It may be a cyclic group, and preferably has 3 to 15 total carbon atoms. For example, 3-pyridyl group, 2-pyrimidyl group, 2-pyrazinyl group, 1-piperidyl group and the like can be mentioned.

Among the above, R ^a1 or R ^a2 is preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom or an alkyl group, from the viewpoint of more effectively achieving the effects of the present invention. Most preferred is a hydrogen atom.
From the standpoint of more effectively achieving the effects of the present invention, R ^a3 and R ^a4 are preferably a hydrogen atom, an alkyl group, or an aryl group, and more preferably a hydrogen atom or an alkyl group.
From the standpoint of more effectively achieving the effects of the present invention, i is preferably 1. L ¹ is preferably (L-1) or (L-2), and more preferably (L-2).
From the viewpoint of more effectively achieving the effects of the present invention, i is preferably ¹ , and L ¹ is preferably (L-1) or (L-2), and is (L-2). The case is more preferred.
In general formula (P), R ^a1 is a hydrogen atom or an alkyl group, R ^a2 is a hydrogen atom or an alkyl group, and L ¹ is (L-1) or (L-2), A compound in which Q is the general formula (1) is preferable, R ^a1 is a hydrogen atom or an alkyl group, R ^a2 is a hydrogen atom, and L ¹ is (L-1) or (L-2). And a compound in which Q is the general formula (1) is more preferable, R ^a1 is a hydrogen atom, R ^a2 is a hydrogen atom, and L ¹ is (L-1) or (L-2). Further, a compound in which Q is the general formula (1) is more preferable, R ^a1 is a hydrogen atom, R ^a2 is a hydrogen atom, L ¹ is (L-1), and Q is the general formula The compound (1) is particularly preferred.

Next, the dye represented by the general formula (1) will be described in detail.

In the general formula (1), R ³⁰¹ , R ³⁰² , R ³⁰³ , R ³⁰⁴ , R ³⁰⁵ and R ³⁰⁶ each independently represent a hydrogen atom or a substituent. The substituents represented by R ^{301 to} R ³⁰⁶ may be any substituents as long as they are substitutable groups, and are preferably the groups described in the above-mentioned substituents, preferably each independently a halogen atom, Group, aryl group, heterocyclic group, cyano group, carboxyl group, carbamoyl group, aliphatic oxycarbonyl group, aryloxycarbonyl group, acyl group, hydroxy group, aliphatic oxy group, aryloxy group, acyloxy group, carbamoyloxy Group, heterocyclic oxy group, amino group, aliphatic amino group, arylamino group, heterocyclic amino group, acylamino group, carbamoylamino group, sulfamoylamino group, aliphatic oxycarbonylamino group, aryloxycarbonylamino group, Aliphatic sulfonylamino group, arylsulfonylamino group, nitro group, aliphatic thio group, Riruchio group, an aliphatic sulfonyl group, an arylsulfonyl group, a sulfamoyl group, a sulfo group, an imide group, or a heterocyclic thio group.
If at least two R ³⁰¹ to R ³⁰⁶ is in the adjacent position, i.e. when it has a positional relationship such as being attached to a carbon atom in which a plurality of groups, for example, adjacent of ^R 301 ^{to R 306} are bonded to each other, A 5- to 6-membered ring may be formed, and the ring may further have a substituent. Examples of the 5-membered or 6-membered ring include a benzene ring, a naphthalene ring, a cyclohexane ring, a furan ring, and the like, and may further have a substituent. Any group can be used as long as it is a group listed in the section and can be substituted.

Next, among the substituents represented by R ^{301 to} R ³⁰⁶ , preferred ones will be described in detail.
Examples of the halogen atom represented by R ^{301 to} R ³⁰⁶ include a fluorine atom, a chlorine atom, and a bromine atom.

The aliphatic group represented by R ^{301 to} R ³⁰⁶ may be unsubstituted or substituted, may be saturated or unsaturated, and may be cyclic. For example, an alkyl group, substituted alkyl Group, alkenyl group, substituted alkenyl group, alkynyl group, substituted alkynyl group, aralkyl group, substituted aralkyl group and the like. The total number of carbon atoms of the aliphatic group is preferably 1-30, more preferably 1-16, such as methyl, ethyl, butyl, isopropyl, t-butyl, hydroxyethyl, methoxyethyl, Examples include cyanoethyl, trifluoromethyl, 3-sulfopropyl, 4-sulfobutyl, cyclohexyl, benzyl, 2-phenethyl, vinyl, and allyl.

The aryl group represented by R ^{301 to} R ³⁰⁶ may be unsubstituted or substituted, and the total number of carbon atoms is preferably 6 to 30, more preferably 6 to 16, for example, Examples include phenyl, p-tolyl, p-methoxyphenyl, o-chlorophenyl, and m- (3-sulfopropylamino) phenyl.

The heterocyclic group represented by R ^{301 to} R ³⁰⁶ may be saturated or unsaturated, may be unsubstituted or have a substituent, and has 1 to 30 total carbon atoms. It is more preferable that it is 1-15, for example, 2-pyridyl, 2-thienyl, 2-thiazolyl, 2-benzothiazolyl, 2-benzoxazolyl, 2-furyl, etc. are mentioned.

The carbamoyl group represented by R ^{301 to} R ³⁰⁶ may be unsubstituted or substituted, and the total number of carbon atoms of the carbamoyl group is preferably 1 to 30, and preferably 1 to 16. More preferably, examples include methylcarbamoyl, dimethylcarbamoyl, phenylcarbamoyl and N-methyl-N-phenylcarbamoyl.

The aliphatic oxycarbonyl group represented by R ^{301 to} R ³⁰⁶ may be unsubstituted or substituted, may be saturated or unsaturated, may be cyclic, The total number of carbon atoms of the aliphatic oxycarbonyl group is preferably 2 to 30, more preferably 2 to 16 carbon atoms, and examples thereof include methoxycarbonyl, ethoxycarbonyl, and 2-methoxyethoxycarbonyl. It is done.

The aryloxycarbonyl group represented by R ^{301 to} R ³⁰⁶ may be unsubstituted or substituted, and the total number of carbon atoms of the aryloxycarbonyl group is preferably 7 to 30, -16 is preferable, and examples thereof include a phenoxycarbonyl group, a 4-methylphenoxycarbonyl group, and a 3-chlorophenoxycarbonyl group.

The acyl group represented by R ^{301 to} R ³⁰⁶ may be an aliphatic carbonyl group, an arylcarbonyl group, or a heterocyclic carbonyl group, and preferably has 1 to 30 total carbon atoms in the acyl group. When the total number of carbon atoms is 1 to 16, it is more preferable, and examples thereof include acetyl, methoxyacetyl, thienoyl and benzoyl.

The aliphatic oxy group represented by R ^{301 to} R ³⁰⁶ may be unsubstituted or substituted, may be saturated or unsaturated, may be cyclic, and may be an aliphatic oxy group. The total number of carbon atoms is preferably an alkoxy group of 1 to 30, more preferably 1 to 15, such as methoxy, ethoxy, isopropoxy, methoxyethoxy, hydroxyethoxy and 3-carboxypropoxy. Can be mentioned.

The aryloxy group represented by R ^{301 to} R ³⁰⁶ may be unsubstituted or substituted, and the total number of carbon atoms of the aryloxy group is preferably 6 to 30, More preferably, it is -16, for example, phenoxy, p-methoxyphenoxy, o-methoxyphenoxy, etc. are mentioned.

The acyloxy group represented by R ^{301 to} R ³⁰⁶ may be an aliphatic carbonyloxy group, an arylcarbonyloxy group, or a heterocyclic carbonyloxy group, and the acyloxy group has 1 to 30 total carbon atoms. Is more preferable, and examples thereof include acetoxy, nicotinoyl and benzoyloxy.

The carbamoyloxy group represented by R ^{301 to} R ³⁰⁶ may be unsubstituted or substituted, and the carbamoyloxy group preferably has 1 to 30 total carbon atoms, and preferably has 1 to 16 carbon atoms. In some cases, more preferable examples include N-methylcarbamoyloxy, dimethylcarbamoyloxy, phenylcarbamoyloxy and the like.

In the heterocyclic oxy group represented by R ^{301 to} R ³⁰⁶ , the heterocyclic moiety may be either saturated or unsaturated, and may be unsubstituted or substituted, and the heterocyclic oxy group The total number of carbon atoms is preferably 1-30, more preferably 1-15, such as 2-pyridyloxy, 2-thienyloxy, 2-thiazolyloxy, 2-benzothiazolyloxy, Examples include 2-benzoxazolyloxy and 2-furyloxy.

The aliphatic amino group represented by R ^{301 to} R ³⁰⁶ may be unsubstituted or further substituted, may be saturated or unsaturated, may be cyclic, The aliphatic amino group preferably has 1 to 30 total carbon atoms, more preferably 1 to 16 carbon atoms, such as methylamino, diethylamino, bis-2-ethoxyethylamino and N-methyl-N. -2-methoxyethylamino and the like.

The arylamino group represented by R ^{301 to} R ³⁰⁶ may be unsubstituted or substituted, and the total number of carbon atoms of the arylamino group is preferably 6 to 30, More preferably, it is -16, for example, anilino, 4-methoxyphenylamino, etc. are mentioned.

The heterocyclic amino group represented by R ^{301 to} R ³⁰⁶ may be unsubstituted or further substituted, may be saturated or unsaturated, may be cyclic, and may have total carbon. The number is preferably 1-30, more preferably 1-16, and examples include 2-pyridylamino, 2-thienylamino, 2-thiazolylamino, 2-benzothiazolyloxy, and the like.

The acylamino group represented by R ^{301 to} R ³⁰⁶ may be an aliphatic carbonylamino group, an arylcarbonylamino group, or a heterocyclic carbonylamino group, and the total number of carbon atoms of the acylamino group is as follows. The case of 2 to 30 is preferable, and the case of 2 to 16 is more preferable, and examples thereof include acetylamino, propionylamino, benzoylamino, N-phenylacetylamino and 3,5-disulfobenzoylamino.

The carbamoylamino group represented by R ^{301 to} R ³⁰⁶ may be unsubstituted or substituted, and the total number of carbon atoms in the carbamoylamino group is preferably 1 to 30. It is more preferable that it is ˜16, and examples thereof include dimethylcarbamoylamino and phenylcarbamoylamino.

The sulfamoylamino group represented by R ^{301 to} R ³⁰⁶ may be unsubstituted or substituted, and the total number of carbon atoms of the sulfamoylamino group is 0 to 30. Is more preferable, and examples thereof include sulfamoylamino and N, N-dipropylsulfamoylamino.

The aliphatic oxycarbonylamino group represented by R ^{301 to} R ³⁰⁶ may be unsubstituted or substituted, may be saturated or unsaturated, and may be cyclic. The total number of carbon atoms of the group oxyamino group is preferably 1 to 30, more preferably 1 to 16, and examples thereof include methoxycarbonylamino and methoxyethoxycarbonylamino groups.

The aryloxycarbonylamino group represented by R ^{301 to} R ³⁰⁶ may be unsubstituted or substituted, and the total number of carbon atoms of the aryloxyamino group is 7 to 30. Is more preferable, and examples thereof include phenoxycarbonylamino and 3-chlorophenoxycarbonylamino.

The aliphatic sulfonylamino group represented by R ^{301 to} R ³⁰⁶ may be unsubstituted or substituted, may be saturated or unsaturated, may be cyclic, The total number of carbon atoms of the aliphatic sulfonylamino group is preferably 1-30, more preferably 1-16, such as methanesulfonylamino, N-phenylmethanesulfonylamino, benzenesulfonylamino, and 3 -Carboxybenzenesulfonylamino and the like.

The arylsulfonylamino group represented by R ^{301 to} R ³⁰⁶ may be unsubstituted or substituted, and the arylsulfonylamino group preferably has 6 to 30 total carbon atoms. 6 to 18 are more preferable, and examples thereof include benzenesulfonylamino and toluenesulfonamino.

The aliphatic thio group represented by R ^{301 to} R ³⁰⁶ may be unsubstituted or substituted, may be saturated or unsaturated, may be cyclic, and the aliphatic thio group The total number of carbon atoms in the group is preferably 1-30, more preferably 1-16, and examples include methylthio, (t) butylthio and ethoxyethylthio.

The arylthio group represented by R ^{301 to} R ³⁰⁶ may be unsubstituted or substituted, and the total number of carbon atoms of the arylthio group is preferably 6 to 30, preferably 6 to 18 Is more preferable, and examples thereof include phenylthio and 4-methylphenylthio.

As the heterocyclic thio group represented by R ^{301 to} R ³⁰⁶ , the heterocyclic moiety may be either saturated or unsaturated, unsubstituted or substituted, and the total of the heterocyclic oxy groups The number of carbon atoms is preferably 1-30, more preferably 1-15, such as 2-pyridylthio, 2-thienylthio, 2-thiazolylthio, 2-benzothiazolylthio, 2-benzoxazolylthio. And 2-furylthio.

The aliphatic sulfonyl group represented by R ^{301 to} R ³⁰⁶ may be unsubstituted or substituted, may be saturated or unsaturated, may be cyclic, and the aliphatic sulfonyl group. The total carbon number of the group is preferably 1-30, more preferably 1-16, and examples thereof include methanesulfonyl, methoxymethanesulfonyl and ethoxyethanesulfonyl.

The arylsulfonyl group represented by R ^{301 to} R ³⁰⁶ may be unsubstituted or substituted, and the total number of carbon atoms of the arylsulfonyl group is preferably 6 to 30, More preferably, it is -18, for example, benzenesulfonyl, toluenesulfonyl, etc. are mentioned.

The sulfamoyl group represented by R ^{301 to} R ³⁰⁶ may be unsubstituted or substituted, and the total number of carbon atoms of the sulfamoyl group is preferably 0 to 30, and preferably 0 to 16 Is more preferable, and examples thereof include sulfamoyl, dimethylsulfamoyl and di- (2-hydroxyethyl) sulfamoyl.
The imide group represented by R ^{301 to} R ³⁰⁶ may be unsubstituted or substituted, and is preferably a 5- to 6-membered imide group, preferably having a total carbon number of 4 to 30. 4 to 20 is more preferable, and examples thereof include succinimide and phthalimide.

Among the above, R ³⁰¹ and R ³⁰² are each independently a hydrogen atom, a halogen atom, an aliphatic group, an aliphatic oxy group, an aliphatic oxycarbonyl group, an aryloxycarbonyl, or the like in that the effects of the present invention can be effectively achieved. And a carbamoyl group is preferable, and an embodiment in which a 6-membered ring is formed together with carbon atoms bonded to R ³⁰¹ and R ³⁰² is more preferable.

Similarly, R ³⁰³ is preferably a hydrogen atom, a halogen atom, an aliphatic oxycarbonyl group, a carbamoyl group, an acylamino group, an aliphatic sulfonylamino group, or an arylsulfonylamino group in that the effect of the present invention can be effectively achieved. An embodiment that is an atom, a halogen atom, an acylamino group, an aliphatic sulfonylamino group, or an arylsulfonylamino group is more preferred, and an embodiment that is a hydrogen atom is most preferred.

Similarly, from the viewpoint that the effects of the present invention can be effectively achieved, an embodiment in which R ³⁰⁴ is a hydroxy group or an aliphatic oxy group is further preferred, and an embodiment in which a R group is a hydroxy group is most preferred.

Similarly, R ³⁰⁵ and R ³⁰⁶ are each independently a hydrogen atom, a halogen atom, an aliphatic group, an aliphatic oxy group, an aliphatic oxycarbonyl group, an aryloxy group in that the effects of the present invention can be effectively achieved. An embodiment that is a carbonyl group or a carbamoyl group is preferred, and an embodiment in which a 6-membered ring is formed together with the carbon atom is more preferred.

  From the viewpoint of more effectively achieving the effect of the present invention, among the dyes represented by the general formula (1), the dye represented by the general formula (2) is preferable.

In the general formula ^{(2), R 303} and ^{R 304} it is, are each synonymous with ^{R 303} and ^{R 304} in the general formula above (1). R ³⁰⁷ and R ³⁰⁸ each independently represent a substituent, and m and n each independently represent an integer of 0 to 4.
The substituent represented by R ³⁰⁷ and R ³⁰⁸ may be any group that can be substituted, and examples thereof include the same groups as the preferred substituents as R ^{301 to} R ³⁰⁶ in General Formula (1) described above. .
In the general formula (2), R ³⁰³ is preferably a hydrogen atom, a halogen atom, an aliphatic group, an aliphatic oxy group, an aliphatic oxycarbonyl group, an aryloxycarbonyl group, or a carbamoyl group. An embodiment that is an atom is more preferable, and an embodiment in which R ³⁰⁴ is a hydrogen atom, a hydroxy group, or an aliphatic oxy group is preferable, and an embodiment that is a hydroxy group is more preferable.

From the point that the effects of the present invention can be more effectively achieved, R ³⁰⁷ in the general formula (2) is a halogen atom, aliphatic group, aliphatic oxy group, aryloxy group, aliphatic oxycarbonyl group, aryloxycarbonyl group. , A carbamoyl group, an aliphatic sulfonyl group, an arylsulfonyl group, a sulfamoyl group, an aliphatic thio group, an arylthio group, an imide group, an acylamino group, and an aliphatic sulfonylamino group, preferably a halogen atom, an aliphatic group, an aliphatic group A more preferred embodiment is an oxycarbonyl group, a carbamoyl group, an aliphatic sulfonyl group, a sulfamoyl group, an aliphatic thio group, an imide group, an aliphatic carbonylamino group, or an aliphatic sulfonylamino group.
Similarly, from the viewpoint of the effect of the present invention, R ³⁰⁸ is a halogen atom, aliphatic group, aliphatic oxy group, aryloxy group, aliphatic oxycarbonyl group, aryloxycarbonyl group, carbamoyl group, aliphatic sulfonyl group, arylsulfonyl group. Group, sulfamoyl group, aliphatic thio group, arylthio group, and acylamino group, preferably a halogen atom, aliphatic group, aliphatic oxy group, aliphatic oxycarbonyl group, carbamoyl group, aliphatic thio group, arylthio group. Certain embodiments are more preferred.

Similarly, in the general effect (2), m is preferably 0 or 1, and n is 1 or 2 from the viewpoint of the effect of the present invention.
In the general formula (2), the R ³⁰³ is a hydrogen atom or a halogen atom, and the R ³⁰⁴ is a hydrogen atom, a hydroxy group or an aliphatic oxy group in that the effect of the present invention can be effectively achieved. R ³⁰⁷ is a halogen atom, aliphatic group, aliphatic oxy group, aryloxy group, aliphatic oxycarbonyl group, aryloxycarbonyl group, carbamoyl group, aliphatic sulfonyl group, arylsulfonyl group, sulfamoyl group, aliphatic thio group An arylthio group, wherein R ³⁰⁸ is a halogen atom, aliphatic group, aliphatic oxy group, aryloxy group, aliphatic oxycarbonyl group, aryloxycarbonyl group, carbamoyl group, aliphatic sulfonyl group, arylsulfonyl group, sulfamoyl A group, an aliphatic thio group, an arylthio group, an acylamino group, and m is 0 or 1 and n are preferably 1 or 2.

Furthermore, in view of the effects of the present invention, R ³⁰³ is a hydrogen atom or a halogen atom, R ³⁰⁴ is a hydroxy group, and R ³⁰⁷ is a halogen atom, an aliphatic group, an aliphatic oxycarbonyl group, a carbamoyl group. Group, aliphatic sulfonyl group, sulfamoyl group, aliphatic thio group, wherein R ³⁰⁸ is a halogen atom, aliphatic group, aliphatic oxy group, aryloxy group, aliphatic oxycarbonyl group, aryloxycarbonyl group, carbamoyl group , An aliphatic sulfonyl group, an arylsulfonyl group, a sulfamoyl group, an aliphatic thio group, an arylthio group, and an acylamino group, wherein m is 0 or 1, and n is 1 or 2.

Still further, in terms of the effects of the present invention, R ³⁰³ is a hydrogen atom, R ³⁰⁴ is a hydroxy group, and R ³⁰⁷ is a halogen atom, an aliphatic group, an aliphatic oxycarbonyl group, a carbamoyl group, an aliphatic group. An aromatic sulfonyl group, a sulfamoyl group, and an aliphatic thio group, wherein R ³⁰⁸ is a halogen atom, an aliphatic group, an aliphatic oxy group, an aliphatic oxycarbonyl group, a carbamoyl group, an aliphatic sulfonyl group, a sulfamoyl group, an aliphatic thio group. And an arylthio group in which m is 0 or 1, and n is 1 or 2.

  Specific examples (example compounds (1) to (48)) of the dye monomer represented by the general formula (P) are shown below, but the dye monomer used in the present invention is the following example. It is not limited to.

  The method for synthesizing the dye monomer in the present invention is in accordance with the method for synthesizing the dye of the general formula (1) described in JP-B-7-49583 and the dye of the general formula (1) described in JP-B-5-5257. Can be synthesized.

[Colorless monomer having an ethylenic double bond]
Next, as a colorless monomer having an ethylenic double bond, acrylic acid, α-chloroacrylic acid, α-alkylacrylic acid (for example, methacrylic acid), β-alkylacrylic acid (for example, crotonic acid), etc. (Meth) acrylic acids and salts, esters or amides derived therefrom (for example, acrylamide, methacrylamide, t-butylacrylamide, 2-acrylamide-2-methylpropanesulfonic acid, 2-acrylamide-2- Sodium methylpropanesulfonate, sodium 3-acryloyloxypropanesulfonate, methyl acrylate, methyl methacrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, t-butyl acrylate, n-butyl methacrylate Rate, 2-ethylhexyl acrylate, n-hexyl acrylate, n-octyl acrylate, glycidyl methacrylate, and methylene bisacrylamide, etc.), maleic acid, fumaric acid, itaconic acid, vinyl esters (eg, vinyl acetate, vinyl propionate, and Vinyl laurate, etc.), acrylonitrile, methacrylonitrile, aromatic vinyl compounds (eg, styrene and styrene derivatives (eg, potassium styrenesulfinate, sodium styrenesulfonate, etc.)), vinylidene chloride, vinyl alkyl ether (eg, vinylethyl) Ether), maleic acid ester, N-vinyl-2-pyrrolidone, N-vinylpyridine, 2- and 4-vinylpyridine, etc. It may be Irotan monomer.
From the standpoint of more effectively achieving the effects of the present invention, colorless monomers having an ethylenic double bond are acrylic acids, methacrylic acids, acrylic esters, methacrylic esters, acrylamides, styrene and styrene derivatives. Furthermore, acrylic acid, methacrylic acid, acrylic acid ester, methacrylic acid ester, acrylamide, styrene, and styrene derivatives containing a water-soluble group such as a hydroxy group, a carboxyl group, and a sulfo group are more preferable.
Specifically, methyl acrylate, methacrylic acid, crotonic acid, acrylic acid, styrene, t-butylacrylamide, acrylamide, potassium styrenesulfinate, sodium styrenesulfonate, sodium 2-acrylamido-2-methylpropanesulfonate, 3- More preferred is sodium acryloyloxypropane sulfonate.

The polymer dye used in the present invention may be water-soluble or water-insoluble, and the water-soluble group may be a dye monomer or a colorless monomer having an ethylenic double bond. Well, you can be in both. From the viewpoint of more effectively achieving the effects of the present invention, those having a hydrophilic group in the polymer dye of the present invention are preferred. For example, phosphoric acid sites, phosphate ester sites, quaternary ammonium salt sites, ethyleneoxy chains, propyleneoxy It is more preferably a site of a chain, a hydroxy group, a carboxylic acid, a sulfonic acid or a salt thereof, and a site of an ethyleneoxy chain, a propyleneoxy chain, a hydroxy group, a carboxylic acid, a sulfonic acid or a salt thereof.
As the polymer dye used in the present invention, one kind of dye monomer represented by the general formula (P) may be used, two or more kinds may be used, and other ethylenic double bonds may be used. You may use with the polymerizable group containing dye monomer which has. One kind of colorless monomer having an ethylenic double bond may be used, or two or more kinds may be used.
Hereinafter, specific examples (Exemplary Compounds P-1 to P-46) of the dyes according to the present invention are shown in Tables 1 to 3. However, the present invention is not limited to these.

＊略称
ＭＡＡ：メタクリル酸
ＡＡ：アクリル酸
ＳＳＫ：スチレンスルフィン酸カリウム
ＳＳＮ：スチレンスルホン酸ナトリウム
ＡＭＰＳＮ：２−アクリルアミド−２−メチルプロパンスルホン酸ナトリウム

* Abbreviations MAA: Methacrylic acid AA: Acrylic acid SSK: Potassium styrenesulfinate SSN: Sodium styrenesulfonate AMPSN: Sodium 2-acrylamido-2-methylpropanesulfonate

＊略称
ＭＡ：メチルアクリレート
ＭＡＡ：メタクリル酸
ＣＡ：クロトン酸
ＡＡ：アクリル酸
Ｓｔ：スチレン
ｔ−ＢＡＭ：ｔ−ブチルアクリルアミド
ＡＡＭ：アクリルアミド
ＳＳＫ：スチレンスルフィン酸カリウム
ＳＳＮ：スチレンスルホン酸ナトリウム
ＡＭＰＳＮ：２−アクリルアミド−２−メチルプロパンスルホン酸ナトリウム
ＡＰＳＮ：３−アクリロイルオキシプロパンスルホン酸ナトリウム

* Abbreviations MA: methyl acrylate MAA: methacrylic acid CA: crotonic acid AA: acrylic acid St: styrene t-BAM: t-butylacrylamide AAM: acrylamide SSK: potassium styrenesulfinate SSN: sodium styrenesulfonate AMPSN: 2-acrylamide- Sodium 2-methylpropanesulfonate APSN: Sodium 3-acryloyloxypropanesulfonate

＊略称
ＭＡ：メチルアクリレート
ＡＡ：アクリル酸

* Abbreviation MA: Methyl acrylate AA: Acrylic acid

The method of synthesizing the polymer dye used in the present invention is to be synthesized according to the method described in US Pat. No. 3,451,820, JP-A-62-276548, JP-A-60-218646, etc. Can do.
The proportion of the dye portion incorporated in the polymer dye used in the present invention is preferably 2 to 100% by mass, more preferably 15 to 90% by mass from the viewpoint of more effectively achieving the effects of the present invention, 30 The case where it is -90 mass% is especially preferable.
As a mass average molecular weight (polystyrene conversion value measured by GPC method) of the polymer dye used in the present invention, 1 × 10 ³ to 2 × 10 ⁵ is preferable, and a polymer of 2 × 10 ³ to 1 × 10 ⁵ is used. Is more preferable, and 3 × 10 ^{3 to} 5 × 10 ⁴ is particularly preferable.
The total concentration of the polymer dye according to the present invention in the colored curable composition varies depending on the molecular weight and molar extinction coefficient, but is preferably 0.5 to 80% by mass based on the total solid components of the composition. 5 to 70% by mass is more preferable, and 1 to 70% by mass is particularly preferable.

  When the polymer dye is at least one copolymer of at least one dye monomer represented by the general formula (P) and a colorless monomer having at least one ethylenic double bond, The molar ratio is preferably 5: 1 to 1:20, more preferably 4.5: 1 to 1:10.

〔binder〕
The colored curable composition of the present invention can contain at least one binder. The binder according to the present invention is not particularly limited as long as it is alkali-soluble, but is preferably selected from the viewpoints of heat fastness, developability, availability, and the like.
The alkali-soluble binder is preferably a linear organic polymer, soluble in an organic solvent, and developable with a weak alkaline aqueous solution. Examples of such linear organic high molecular polymers include polymers having a carboxylic acid in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, and JP-B-54-. Methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid as described in the specifications of No. 25957, JP-A-59-53836, JP-A-59-71048, etc. There are a copolymer, a maleic acid copolymer, a partially esterified maleic acid copolymer, and the like. Similarly, an acidic cellulose derivative having a carboxylic acid in the side chain is useful. In addition to this, an acid anhydride added to a polymer having a hydroxyl group, a polyhydroxystyrene resin, a polysiloxane resin, poly (2-hydroxyethyl (meth) acrylate), polyvinylpyrrolidone, polyethylene oxide, polyvinyl alcohol, etc. Is also useful.
In addition, a monomer having a hydrophilic group may be copolymerized. Examples thereof include alkoxyalkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, glycerol (meth) acrylate, (meth) acrylamide, and N-methylolacrylamide. Secondary and tertiary alkylacrylamides, dialkylaminoalkyl (meth) acrylates, morpholino (meth) acrylates, N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, vinyltriazole, methyl (meth) acrylate, ethyl (meth) Examples include acrylate, branched or linear propyl (meth) acrylate, branched or linear butyl (meth) acrylate, phenoxyhydroxypropyl (meth) acrylate, and the like.
In addition to the above, the monomer having a hydrophilic group includes a tetrahydrofurfuryl group, a phosphoric acid moiety, a phosphoric acid ester moiety, a quaternary ammonium salt moiety, an ethyleneoxy chain, a propyleneoxy chain, a sulfonic acid or its salt moiety, a morpholinylethyl group, etc. Including monomers are also useful.

From the viewpoint of improving the crosslinking efficiency, a polymer having a polymerizable group in the side chain and a polymer containing an allyl group, a (meth) acryl group, an allyloxyalkyl group or the like in the side chain is also useful. .
Examples of the polymer having these polymerizable groups include KS resist-106 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), cyclomer P series (manufactured by Daicel Chemical Industries, Ltd.), and the like.
In order to increase the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are also useful.
Of the various binders described above, from the viewpoint of heat fastness, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferable, and from the viewpoint of control of developability. Then, an acrylic resin, an acrylamide resin, and an acrylic / acrylamide copolymer resin are preferable. Examples of the acrylic resin include a copolymer composed of monomers selected from benzyl (meth) acrylate, (meth) acryl, hydroxyethyl (meth) acrylate, (meth) acrylamide, and the like, and KS-resist-106 (Osaka Organic Chemical). Industrial Co., Ltd.) and Cyclomer P-series (Daicel Chemical Industries, Ltd.) are preferred.
Moreover, an alkali-soluble phenol resin can be used as a binder used for this invention. The alkali-soluble phenol resin can be suitably used when the colored curable composition of the present invention is configured as a positive type, and examples thereof include novolak resins and vinyl polymers.

Examples of the novolak resin include those obtained by condensing phenols and aldehydes in the presence of an acid catalyst. Examples of phenols include phenol, cresol, ethylphenol, butylphenol, xylenol, phenylphenol, catechol, resorcinol, pyrogallol, naphthol, and bisphenol A. Phenols can be used alone or in combination of two or more.
Examples of aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, or benzaldehyde.
Specific examples of the novolak resin include, for example, a condensation product of metacresol, paracresol or a mixture thereof and formalin. The novolak resin may be adjusted in molecular weight distribution using means such as fractionation. Moreover, you may mix the low molecular weight component which has phenolic hydroxyl groups, such as bisphenol C and bisphenol A, with the said novolak resin.
The binder is preferably a polymer having a mass average molecular weight (polystyrene equivalent value measured by GPC method) of 1 × 10 ³ to 2 × 10 ⁵ , more preferably a polymer of 2 × 10 ³ to 1 × 10 ⁵ , A polymer of 5 × 10 ^{3 to} 5 × 10 ⁴ is particularly preferred.

  As content in the colored curable composition of this invention of a binder, 0-90 mass% is preferable with respect to the total solid in this composition, and 0-70 mass% is still more preferable. 0-60 mass% is especially preferable.

[Crosslinking agent]
The present invention uses the dye according to the present invention described above, and the curing reaction of the film proceeds to a higher degree than before, and a film having good curability can be obtained. It is also possible to obtain a more highly cured film using an agent. This is useful from the viewpoint of achieving high resolution of the colored curable composition of the present invention.
The crosslinking agent that can be used in the present invention is not particularly limited as long as the film can be cured by a crosslinking reaction. For example, (a) an epoxy resin, (b) a methylol group, an alkoxymethyl group, and an acyloxymethyl group. Substitution with at least one group selected from melamine compound, guanamine compound, glycoluril compound, or urea compound substituted with at least one selected group, (c) methylol group, alkoxymethyl group, and acyloxymethyl group Phenolic compounds, naphthol compounds or hydroxyanthracene compounds produced. Of these, polyfunctional epoxy resins are particularly preferred.

  The (a) epoxy resin may be any epoxy resin having an epoxy group and crosslinkability. For example, bisphenol A-glycidyl ether, ethylene glycol diglycidyl ether, ethylene glycol diglycidyl ether, butanediol Divalent glycidyl group-containing low molecular weight compounds such as diglycidyl ether, hexanediol diglycidyl ether, dihydroxybiphenyl diglycidyl ether, diglycidyl phthalate, and N, N-diglycidylaniline, as well as trimethylolpropane triglycidyl Trivalent glycidyl group-containing low molecular weight compounds represented by ether, trimethylolphenol triglycidyl ether, TrisP-PA triglycidyl ether, etc., as well as pentaerythritol tetraglycol Tetravalent glycidyl group-containing low molecular weight compounds typified by dil ether, tetramethylol bisphenol-A-tetraglycidyl ether and the like, as well as polyvalent glycidyl groups such as dipentaerythritol pentaglycidyl ether and dipentaerythritol hexaglycidyl ether Low molecular weight compounds, polyglycidyl (meth) acrylate, 2,2-bis (hydroxymethyl) -1-butanol 1,2-epoxy-4- (2-oxiranyl) cyclohexane adducts and the like containing glycidyl groups Examples thereof include molecular compounds.

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

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

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

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

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

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

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

  The number of methylol groups, acyloxymethyl groups or alkoxymethyl groups contained in the crosslinking agent (c) component is at least 2 per molecule, and from the viewpoint of thermal crosslinkability and storage stability, A compound in which all of the 2- and 4-positions are substituted is preferred. In addition, the naphthol compound and hydroxyanthracene compound as the skeleton are preferably compounds in which all of the ortho-position and para-position of the OH group are substituted.

  The 3-position or 5-position of the phenolic compound that serves as the skeleton may be unsubstituted or may have a substituent. Also in the naphthol compound, other than the ortho position of the OH group may be unsubstituted or may have a substituent.

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

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

  Specific examples of the crosslinking agent (c) include, for example, trimethylolphenol, tri (methoxymethyl) phenol, a compound obtained by methoxymethylating one or two methylol groups of trimethylolphenol, trimethylol-3-cresol, Tri (methoxymethyl) -3-cresol, a compound obtained by methoxymethylating one or two methylol groups of trimethylol-3-cresol, dimethylolcresol such as 2,6-dimethylol-4-cresol, tetramethylolbisphenol- A, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethoxymethyl bisphenol-A and tetramethylol bisphenol-A, tetramethylol-4,4_-bishydroxybiphenyl, tetramethoxymethyl-4,4_-bishydroxy Biff Cycloalkenyl, hexamethylol of Tris P-PA, hexamethoxymethyl of Tris P-PA, compounds in which 1 to 5 methylol groups have been methoxymethylated hexamethylol of Tris P-PA, there is bishydroxymethyl naphthalene diol.

Examples of the hydroxyanthracene compound include 1,6-dihydroxymethyl-2,7-dihydroxyanthracene.
Examples of the acyloxymethyl group-containing compound include compounds obtained by partially or fully acyloxymethylating the methylol group of the methylol group-containing compound.

  Among these compounds, trimethylol phenol, bishydroxymethyl-p-cresol, tetramethylol bisphenol A, hexamethylol body of TrisP-PA (manufactured by Honshu Chemical Industry Co., Ltd.) or their methylol group is alkoxy. Mention may be made of phenolic compounds substituted with both methyl and methylol groups and alkoxymethyl groups. These compounds according to (c) may be used alone or in combination.

  When it contains a crosslinking agent in the present invention, the total content of the curable compositions (a) to (c) in the colored curable composition varies depending on the material, but is 1 for the solid content of the composition. -70 mass% is preferable, 5-50 mass% is more preferable, 7-30 mass% is especially preferable.

(Polymerizable monomer)
The colored curable composition of this invention can be comprised suitably by containing at least 1 sort (s) of a polymerizable monomer. The polymerizable monomer is mainly contained when the colored curable composition is constituted as a negative type. In addition, it can further contain in the positive type | system | group containing the below-mentioned naphthoquinone diazide compound with the below-mentioned photoinitiator, and in this case, the hardening degree of the pattern formed can be promoted more.
This polymerizable monomer is useful in that it can achieve high sensitivity and high resolution of the colored curable composition of the present invention by using it together with a photopolymerization initiator described later. Hereinafter, the polymerizable monomer will be described.
As the polymerizable monomer, a compound having an ethylenically unsaturated group having a boiling point of 100 ° C. or higher under normal pressure is preferable. Examples thereof include polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxy Monofunctional acrylates and methacrylates such as ethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, Pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate Trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, polymethic alcohol such as glycerin and trimethylolethane, and then (meth) acrylated after adding ethylene oxide or propylene oxide, Urethane acrylates as described in JP-B-48-41708, JP-B-50-6034, JP-A-51-37193, JP-A-48-64183, JP-B-49-43191, Polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid, and mixtures thereof described in JP-B 52-30490 Can do.

Furthermore, the Japan Adhesion Association Vol. 20, no. 7, pages 300 to 308 are introduced as photocurable monomers and oligomers.
As content in the colored curable composition of the said polymerizable monomer, 0.1-90 mass% is preferable with respect to solid content of this composition, 1.0-80 mass% is more preferable, 2.0 -70 mass% is especially preferable.

[Radiosensitive compounds]
The colored curable composition of this invention can be comprised suitably by containing at least 1 sort (s) of a radiation sensitive compound. The radiation-sensitive compound according to the present invention is a compound that can cause a chemical reaction such as generation of a radical, generation of an acid, generation of a base with respect to radiation such as UV, Deep UV, visible light, infrared light, and electron beam. The coating film is alkali-developed by insolubilizing the above-mentioned alkali-soluble resin by reactions such as crosslinking, polymerization, decomposition of acidic groups, polymerization of polymerizable monomers and oligomers coexisting in the coating film, crosslinking of the crosslinking agent, etc. It is used for the purpose of making it insoluble in liquid.
This radiation sensitive compound is useful from the viewpoint of achieving high sensitivity and high resolution of the colored curable composition of the present invention.
When the colored curable composition is configured as a negative type, it contains a photopolymerization initiator, and when it is configured as a positive type, it contains a naphthoquinone diazide compound as an essential component.

(Photopolymerization initiator, etc.)
First, a photopolymerization initiator used in the case of forming a negative type will be described. The photopolymerization initiator is not particularly limited as long as it can cause the polymerization monomer (a monomer having a polymerizable group) to undergo a polymerization reaction, but is selected from the viewpoints of characteristics, initiation efficiency, absorption wavelength, availability, cost, and the like. It is preferable. In addition, you may further contain in the positive type | system | group containing a naphthoquinone diazide compound, In this case, the hardening degree of the pattern formed can be promoted more.
Examples of the photopolymerization initiator include at least one active halogen compound selected from a halomethyloxadiazole compound and a halomethyl-s-triazine compound, a 3-aryl-substituted coumarin compound, a lophine dimer, a benzophenone compound, an acetophenone compound, and the like. Examples thereof include cyclopentadiene-benzene-iron complexes and salts thereof, and oxime compounds.

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

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

Other specific examples include 2,4-bis (trichloromethyl) -6-p-methoxystyryl-s-triazine, 2,6-bis (trichloromethyl) -4- (3,4-methylenedioxyphenyl) -1,3,5-triazine, 2,6-bis (trichloromethyl) -4- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (1 -P-dimethylaminophenyl-1,3-butadienyl) -s-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyryl-s-triazine, 2- (naphth-1-yl) -4, 6-bis-trichloromethyl-s-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine,
2- (4-Ethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-butoxy-naphth-1-yl) -4,6-bis-trichloromethyl- s-triazine, 2- [4- (2-methoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2-ethoxyethyl) -naphtho 1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2-butoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- (2-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-methoxy-5-methyl-naphth-2-yl) -4,6-bis -Trichloromethyl-s-triazi 2- (6-methoxy-naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (5-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl -S-triazine, 2- (4,7-dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-ethoxy-naphth-2-yl) -4, 6-bis-trichloromethyl-s-triazine, 2- (4,5-dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 4- [p-N, N-di (Ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-methyl-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6- Di (Trik (Romethyl) -s-triazine, 4- [p-N, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-methyl-pN, N -Di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (p-N-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (p-N-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- [p-N, N-di (phenyl) aminophenyl] -2,6-di (Trichloromethyl) -s-triazine, 4- (pN-chloroethylcarbonylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- [pN- (p-methoxy) Ciphenyl) carbonylaminophenyl] 2,6-di (trichloromethyl) -s-triazine, 4- [m-N, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s -Triazine, 4- [m-bromo-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine,

4- [m-chloro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-fluoro-pN, N- Di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-bromo-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6 -Di (trichloromethyl) -s-triazine, 4- [o-chloro-pN, N-di (ethoxycarbonylmethyl) aminophenyl-2,6-di (trichloromethyl) -s-triazine, 4- [ o-Fluoro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-bromo-pN, N-di (chloro) Ethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-chloro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -S-triazine, 4- [o-fluoro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-bromo-pN , N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-chloro-pN, N-di (chloroethyl) aminophenyl] -2,6- Di (trichloromethyl) -s-triazine, 4- [m-fluoro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (m- Bromo-p N-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-chloro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -S-triazine, 4- (m-fluoro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN-ethoxycarbonyl) Methylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-chloro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine 4- (o-fluoro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-tri Azine, 4- (m-bromo-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-chloro-pN-chloroethylaminophenyl)- 2,6-di (trichloromethyl) -s-triazine, 4- (m-fluoro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o- Bromo-p-N-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-chloro-pN-chloroethylaminophenyl) -2,6-di (trichloro Methyl) -s-triazine, 4- (o-fluoro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, and the like.

  In addition, TAZ series, TAZ-107, TAZ-110, TAZ-104, TAZ-109, TAZ-140, TAZ-204, TAZ-113, TAZ-123, TAZ-104, PANCHIM T series manufactured by Midori Chemical , T-OMS, T-BMP, TR, T-B, Ciba Specialty Chemicals Irgacure series, Irgacure 369, Irgacure 784, Irgacure 651, Irgacure 184, Irgacure 500, Irgacure 1000, Irgacure 149, Irgacure 819, Irgacure 261, Darocur Series, Darocur 1173, 4,4-bis (diethylamino) -benzophenone, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octane ON, 2-benzyl-2-dimethylamino-4-morpholinobutyrophenone, 2,2-dimethoxy-2-phenylacetophenone, 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o -Fluorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazolyl dimer 2-mer, 2- (p-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-methylmercapto Phenyl) -4,5-diphenylimidazolyl dimer, benzoin isopropyl ether and the like are also usefully used.

  Other known photopolymerization initiators other than the photopolymerization initiator can be used in combination with the colored curable composition of the present invention. Specifically, the vicinal polyketol aldonyl compound described in U.S. Pat. No. 2,367,660, the α-form described in U.S. Pat. Nos. 2,367,661 and 2,367,670. Carbonyl compounds, acyloin ethers described in US Pat. No. 2,448,828, aryl acyloin compounds substituted with α-hydrocarbons described in US Pat. No. 2,722,512, US Pat. , 046,127 and 2,951,758, a triarylimidazole dimer / P-aminophenylketone combination described in US Pat. No. 3,549,367, Examples include benzothiazole compounds / trihalomethyl-s-triazine compounds described in JP-B 51-48516.

  The content of the photopolymerization initiator in the colored curable composition is preferably 0.01 to 50% by mass, more preferably 1 to 30% by mass, based on the solid content (mass) of the polymerizable monomer. -20% by weight is particularly preferred. When the content is less than 0.01% by mass, the polymerization may be difficult to proceed. When the content exceeds 50% by mass, the polymerization rate is increased, but the molecular weight is decreased and the film strength may be decreased.

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

  In addition to the above, it is preferable to add a thermal polymerization inhibitor. For example, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4, 4-thiobis (3-methyl-6-tert-butylphenol), 2,2-methylenebis (4-methyl-6-tert-butylphenol), 2-mercaptobenzimidazole and the like are useful.

(Naphthoquinonediazide compound)
Next, the naphthoquinone diazide compound used in the case of constituting the positive type will be described. A naphthoquinonediazide compound is a compound having at least one o-quinonediazide, such as o-naphthoquinonediazide-5-sulfonic acid ester, o-naphthoquinonediazide-5-sulfonic acid amide, o-naphthoquinonediazide-4-sulfone Acid ester, o-naphthoquinonediazide-4-sulfonic acid amide, and the like. These esters and amide compounds can be produced by a known method using, for example, the phenol compound described in the general formula (I) in JP-A-2-84650 and JP-A-3-49437. .

  When the colored curable composition is constituted as a positive type, the binder and the crosslinking agent are usually dissolved in an organic solvent at a ratio of about 2 to 50% by mass and 2 to 30% by mass, respectively. Is preferred. The contents of the naphthoquinone diazide compound and the dye are usually added at a ratio of about 2 to 30% by mass and 2 to 50% by mass with respect to the mass of the solution in which the binder and the crosslinking agent are dissolved. Is preferred.

〔solvent〕
In preparing the colored curable composition of the present invention, a solvent can generally be contained. The solvent is basically not particularly limited as long as the solubility of each component and the coating property of the colored curable composition are satisfied, but it is particularly preferable to select the solvent in consideration of the solubility, coating property and safety of the binder.
Specific examples of the solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, and lactic acid. Methyl, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate and the like;

3-oxypropionic acid alkyl esters such as methyl 3-oxypropionate and ethyl 3-oxypropionate, such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropionate Ethyl 2-oxypropionate, alkyl 2-oxypropionate such as methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, Propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, 2-methoxy-2-methyl Propionate Le, 2-ethoxy-2-methylpropionic acid ethyl, and the like; methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl and 2-oxobutanoate;

Ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether, propylene glycol monomethyl ether Acetates, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate and the like; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone and 3-heptanone; aromatic hydrocarbons such as toluene and xylene are preferred.

  Among the above, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl Carbitol acetate, propylene glycol methyl ether, propylene glycol monomethyl ether acetate and the like are more preferable.

[Various additives]
In the colored curable composition of the present invention, various additives as necessary, for example, fillers, polymer compounds other than the above, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation agents, etc. Can be blended.

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

Further, when the alkali solubility of the non-cured part is promoted and the developability of the colored curable composition of the present invention is further improved, the composition has an organic carboxylic acid, preferably a low molecular weight having a molecular weight of 1000 or less. An organic carboxylic acid can be added.
Specifically, aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid; oxalic acid, malonic acid, succinic acid, glutar Aliphatic dicarboxylic acids such as acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid; Aliphatic tricarboxylic acids such as carbaryl acid, aconitic acid, and camphoronic acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, and mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesin Aromatic polycarboxylic acids such as acid, merophanic acid, pyromellitic acid; phenylacetic acid, Doroatoropa acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetic acid, coumaric acid, other carboxylic acids such as umbellic acid.

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

<Color filter and manufacturing method thereof>
Next, the color filter of the present invention will be described in detail through its manufacturing method.
In the method for producing a color filter of the present invention, the above-described colored curable composition of the present invention is used. The color filter of the present invention uses the above-described colored curable composition of the present invention, and this colored curable composition is applied to a support by a coating method such as spin coating, cast coating, roll coating, etc. It can be most suitably prepared by forming a radiation composition layer, exposing the layer through a predetermined mask pattern, and developing with a developer to form a negative or positive colored pattern. it can. (Image Forming Step) At this time, if necessary, a curing step for curing the formed colored pattern by heating and / or exposure can be provided. As light or radiation used at this time, ultraviolet rays such as g-line, h-line and i-line are particularly preferably used. Further, when the colored curable composition is configured as a positive type, a step of post-baking the colored pattern after the image forming step can be provided.
When producing a color filter, in the case of a negative type, the image forming step (and curing step if necessary) is repeated according to the desired number of hues, and in the case of a positive type, the image forming step and post-baking are desired. By repeating according to the hue, it is possible to produce a color filter having a desired number of hues.

  As the support, for example, soda glass, Pyrex (registered trademark) glass, quartz glass used for liquid crystal display elements and the like, and a transparent conductive film attached thereto, a photoelectric conversion element substrate used for an imaging element, For example, a silicon substrate, a complementary metal oxide semiconductor (CMOS), or the like can be given. These substrates may have black stripes that separate pixels.

  Further, if necessary, an undercoat layer may be provided on these supports in order to improve adhesion to the upper layer, prevent diffusion of substances, or flatten the substrate surface.

  As the developer used in the method for producing the color filter of the present invention, a part to be developed and removed of the colored curable composition of the present invention (for example, an uncured part in the case of a negative type) is dissolved, and a filter is formed. Any hardened part can be used as long as it has a composition that does not dissolve. Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used.

  As said organic solvent, the above-mentioned solvent used when preparing the colored curable composition of this invention is mentioned.

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

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

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples as long as the gist thereof is not exceeded. Unless otherwise specified, “part” is based on mass.
Example 1
1) Preparation of resist solution A (negative type)
Propylene glycol monomethyl ether acetate (PGMEA) ... 5.20 partsCyclohexanone ... 52.6 partsBinder ... 30.5 parts (benzyl methacrylate / methacrylic acid / -2-hydroxyethyl methacrylate) Copolymer (molar ratio = 60: 20: 20) 41% cyclohexanone solution, dipentaerythritol hexaacrylate 10.2 parts, polymerization inhibitor (p-methoxyphenol) 0.006 parts, fluorine-based Surfactant: 0.80 part (trade name: F-475, manufactured by Dainippon Ink & Chemicals, Inc.)
-Photopolymerization initiator TAZ-107 (manufactured by Midori Chemical Co., Ltd.) 0.58 part was mixed and dissolved to prepare a resist solution A.

2) Production of glass substrate with undercoat layer A glass substrate (Corning 1737) was ultrasonically washed with 0.5% NaOH water, and then washed with water and dehydrated (200 ° C./20 minutes).
Next, the resist solution A obtained in 1) above was applied on a cleaned glass substrate using a spin coater so as to have a film thickness of 2 μm, and dried by heating at 220 ° C. for 1 hour to prepare a cured film (undercoat layer). did.

3) Preparation of resist solution B (negative type)
Propylene glycol monomethyl ether acetate (PGMEA) ... 5.20 parts Cyclohexanone ... 64.6 parts Binder ... 10.2 parts (benzyl methacrylate / methacrylic acid / -2-hydroxyethyl methacrylate) Copolymer (molar ratio = 60: 20: 20) 41% cyclohexanone solution / dipentaerythritol hexaacrylate 18.5 parts polymerization inhibitor (p-methoxyphenol) 0.006 parts fluorine-based Surfactant: 0.80 part (trade name: F-475, manufactured by Dainippon Ink & Chemicals, Inc.)
-Photopolymerization initiator TAZ-107 (manufactured by Midori Chemical Co., Ltd.) 0.58 part was mixed and dissolved to prepare a resist solution B.

4) Preparation of dye resist solution (colored curable composition [negative type]) 9.4 g of resist solution B obtained in 3) above and the exemplified compound (P-1) described above which is a dye according to the present invention (above-mentioned A dye monomer represented by the general formula (P) and a copolymer of a colorless monomer having an ethylenic bond (1.20 g) are mixed and dissolved to obtain a dye resist solution (colored curable composition [negative] Type] solution).

5) Exposure and development of resist (image formation)
The dye resist solution obtained in 4) above was applied on the undercoat layer of the glass substrate with the undercoat layer obtained in 2) above using a spin coater so as to have a film thickness of 1.0 μm. Pre-baked for 120 seconds.
Next, using an exposure apparatus, the coating film was irradiated with an exposure dose of 500 mJ / cm ² through a mask having a wavelength of 365 nm and a line width of 20 μm. After the exposure, development was performed using a developer CD-2000 (manufactured by FUJIFILM Electromaterials) at 25 ° C. for 40 seconds. Then, after rinsing with running water for 30 seconds, spray drying was performed. Thereafter, post-baking was performed at 200 ° C. for 15 minutes.
As described above, a pattern suitable as a yellow color constituting the color filter was obtained.

6) Evaluation The storage stability of the dye resist solution prepared above over time and the heat fastness, light fastness and solvent resistance of the coating film coated on the glass substrate using the dye resist solution are as follows. Evaluation was performed as described above. The evaluation results are shown in Table 4 below.

[Storage stability over time]
After the dye resist solution was stored at room temperature for 1 month, the degree of precipitation of foreign matters in the solution was visually evaluated according to the following criteria.
-Criteria-
○: No precipitation was observed Δ: Slight precipitation was observed ×: Precipitation was observed

[Thermal fastness]
The glass substrate coated with the dye resist solution is placed on a hot plate at 200 ° C. so as to be in contact with the substrate surface, heated for 1 hour, and then heated with a chromaticity meter MCPD-1000 (manufactured by Otsuka Electronics). The color difference (ΔEab value) was measured as an index for evaluating thermal fastness and evaluated according to the following criteria. A smaller ΔEab value indicates better heat fastness.
-Criteria-
○: ΔEab value <5
Δ: 5 ≦ ΔEab value ≦ 10
×: ΔEab value> 10

(Light fastness)
After irradiating a glass substrate coated with a dye resist solution with a xenon lamp at 50,000 lux for 20 hours (equivalent to 1 million lux · h), the color difference (ΔEab value) before and after irradiation is measured to increase light fastness. As an index to be evaluated, evaluation was performed according to the following criteria.
A smaller ΔEab value indicates better light fastness.
-Criteria-
○: ΔEab value <3
Δ: 3 ≦ ΔEab value ≦ 10
×: ΔEab value> 10

[Solvent resistance]
The spectra of the various coating films after post-baking obtained in 5) above were measured (spectrum A). On this coating film, the resist solution A obtained in 1) above was applied so as to have a film thickness of 1 μm and prebaked, and then a CD-2000 (manufactured by Fuji Film Electromaterials) developer was added. Development was performed under the conditions of 23 ° C. and 120 seconds, and the spectrum was measured again (spectrum B). The dye residual ratio (%) was calculated from the difference between the spectra A and B, and this was used as an index for evaluating the solvent resistance. This value indicates that the closer to 100%, the better the solvent resistance.

(Examples 2 to 10)
Example 1 4) In the preparation of the dye resist solution, a pattern was formed in the same manner as in Example 1 except that the dye according to the present invention and the resist solution were changed as shown in Table 4 below (but with equal weight). Further, the same evaluation was performed. The evaluation results are shown in Table 4 below.
The resist solution C in the table is as follows.

Preparation of resist solution C (negative type)
Propylene glycol monomethyl ether acetate (PGMEA) ... 5.20 partsCyclohexanone ... 52.6 partsDipentaerythritol hexaacrylate ... 20.2 partsPolymerization inhibitor (p-methoxyphenol)・ 0.006 parts ・ Fluorosurfactant 0.80 parts (trade name: F-475, manufactured by Dainippon Ink & Chemicals, Inc.)
-Photopolymerization initiator TAZ-107 (manufactured by Midori Chemical Co., Ltd.)... 0.68 part was mixed and dissolved to prepare a resist solution C.

(Comparative Examples 1-2)
In the preparation of the dye resist solution of Example 1 4), the dye according to the present invention was changed to the following comparative dye 1 (Comparative Example 1) or comparative dye 2 (Comparative Example 2) (but equal weight), and the resist solution was further changed. A pattern was formed in the same manner as in Example 1 except that the changes were made as shown in Table 4, and the same evaluation was performed. The evaluation results are shown in Table 4 below together with the results of the examples.

  As shown in Table 4, in the examples using the dyes according to the present invention, the dye resist solution (colored curable composition) prepared in a solution state was higher than in the comparative examples using other dyes. In addition, the storage stability over time was excellent, and the pattern formed using this colored curable composition exhibited good heat fastness, light fastness, and solvent resistance.

(Comparative dye 1)
C i Solvent Yellow 162

(Comparative dye 2)
C eye solvent yellow 82

(Example 11)
-Preparation of colored curable composition [positive type]-
The following composition was mixed and dissolved to prepare a solution-like colored curable composition [positive type].
・ Ethyl lactate (EL): 30 parts ・ Resin P-1: 3.0 parts ・ Naphthoquinone diazide compound N-1: 1.8 parts ・ Hexamethoxymethylolated melamine (crosslinking agent) 0.6 parts TAZ-107 (manufactured by Midori Chemical Co .; photoacid generator) ... 1.2 parts F-475 0.0005 parts (Dainippon Ink Chemical Co., Ltd .; fluorine-based) Surfactant)
-Illustrative compound of dye according to the present invention (P-1) 1.5 parts

-Synthesis of Resin P-1-
A three-necked flask was charged with 70.0 g of benzyl methacrylate, 13.0 g of methacrylic acid, 17.0 g of methacrylic acid-2-hydroxyethyl, and 600 g of 2-methoxypropanol, and a stirrer, a reflux condenser, and a thermometer were attached. A polymerization amount of a polymerization initiator V-65 (manufactured by Wako Pure Chemical Industries, Ltd.) was added at ° C and stirred for 10 hours. The obtained resin solution was added dropwise to 20 L of ion exchange water with vigorous stirring to obtain a white powder. This white powder was vacuum-dried at 40 ° C. for 24 hours to obtain 145 g of resin PX. When this molecular weight was measured by GPC, it was weight average molecular weight Mw = 28,000 and number average molecular weight Mn = 11,000.

-Synthesis of naphthoquinonediazide compound N-1-
Trisp-PA (Honshu Chemical Co., Ltd.) 42.45 g, o-naphthoquinonediazide-5-sulfonyl chloride 61.80 g, and acetone 300 ml were charged into a three-necked flask, and 24.44 g of triethylamine was added dropwise at room temperature over 1 hour. After completion of the dropwise addition, the mixture was further stirred for 2 hours, and then the reaction solution was poured while stirring a large amount of water. Precipitated naphthoquinone diazide sulfonic acid ester was collected by suction filtration and vacuum dried at 40 ° C. for 24 hours to obtain photosensitive naphthoquinone azide compound N-1.

-Exposure and development of colored curable composition (image formation)-
A glass substrate with an undercoat layer was prepared in the same manner as in Example 1, and the colored curable composition prepared as described above was applied onto the glass substrate with an undercoat layer, prebaked, irradiated, Development, rinsing and spray drying were performed to obtain a pattern, and then this pattern was heated at 180 ° C. for 5 minutes (post-baking). The formed cyan pattern showed a good rectangular profile.
Subsequently, the storage stability of the dye resist solution prepared above and the heat fastness and light fastness of the coating film coated on the glass substrate using the dye resist solution were evaluated in the same manner as in Example 1. However, as in the case of the negative type, storage stability, light fastness and heat fastness were all good.

(Examples 12 to 21)
Except having changed the glass substrate of Examples 1-10 into the silicon wafer substrate, all the same operations as Example 1-10 were performed, and the coating film was coated on the silicon wafer substrate. Next, using a i-line reduction projection exposure apparatus, a 2 μm square pattern was exposed at an exposure amount of 500 mJ / cm ² , and a developer obtained by diluting CD-2000 (manufactured by Fujifilm Electromaterials) to 60% was prepared. And developed at 23 ° C. for 60 seconds. Subsequently, after rinsing with running water for 30 seconds, spray drying was performed. As a result, a pattern suitable as a color filter for CCD having a square cross section and a good profile was obtained.

Claims (3)

The polymer dye contains at least one dye monomer represented by the following general formula (P) and at least one colorless monomer having at least one ethylenic double bond. Colored curability characterized by being one or more selected from the group consisting of a copolymer and a polymer derived from at least one dye monomer represented by the following general formula (P) Composition.

[In General Formula (P), R ^a1 and R ^a2 each independently represent a hydrogen atom, an aliphatic group, an aryl group or a heterocyclic group, and L ¹ represents the following (L-1), (L-2), ( L-3) represents any one of (L-4), and i represents 0 or 1. Q represents a pigment residue obtained by removing a hydrogen atom from any possible position of the dye represented by the following general formula (1). ]

[In (L-1) to (L-4), R ^a3 and R ^a4 each independently represent a hydrogen atom, an aliphatic group, an aryl group, or a heterocyclic group. In (L-1) to (L-4), the dye residue and the group having an ethylenic double bond may be bonded to either side. ]

[In General Formula (1), R ^{301 to} R ³⁰⁶ each independently represent a hydrogen atom or a substituent. When at least two of R ^{301 to} R ³⁰⁶ are adjacent to each other, they may be bonded to each other to form a 5- to 6-membered ring, and the ring may further have a substituent. ] The polymer dye contains at least one dye monomer represented by the following general formula (P) and at least one colorless monomer having at least one ethylenic double bond. A color filter comprising at least one selected from the group consisting of a copolymer and a polymer derived from at least one dye monomer represented by the following general formula (P).

[In General Formula (P), R ^a1 and R ^a2 each independently represent a hydrogen atom, an aliphatic group, an aryl group or a heterocyclic group, and L ¹ represents the following (L-1), (L-2), ( L-3) represents any one of (L-4), and i represents 0 or 1. Q represents a pigment residue obtained by removing a hydrogen atom from any possible position of the dye represented by the following general formula (1). ]

[In (L-1) to (L-4), R ^a3 and R ^a4 each independently represent a hydrogen atom, an aliphatic group, an aryl group, or a heterocyclic group. In (L-1) to (L-4), the dye residue and the group having an ethylenic double bond may be bonded to either side. ]

[In General Formula (1), R ^{301 to} R ³⁰⁶ each independently represent a hydrogen atom or a substituent. When at least two of R ^{301 to} R ³⁰⁶ are adjacent to each other, they may be bonded to each other to form a 5- to 6-membered ring, and the ring may further have a substituent. ]   A method for producing a color filter, comprising: applying a colored curable composition according to claim 1 onto a support; and exposing and developing through a mask to form a pattern image.