JP2005250224A - Colored curable composition, color filter and its production method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a colored curable composition having a good hue, high heat fastness and light fastness, and excellent temporal stability as well as high sensitivity, high resolution and high transmittance properties. <P>SOLUTION: The colored curable composition contains a compound represented by formula (1) as a dye, wherein X is S or -N(-Q<SP>1</SP>)-; Q is a group of nonmetallic atoms required to form a 5-membered heterocycle in combination with X; Q<SP>1</SP>is H, an aliphatic group, a heterocyclic group, aryl, acyl, aliphatic oxycarbonyl, aryloxycarbonyl, carbamoyl, aliphatic sulfonyl, arylsulfonyl or sulfamoyl; B<SP>1</SP>is -CR<SP>4</SP>= or N; B<SP>2</SP>is -CR<SP>5</SP>= or N (with the proviso that B<SP>1</SP>and B<SP>2</SP>are not simultaneously N); R<SP>4</SP>and R<SP>5</SP>are each H or a substituent; G<SP>1</SP>and G<SP>2</SP>are each a substituent (with the proviso that G<SP>2</SP>is not a group linked through N). <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a color filter suitable for a liquid crystal display element and a solid-state image sensor, a method for producing the same, and a colored curable composition suitable for forming the color filter.

  As a color filter formed on a device for colorizing a solid-state imaging device or a liquid crystal display device, a yellow filter layer, a magenta filter layer, and a cyan filter layer formed adjacent to each other on the same plane of the substrate Known color filters include color filters, red filter layers, green filter layers, and blue filter layers. A band-like pattern or a mosaic pattern is formed by these filter layers.

  Various methods have been proposed so far for producing 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 a patterning process a required number of times has been 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, and the like, and has a sufficient positional accuracy because it is patterned by a photolithography method, and is a suitable method for manufacturing a color filter for a large screen and a high-definition color display.

  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 a 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 is known. (For example, see Patent Documents 1 to 8 and 12.)

  However, in recent years, further enhancement in definition has been desired for color filters for solid-state imaging devices. However, the conventional pigment dispersion system as described above does not improve the resolution, and also has problems such as color unevenness due to coarse pigment particles. Was not suitable for applications that required

Conventionally, the use of dyes has been proposed for such problems (see, for example, Patent Documents 9 to 10). There are also positive photosensitive compositions (see, for example, Patent Documents 11 to 12). However, the dye-containing curable composition has the following problems, and further improvement has been demanded. That is,
(1) Dyes are generally inferior in heat resistance, light resistance, etc. compared to pigments, and have insufficient fastness.
(2) When the molar absorption coefficient of the dye is low, a large amount of dye must be added. In this case, other compounds such as a polymerizable compound, a binder, and a photopolymerization initiator in the curable composition are added. The components must be relatively reduced, and the curability at the time of curing the composition, the heat resistance of the cured portion that has been cured, the developability of the non-cured portion, and the like are reduced.
(3) Dyes often interact with other components in the curable composition, and it is difficult to adjust the developability (solubility) of the cured part and the non-cured part.
As described above, the dyes conventionally used in the photosensitive composition are not particularly satisfactory in fastness, and further have low solubility in the photosensitive composition, so that they are in the liquid or coated. Dye may precipitate in the state of the film, and it is difficult to contain the dye at a high concentration.

On the other hand, it is known that a yellow dye is used for the green and red filter arrays of the color filter (see, for example, Patent Document 12). However, the pyridone azo dyes used have insufficient heat resistance and light resistance.
Similarly, in the case of a color filter composed of a yellow filter layer, a magenta filter layer, and a cyan filter layer, it has been desired to further improve the fastness and hue of the yellow dye used in the yellow filter layer. The same applies to other hues such as magenta dyes.

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

  As described above, although a curable composition containing a dye is useful in applications such as a solid-state imaging device that requires high definition and uniform color, the color density and hue of a dye such as amber can be stably maintained. However, improvement of fastness such as heat resistance and light resistance of dyes, particularly yellow dyes, has been an issue. In addition, due to low solubility, improvement of dye precipitation due to low stability over time when a liquid preparation or a coated film is formed was also an issue.

The present invention has been made in view of the above, and has high sensitivity, high resolution, high transmittance characteristics, good hue, high heat fastness and high light fastness, and excellent color stability. Intended to provide a sexual composition, and
An object of the present invention is to provide a color filter having high resolution and high transmittance characteristics and having high heat fastness and light fastness, and a color filter manufacturing method capable of producing the color filter with high productivity. The object of the present invention is to achieve the object.

  In the present invention, various dye compound derivatives having a good hue and high fastness to light and heat are examined in detail. As a result, a specific heterocyclic azo dye (dye) has particularly high heat resistance and light resistance. The knowledge that it is useful for improving the fastness was obtained, and based on this knowledge, a colored curable composition, a color filter and a production method thereof having the following constitution were provided, and the object was achieved. Specific means for achieving the above object are as follows.

<1> A colored curable composition comprising a dye represented by the following general formula (1).

In the general formula (1), X represents a sulfur atom or —N (—Q ¹ ) —, Q represents a nonmetallic atom group necessary for forming a 5-membered heterocyclic ring together with X, The heterocycle may be condensed. Q ¹ represents a hydrogen atom, aliphatic group, heterocyclic group, aryl group, acyl group, aliphatic oxycarbonyl group, aryloxycarbonyl group, carbamoyl group, aliphatic sulfonyl group, arylsulfonyl group, or sulfamoyl group. B ¹ represents —CR ⁴ ═ or a nitrogen atom, B ² represents —CR ⁵ ═ or a nitrogen atom, and B ¹ and B ² do not represent a nitrogen atom at the same time. R ⁴ and R ⁵ each independently represents a hydrogen atom or a substituent. G ¹ and G ² each independently represent a substituent. However, G ² is not a group linked by a nitrogen atom. R ⁴ and R ⁵ and / or R ⁵ and G ² may be bonded to each other to form a 5- to 7-membered hydrocarbon ring or a 5- to 7-membered heterocyclic ring.

<2> A color filter comprising a dye represented by the following general formula (1).

In the general formula (1), as described above, X represents a sulfur atom or —N (—Q ¹ ) —, and Q represents a group of nonmetallic atoms necessary to form a 5-membered heterocyclic ring together with X. Further, the 5-membered heterocyclic ring may be condensed. Q ¹ represents a hydrogen atom, aliphatic group, heterocyclic group, aryl group, acyl group, aliphatic oxycarbonyl group, aryloxycarbonyl group, carbamoyl group, aliphatic sulfonyl group, arylsulfonyl group, or sulfamoyl group. B ¹ represents —CR ⁴ ═ or a nitrogen atom, B ² represents —CR ⁵ ═ or a nitrogen atom, and B ¹ and B ² do not represent a nitrogen atom at the same time. R ⁴ and R ⁵ each independently represents a hydrogen atom or a substituent. G ¹ and G ² each independently represent a substituent. However, G ² is not a group linked by a nitrogen atom. R ⁴ and R ⁵ and / or R ⁵ and G ² may be bonded to each other to form a 5- to 7-membered hydrocarbon ring or a 5- to 7-membered heterocyclic ring.
The color filter described in <2> is preferably formed using the colored curable composition described in <1>.

<3> A method for producing a color filter, comprising: applying the colored curable composition according to the above <1> onto a support, exposing through a mask, and developing to form a pattern image. is there.
In the method for producing a color filter, when producing a color filter having a desired hue, the above steps are repeated according to the desired number of hues. Moreover, the aspect which has the process of hardening | curing the said pattern image by heating and / or exposure as needed is also suitable.

According to the present invention, it is possible to provide a colored curable composition having high sensitivity, high resolution, and high transmittance, a good hue, high heat fastness and light fastness, and excellent temporal stability. it can. Also,
According to the present invention, there are provided a color filter having high resolution and high transmittance characteristics, high heat fastness and high light fastness, and a color filter manufacturing method capable of producing the color filter with high productivity. can do.

Hereinafter, the colored curable composition of the present invention, the color filter, and the production method thereof will be described in detail.
[Colored curable composition]
The colored curable composition of the present invention comprises a compound represented by the following general formula (1) as a pigment (hereinafter also referred to as “azo dye according to the present invention”), preferably a binder or radiation sensitive. It comprises a compound and a polymerizable monomer. Moreover, generally, it can be further constituted by using a solvent, and if necessary, it can be constituted by using other components such as a crosslinking agent.

-Dye represented by general formula (1)-
The colored curable composition of this invention contains at least 1 type of the pigment | dye (azo dye which concerns on this invention) represented by following General formula (1). This azo dye exhibits a good hue, does not precipitate over time when it is in the form of a liquid preparation or a coated film, and has excellent stability, and particularly has resistance to heat and light.

  In the present specification, the term “aliphatic” means that the aliphatic moiety is linear, branched, or cyclic and may be either saturated or unsaturated, such as an alkyl group, an alkenyl group, a cycloalkyl group. A cycloalkenyl group, which may be unsubstituted or substituted with a substituent. In addition, “aryl” in the present specification may be either a single ring or a condensed ring, and includes, for example, an aromatic group, which may be unsubstituted or substituted with a substituent. In the present specification, “heterocycle” means that the heterocycle moiety has a heteroatom (eg, nitrogen atom, sulfur atom, oxygen atom) in the ring, and is either a saturated ring or an unsaturated ring. It may be either a single ring or a condensed ring, and may be unsubstituted or substituted with a substituent.

  Further, the “substituent” in the present specification may be any group that can be substituted, for example, an aliphatic group, an aryl group, a heterocyclic group, an acyl group, an acyloxy group, an acylamino group, an aliphatic oxy group, an aryl group. Oxy 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, arylsulfonyl Oxy group, heterocyclic sulfonyloxy group, sulfamoyl group, aliphatic sulfonamide group, aryl sulfonamide group, heterocyclic sulfonamide group, amino group, aliphatic amino group, arylamino group, heterocyclic amino group, aliphatic oxycarbonyl An amino group, an aryloxycarbonylamino group, Terrocyclic oxycarbonylamino group, aliphatic sulfinyl group, arylsulfinyl group, aliphatic thio group, arylthio group, hydroxy group, cyano group, sulfo group, carboxyl group, aliphatic oxyamino group, aryloxyamino group, carbamoylamino group And sulfamoylamino group, halogen atom, sulfamoylcarbamoyl group, carbamoylsulfamoyl group, dialiphatic oxyphosphinyl group, diaryloxyphosphinyl group and the like.

Hereinafter, each group in the general formula (1) will be described in more detail.
In the general formula (1), X represents a sulfur atom or —N (—Q ¹ ) —, and Q ¹ represents a hydrogen atom, an aliphatic group, a heterocyclic group, an aryl group, an acyl group, or an aliphatic oxycarbonyl. A group, an aryloxycarbonyl group, a carbamoyl group, an aliphatic sulfonyl group, an arylsulfonyl group, or a sulfamoyl group;

The aliphatic group represented by Q ¹ may be unsubstituted or substituted, may be a saturated group or an unsaturated group, and is preferably an aliphatic group having 1 to 15 carbon atoms in total. Examples thereof include a methyl group, an ethyl group, a vinyl group, an allyl group, an ethynyl group, an isopropenyl group, and a 2-ethylhexyl group.
The heterocyclic group represented by Q ¹ may be an aromatic ring or a non-aromatic ring, and is preferably a heterocyclic group having 1 to 16 carbon atoms in total. Examples thereof include groups such as a benzothiazole ring and a thiadiazole ring.
The aryl group represented by Q ¹ may be unsubstituted or substituted, and an aryl group having 6 to 16 carbon atoms is preferable. For example, phenyl group, 4-nitrophenyl group, 2-nitrophenyl group, 2-chlorophenyl group, 2,4-dichlorophenyl group, 2,4-dimethylphenyl group, 2-methylphenyl group, 4-methoxyphenyl group, 2 -Methoxyphenyl group, 2-methoxycarbonyl-4-nitrophenyl group and the like.
The acyl group represented by Q ¹ may be aromatic or aliphatic, and preferably has 2 to 15 carbon atoms in total. For example, acetyl group, pivaloyl group, benzoyl group and the like can be mentioned.
The aliphatic oxycarbonyl group represented by Q ¹ may be unsubstituted or substituted, may be a saturated group or an unsaturated group, and an aliphatic oxycarbonyl group having 1 to 16 carbon atoms in total. preferable. For example, a methoxycarbonyl group, a butoxycarbonyl group, etc. are mentioned.
The aryloxycarbonyl group represented by Q ¹ may be unsubstituted or substituted, and is preferably an aryloxycarbonyl group having 7 to 17 carbon atoms in total. For example, a phenoxycarbonyl group etc. are mentioned.

The carbamoyl group represented by Q ¹ may be unsubstituted or substituted, and is preferably a carbamoyl group having 1 to 12 carbon atoms in total. For example, a carbamoyl group, a dimethylcarbamoyl group, etc. are mentioned.
The aliphatic sulfonyl group represented by Q ¹ may be unsubstituted or substituted, may be a saturated group or an unsaturated group, and the total number of carbon atoms in the aliphatic moiety is preferably 1-15. For example, a methanesulfonyl group, a butanesulfonyl group, a methoxyethanesulfonyl group, and the like can be given.
The arylsulfonyl group represented by Q ¹ may be unsubstituted or substituted, and is preferably an arylsulfonyl group having 6 to 16 carbon atoms in total. For example, a phenylsulfonyl group, 4-t-butylphenyl group, 4-toluenesulfonyl group, 2-toluenesulfonyl group and the like can be mentioned.
The sulfamoyl group represented by Q ¹ may be unsubstituted or substituted, and is preferably a sulfamoyl group having 0 to 12 carbon atoms in total. For example, a sulfamoyl group, a dimethylsulfamoyl group, etc. are mentioned.

Wherein X is from the viewpoint of providing the effect of the invention more effectively, -N (-Q ¹⁾ - preferably it may represent. In addition, among the above, Q ¹ is preferably an aliphatic group or an aryl group, and more preferably an aryl group.

  In the general formula (1), Q represents a nonmetallic atom group necessary for forming a 5-membered heterocyclic ring together with X. The formed 5-membered heterocycle may be condensed. The 5-membered heterocyclic ring formed by Q together with X may be unsubstituted or substituted, for example, thiophene, thiazole, isothiazole, 1,3,4-thiadiazole, 1,2,4-thiadiazole , Pyrazole, imidazole, 1,2,4-triazole, benzimidazole and the like.

In the general formula (1), B ¹ represents —CR ⁴ ═ or a nitrogen atom, B ² represents —CR ⁵ ═ or a nitrogen atom, and R ⁴ and R ⁵ each independently represent a hydrogen atom or a substituent. Represents a group. However, B ¹ and B ² do not represent a nitrogen atom at the same time.

The substituent represented by R ⁴ or R ⁵ is a group described in the above-mentioned “Substituent” section and may be any group that can be substituted. R ⁴ and R ⁵ are each a hydrogen atom, an aliphatic group, an aryl group, a heterocyclic group, an acyl group, an acylamino group, an aliphatic oxy group, an aliphatic oxycarbonyl from the viewpoint of more effectively achieving the effects of the present invention. Group, carbamoyl group, sulfamoyl group, aliphatic sulfonamido group, arylsulfonamido group, amino group, aliphatic amino group, hydroxy group, cyano group, sulfo group, carboxyl group are preferred, hydrogen atom, aliphatic group More preferably represents a cyano group.

In the general formula (1), G ¹ and G ² each independently represent a substituent. However, G ² is not a group linked by a nitrogen atom. The substituent represented by G ¹ or G ² is a group described in the above-mentioned “Substituent” section and may be any group that can be substituted. G ¹ and G ² are each an aliphatic group, aryl group, heterocyclic group, acyloxy group, acylamino group, aliphatic oxy group, aryloxy group, heterocyclic oxy group, aliphatic sulfonamido group, arylsulfonamido group , Heterocyclic sulfonamido group, amino group, aliphatic amino group, arylamino group, heterocyclic amino group, aliphatic oxycarbonylamino group, aryloxycarbonylamino group, heterocyclic oxycarbonylamino group, aliphatic thio group, arylthio Group, hydroxy group, cyano group, sulfo group, carboxyl group, carbamoylamino group, sulfamoylamino group, and halogen atom are preferably mentioned, from the viewpoint of more effectively achieving the effects of the present invention, an aliphatic oxy group, May represent an aliphatic amino group, an arylamino group, an aliphatic thio group, or a hydroxy group More preferred.

In particular, an embodiment in which G ¹ is represented by a hydroxy group or an aliphatic amino group is preferable. The aliphatic amino group may be linear or branched, may be unsubstituted or have a substituent, may be an N, N-disubstituted product, and has total carbon. An aliphatic amino group having a number of 1 to 20 is preferred. For example, methylamino group, (i) -butylamino group, (s) -butylamino group, 3-butoxypropylamino group, methoxyethoxyethylamino group, 3-phenoxypropylamino group, and 2-hydroxyethylamino group are preferable. It is mentioned in.

In the above, R ⁴ and R ⁵ may be bonded to each other and / or R ⁵ and G ² may be bonded to each other to form a 5-membered ring to a 7-membered ring. Any of the 5- to 7-membered rings may be an aromatic ring or a non-aromatic ring, and may be a hydrocarbon ring or a heterocyclic ring. For example, a benzene ring, a pyridine ring, etc. are mentioned suitably.

Among the dyes represented by the general formula (1), the dye represented by the following general formula (2) is more preferable from the viewpoint of the effect of the present invention.

In formula ^{(2), B 1, B} 2, G 1, G 2, and Q ¹ is ^{B 1, B 2, G 1} , G 2 in the general formula (1), and Q ^1, interchangeably The same applies to each preferred embodiment.

In the general formula (2), R ² represents a hydrogen atom or a substituent. The substituent represented by R ² is the group described in the above-mentioned “Substituent” section and may be any group that can be substituted. From the standpoint of effectively achieving the effects of the present invention, R ² includes a hydrogen atom, an aliphatic group, an aryl group, an acyloxy group, an acylamino group, an aliphatic oxy group, an aliphatic sulfonyloxy group, an arylsulfonyloxy group, Aliphatic sulfonamido group, arylsulfonamido group, amino group, aliphatic amino group, arylamino group, aliphatic oxycarbonylamino group, aryloxycarbonylamino group, heterocyclic oxycarbonylamino group, aliphatic oxycarbonyl group, cyano Group, carbamoyl group, carbamoylamino group, sulfamoylamino group, aliphatic sulfonyl group, and aromatic sulfonyl group are preferred, hydrogen atom, aliphatic group, aryl group, aliphatic oxy group, aliphatic oxycarbonyl group , A cyano group, a carbamoyl group, an aliphatic sulfonyl group There further preferred.

In the general formula (2), X ¹ represents —CR ³ ═ or a nitrogen atom, and X ² represents —CR ¹ ═ or a nitrogen atom. R ¹ and R ³ each independently represents a hydrogen atom or a substituent. The substituent represented by R ¹ or R ³ is a group described in the above-mentioned “Substituent” section and may be any group that can be substituted. Q ¹ and R ¹ , R ¹ and R ² , R ² and R ³ may be bonded to each other to form a 5-membered ring to a 7-membered ring.

In the general formula ^{(2), Q 1, X} 1, X 2, B 1, B 2, and X ^1, X ² is ^{-CR 3 =, - R 3,} R 1 when it represents a CR ¹ = is From the viewpoint of effectively achieving the effects of the present invention, the following embodiments are preferable.
Q ¹ is preferably an aliphatic group or an aryl group, and more preferably an aryl group.
An embodiment in which at least one of X ¹ and X ² is a nitrogen atom is preferred.
R ¹ in the case where X ² represents —CR ¹ ═ represents a hydrogen atom, aliphatic group, aryl group, acyl group, aliphatic oxycarbonyl group, carbamoyl group, aliphatic sulfonyl group, arylsulfonyl group, cyano group, carboxyl The aspect which is group is preferable, and the aspect which is an aliphatic oxycarbonyl group, a carbamoyl group, and a cyano group is more preferable.
R ³ in the case where X ¹ represents —CR ³ ═ represents a hydrogen atom, an aliphatic group, an aryl group, an acyl group, an acylamino group, an aliphatic oxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an aliphatic sulfonyl group, A preferable embodiment is an arylsulfonyl group, a heterocyclic sulfonyl group, an aliphatic sulfonyloxy group, an arylsulfonyloxy group, an aliphatic sulfonamido group, an arylsulfonamido group, a cyano group, or a carboxyl group, an acyl group, an aliphatic oxycarbonyl group , An aliphatic sulfonyl group, an arylsulfonyl group, a cyano group, a carbamoyl group, and a carboxyl group are more preferable.

If the X ² represents a nitrogen atom, from the viewpoint of providing the effect of the present invention effectively, the X ^1, R ³ is a hydrogen atom, an aliphatic group, an aryl group, an acyl group, an acylamino group, an aliphatic oxycarbonyl Group, aryloxycarbonyl group, carbamoyl group, aliphatic sulfonyl group, arylsulfonyl group, heterocyclic sulfonyl group, aliphatic sulfonyloxy group, arylsulfonyloxy group, aliphatic sulfonamido group, arylsulfonamido group, cyano group, or In the case of representing a carboxyl group, —CR ³ ═ or a nitrogen atom is preferable (particularly preferably —CR ³ ═ in this case), and R ³ is an acyl group, an aliphatic oxycarbonyl group, an aliphatic sulfonyl group, an arylsulfonyl group, a cyano group group, -CR ³ = or a nitrogen atom when it represents a carbamoyl group or carboxyl group, More preferably (particularly preferably in this case -CR ³ =), R ³ is an aliphatic oxycarbonyl group, an aliphatic sulfonyl group or -CR ³ = or a nitrogen atom when it represents a cyano group (particularly preferably in this case, -CR ³ =) it is most preferred.

When X ² represents —CR ¹ ═, from the standpoint of effectively achieving the effects of the present invention, X ¹ is a nitrogen atom, and R ¹ is a hydrogen atom, an aliphatic group, an aryl group, an acyl group, An embodiment in which an aliphatic oxycarbonyl group, a carbamoyl group, an aliphatic sulfonyl group, an arylsulfonyl group, a cyano group, or a carboxyl group is preferable, X ¹ is a nitrogen atom, and R ¹ is an aliphatic oxycarbonyl group, a carbamoyl group. The aspect which is group or a cyano group is still more preferable.

Further, from the viewpoint of the effect of the present invention, an embodiment in which B ¹ is —CR ⁴ ═ and B ² is —CR ⁵ ═ or a nitrogen atom is preferable. R ^{4 in} the case where B ¹ represents —CR ⁴ ═ and R ⁵ in the case where B ² represents —CR ⁵ ═ are each independently a hydrogen atom, an aliphatic group, aryl, from the viewpoint of the effect of the present invention. Group, acyl group, acylamino group, aliphatic oxy group, aliphatic oxycarbonyl group, carbamoyl group, sulfamoyl group, aliphatic sulfonamide group, aromatic sulfonamide group, or cyano group are preferred, hydrogen atom, aliphatic group The embodiment which is a group or a cyano group is more preferable.

In the general formula (2), Q ¹ is an aryl group and R ² is a hydrogen atom, an aliphatic group, an aryl group, or an aliphatic oxy group from the viewpoint of more effectively achieving the effects of the present invention. X ¹ is —CR ³ ═, X ² is a nitrogen atom, B ¹ is —CR ⁴ ═, B ² is —CR ⁵ ═ or a nitrogen atom, and G ¹ is a hydroxy group , An aliphatic amino group, or an arylamino group, wherein G ² is a hydroxy group, an aliphatic oxy group, or an aliphatic thio group, and R ² is a hydrogen atom, an aliphatic oxycarbonyl group, or a carbamoyl group Or a cyano group, X ¹ is a nitrogen atom, X ² is -CR ¹ =, B ¹ is -CR ⁴ =, B ² is -CR ⁵ = or a nitrogen atom, G ¹ is hydroxy group, an aliphatic amino group or an arylamino group,, G ² is Dorokishi group, an aliphatic oxy group, or aspects an aliphatic thio group, are preferred.
Furthermore, Q ¹ is an aryl group, R ² is a hydrogen atom, an aliphatic group, an aryl group, or an aliphatic oxy group, X ¹ is —CR ³ ═, and X ² is a nitrogen atom. there are, B ¹ is -CR ⁴ =, B ² is a -CR ⁵ = or a nitrogen atom, a G ¹ is hydroxy group or an aliphatic amino group, G ² is a hydroxy group, an aliphatic oxy group, Or the aspect which is an aliphatic thio group is especially preferable.

In the present invention, a dye represented by the following general formula (3) is particularly preferable.

In Formula ^{(3), R 4, R} 5, G 1, G 2, and Q ¹ is, R ⁵ in R ^4, B ² in B ¹ in the general formula (1) in, G ^1, G ² , And Q ¹ , and the same applies to each preferred embodiment. R ² and R ³ have the same meaning as R ³ in R ² and X ¹ in the general formula (2), and the preferred embodiments thereof are also the same. Further, an embodiment in which G ¹ is represented by an aliphatic amino group is preferable.

In the general formula (3), Q ¹ is an aryl group, R ² is a hydrogen atom or an aliphatic group, and R ³ is an aliphatic oxycarbonyl in order to achieve the effect of the present invention more effectively. A group, an aliphatic sulfonyl group, or a cyano group, R ⁴ is a hydrogen atom or an aliphatic group, R ⁵ is a hydrogen atom or a cyano group, G ¹ is an aliphatic amino group, An embodiment in which G ² is an aliphatic oxy group or an aliphatic thio group is preferred, Q ¹ is an aryl group, R ² is a hydrogen atom or an aliphatic group, and R ³ is an aliphatic sulfonyl group or a cyano group R ⁴ is an aliphatic group, R ⁵ is a cyano group, G ¹ is an aliphatic amino group, and G ² is an aliphatic oxy group or an aliphatic thio group. embodiment is more preferable, and a Q ¹ is an aryl group, R ² is a hydrogen atom or An aliphatic group, and R ³ is a cyano group, a R ⁴ are aliphatic groups, and R ⁵ is a cyano group, a hydrogen atom to the nitrogen atom to which G ¹ is bonded with 6-membered heterocyclic ring The embodiment in which G ² is an aliphatic oxy group or an aliphatic thio group is most preferable.

  Hereinafter, specific examples [Exemplary compounds (1) to (25)] of the coloring matter (azo dye according to the present invention) represented by the general formulas (1) to (3) will be shown. However, the present invention is not limited to these.

  Next, as a synthesis example of the coloring matter (azo dye) represented by the general formula (1), an example in which the exemplified compound (1) is synthesized will be described based on the following scheme.

[Synthesis Example]: Synthesis of Exemplified Compound (1)

  18.7 g (0.10 mol) of compound (A) was gradually added to 45.0 g (0.60 mol) of 1-amino-2-ethylhexane while stirring with water. Then, it stirred at 120 degreeC for 3 hours. After stirring, the temperature of the reaction solution was lowered to room temperature, 300 ml of ethyl acetate and 300 ml of water were added and separated, and the ethyl acetate phase was washed twice with 200 ml of saturated brine. Then, ethyl acetate was distilled off under reduced pressure, and the resulting viscous liquid was crystallized with 100 ml of acetonitrile to obtain 19.7 g of Compound (B) (yield 74.6%).

  Separately, a solution in which 10.0 g (0.06 mol) of compound (C) was dissolved in a mixed solution (0.10 mol) of 35 ml of acetic acid and 8.5 ml of concentrated hydrochloric acid was prepared, and this solution was stirred at 3 ° C. A solution prepared by dissolving 4.3 g (0.062 mol) of sodium nitrite in 13 ml of water was added over 5 minutes, and the mixture was further stirred for 40 minutes to obtain a solution a. On the other hand, a solution was prepared by dissolving 16.0 g (0.06 mol) of the compound (B) obtained from the above in a mixed solution (0.33 mol) of 47 ml of N-methylpyrrolidone and 26.6 ml of pyridine. While stirring at 10 ° C., solution a was added over 20 minutes. Thereafter, the mixture was further stirred at 25 ° C. for 2 hours. To this reaction solution, 300 ml of water was added and stirred for 1 hour, and the precipitated crystals were filtered and washed thoroughly with water. The obtained crystals were dried to obtain 25.4 g of Compound (D) (yield 96.2%).

To 12.5 g (0.028 mol) of this compound (D), 30 ml of dimethylacetamide, 7.8 g (0.057 mol) of potassium carbonate, and 4.4 g (0.031 mol) of p-fluoronitrobenzene were added, and 75 ° C. Stirring under 2 hours. The reaction solution was poured into a mixed solution of 100 ml of water and 100 ml of ethyl acetate and separated, and the ethyl acetate phase was washed twice with 100 ml of saturated brine. Thereafter, ethyl acetate was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography, further crystallized with 70 ml of acetonitrile, filtered, washed with 30 ml of cold acetonitrile, dried, and yellow crystals [Exemplary Compound (1); Azo dye] 7.3 g was obtained. The crystallized product has a yield of 46.5% and a melting point of 200 ° C. or higher, and has a maximum absorption wavelength (λ _max ) and molar extinction coefficient (ε) in ethyl acetate by a spectrophotometer UV-2500PC (manufactured by Shimadzu Corporation). Were λ _max = 499.1 nm and ε = 34,500 [l · mol ⁻¹ · cm ⁻¹ ], respectively.

  In addition, it can synthesize | combine similarly to the above also about another above-mentioned exemplary compound by changing into a desired compound according to the target azo dye.

-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 resistance, 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-. No. 25957, JP-A-59-53836, JP-A-59-71048, and the like, such as methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer. Examples thereof include polymers, maleic acid copolymers, partially esterified maleic acid copolymers, and acidic cellulose derivatives having a carboxylic acid in the side chain are particularly useful. In addition, polymers obtained by adding an acid anhydride to a polymer having a hydroxyl group, polyhydroxystyrene resins, polysiloxane resins, poly (2-hydroxyethyl (meth) acrylate), polyvinylpyrrolidone, polyethylene oxide, polyvinyl alcohol Etc. are also useful.

  In addition, a monomer having a hydrophilic group may be copolymerized, and examples thereof include alkoxyalkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, glycerol (meth) acrylate, (meth) acrylamide, and N-methylolacrylamide. Secondary and tertiary alkyl acrylamide, dialkylaminoalkyl (meth) acrylate, morpholino (meth) acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, vinyltriazole, methyl (meth) acrylate, ethyl (meth) Examples include those obtained by copolymerization using acrylate, branched or linear propyl (meth) acrylate, branched or linear butyl (meth) acrylate, phenoxyhydroxypropyl (meth) acrylate, and the like. .

  In addition to the above, as a monomer having a hydrophilic group, a tetrahydrofurfuryl group, a phosphoric acid site, a phosphoric acid ester site, a quaternary ammonium salt site, an ethyleneoxy chain, a propyleneoxy chain, a sulfonic acid or its salt site, a morpholinylethyl group, etc. Monomers containing are also useful.

From the viewpoint of improving the crosslinking efficiency, a polymer group having a polymerizable group in the side chain and a polymer having an allyl group, a (meth) acryl group, an allyloxyalkyl group or the like in the side chain are also useful. Examples of the polymer having a polymerizable group include KS resist-106 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series (manufactured by Daicel Chemical Industries, Ltd.) and the like.
From the viewpoint of increasing 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 resistance, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferable, and from the viewpoint of control of developability. An acrylic resin, an acrylamide resin, and an acrylic / acrylamide copolymer resin are preferable. Examples of the acrylic resin include copolymers composed of monomers selected from benzyl (meth) acrylate, (meth) acrylic, hydroxyethyl (meth) acrylate, (meth) acrylamide, and the like, and KS resist-106 (Osaka Organic Chemical Industry). And Cyclomer P series (manufactured by Daicel Chemical Industries, Ltd.).

Moreover, an alkali-soluble phenol resin can also be used as a binder in the present 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 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 preferably has a mass average molecular weight (polystyrene equivalent value measured by GPC method) of 1000 to 2 × 10 ⁵ , more preferably 2000 to 1 × 10 ⁵ , and more preferably 5000 to ⁵ × 10 ^4. The polymer is particularly preferred.

  As content in the colored curable composition of this invention of a binder, 10-90 mass% is preferable with respect to the total solid of this composition, 20-80 mass% is more preferable, 30-70 mass% Is particularly preferred.

-Crosslinking agent-
The present invention uses the coloring matter (dye) represented by the general formula (1) described above, and the curing reaction of the film proceeds to a higher degree as compared with the prior art, so that a film having good curability can be obtained. However, it is also possible to obtain a more highly cured film using a cross-linking agent.

  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. Substituted with at least one group selected from melamine compound, guanamine compound, glycoluril compound, or urea compound substituted with at least one group selected from: (c) methylol group, alkoxymethyl group, and acyloxymethyl group Phenolic compounds, naphthol compounds, or hydroxyanthracene compounds. Of these, polyfunctional epoxy resins are particularly preferred.

  The (a) epoxy resin may be any epoxy resin as long as it has an epoxy group and is crosslinkable. For example, bisphenol A glycidyl ether, ethylene glycol diglycidyl ether, ethylene glycol diglycidyl ether, butanediol di Divalent glycidyl group-containing low molecular weight compounds such as glycidyl ether, hexanediol diglycidyl ether, dihydroxybiphenyl diglycidyl ether, diglycidyl phthalate, N, N-diglycidyl aniline, as well as trimethylolpropane triglycidyl ether , Trivalent glycidyl group-containing low molecular weight compounds typified by trimethylolphenol triglycidyl ether, TrisP-PA triglycidyl ether, Tetravalent glycidyl group-containing low molecular weight compounds typified by ruether, tetramethylol bisphenol A tetraglycidyl ether and the like, as well as polyvalent glycidyl group-containing low molecular weight compounds such as dipentaerythritol pentaglycidyl ether and dipentaerythritol hexaglycidyl ether Glycidyl group-containing polymer compounds represented by polyglycidyl (meth) acrylate, 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol, and the like, Etc.

  The number of methylol groups, alkoxymethyl groups, and acyloxymethyl groups substituted in the crosslinking agent (b) is 2 to 6 in the case of melamine compounds, in the case of glycoluril compounds, guanamine compounds, and urea compounds. Although it is 2-4, Preferably it is 5-6 in the case of a melamine compound, and 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 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 compounds in which 1 to 5 methylol groups of melamine are acyloxymethylated, or mixtures thereof.

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

Examples of the urea compound include tetramethylol urea, tetramethoxymethyl urea, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylol urea, a mixture thereof, and tetramethoxyethyl urea.
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 the crosslinking agent (b). As in the case of), intermixing with the overcoated photoresist is suppressed by thermal crosslinking, and the film strength is further increased.
Hereinafter, these compounds may be collectively referred to as a compound according to (c) (a methylol group-containing compound, an alkoxymethyl group-containing compound, or an acyloxymethyl group-containing compound).

  The number of methylol groups, acyloxymethyl groups, and alkoxymethyl groups contained in the cross-linking agent (c) is at least two per molecule, and from the viewpoint of thermal crosslinkability and storage stability, phenol as a skeleton Compounds in which the 2nd and 4th positions of the compound are all substituted are preferred. In addition, the naphthol compound and hydroxyanthracene compound as the skeleton are preferably compounds in which all of the ortho-position and para-position of the OH group are substituted. The 3rd or 5th position of the phenolic compound serving as the skeleton may be unsubstituted or may have a substituent. Also in the naphthol compound, except for the ortho position of the OH group, it 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 a phenol compound, a naphthol compound, a hydroxyanthracene compound, etc., in which the ortho-position or para-position of the phenolic OH group is unsubstituted. 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) Kogyo Co., Ltd.), naphthol, dihydroxynaphthalene, 2,7-dihydroxyanthracene, and the like are used.

  Specific examples of the crosslinking agent (c) include 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, tetra Methoxymethyl bisphenol A, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylol bisphenol A, tetramethylol-4,4′-bishydroxybiphenyl, tetramethoxymethyl-4,4′-bishydroxybiphenyl, Tr Hexamethylol of sP-PA, hexamethoxymethyl of Tris P-PA, compounds in which 1 to 5 methylol groups have been methoxymethylated hexamethylol of Tris P-PA, Bis-hydroxymethyl 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, trimethylolphenol, bishydroxymethyl-p-cresol, tetramethylolbisphenol A, trisP-PA (manufactured by Honshu Chemical Industry Co., Ltd.) or a methylol group thereof is preferable. Examples thereof include an alkoxymethyl group and a phenol compound substituted with both a methylol group and an alkoxymethyl group.
These compounds 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 crosslinking agents (a) to (c) in the colored curable composition varies depending on the material, but relative to the solid content (mass) of the composition. 1 to 70% by mass is preferable, 5 to 50% by mass is more preferable, and 7 to 30% by mass is particularly preferable.

-Polymerizable monomer-
The colored curable composition of the present invention can be suitably constituted by containing at least one polymerizable monomer. The polymerizable monomer is mainly contained when the colored curable composition is configured 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. Hereinafter, the polymerizable monomer will be described.

  As the polymerizable monomer, a compound having an ethylenically unsaturated group having at least one addition-polymerizable ethylene group and having a boiling point of 100 ° C. or higher under normal pressure is preferable. Monofunctional acrylates and methacrylates such as (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (Meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) Ethylene oxide and propylene oxide were added to polyfunctional alcohols such as acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, glycerin and trimethylolethane Later (meth) acrylates, urethane acrylates described in JP-B-48-41708, JP-B-50-6034, JP-A-51-37193, JP-A-48-64183, JP-B-37 No. 49-43191, Japanese Patent Publication No. 52-30490, polyester acrylates, polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid, and this And a mixture of. Furthermore, the Journal of Japan Adhesion Association Vol. 20, no. 7, pages 300 to 308 are introduced as photocurable monomers and oligomers.

  The content of the polymerizable monomer in the colored curable composition is preferably 0.1 to 90 mass%, more preferably 1.0 to 80 mass% with respect to the solid content of the composition, and 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 type of a radiation sensitive compound. The radiation-sensitive compound according to the present invention is a compound capable of causing a chemical reaction such as radical generation, acid generation, base generation, etc., against 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.

  In particular, when the colored curable composition is configured as a negative type, it preferably contains a photopolymerization initiator, and when it is configured as a positive type, it preferably contains a naphthoquinonediazide compound. is there.

~ Photoinitiator etc. ~
First, a photopolymerization initiator suitable for a negative configuration 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 containing said naphthoquinone diazide compound, In this case, the hardening degree of the pattern formed can be accelerated | stimulated more.

  The photopolymerization initiator includes 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, and an acetophenone compound. And derivatives thereof, cyclopentadiene-benzene-iron complex and salts thereof, oxime compounds, and the like.

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

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

  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) -naphth-1-yl] -4,6-bis- Trichloromethyl-s-triazine, 2- [4- (2-butoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- (2-methoxy-naphth-1- Yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-methoxy-5-methyl-naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- ( 6-methoxy-naphtho 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-trichloro Methyl-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 (trichloromethyl) -s-triazine, 4- [p-N, N-di (chloroethyl) aminophenyl] -2,6-di (trichloro Methyl) -s-triazine, 4- [o-methyl-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (pN-chloroethyla) Nophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- [p- N, N-di (phenyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (p-N-chloroethylcarbonylaminophenyl) -2,6-di (trichloromethyl)- s-triazine, 4- [p-N- (p-methoxyphenyl) 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) aminophen Le] -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-pN-ethoxycarbonylmethylamino) Phenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-chloro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4 -(M-Fluoro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN-ethoxycarbonylmethylaminophenyl) -2 , 6-Di (trichloromethyl) -s-triazine, 4- (o-chloro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloro) Methyl) -s-triazine, 4- (o-fluoro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-bromo-pN- Chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-chloro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine 4- (m-fluoro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN-chloroethylaminophenyl) -2 , 6-Di (trichloromethyl) -s-triazine, 4- (o-chloro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4 (O-FLUORO -p-N-chloroethyl aminophenyl) -2,6-di (trichloromethyl) -s-triazine, and the like.

  In addition, TAZ series (for example, TAZ-107, TAZ-110, TAZ-104, TAZ-109, TAZ-140, TAZ-204, TAZ-113, TAZ-123, etc.) manufactured by Midori Chemical, manufactured by PANCHIM T series (for example, T-OMS, T-BMP, T-R, T-B, etc.), Irgacure series (for example, Irgacure 369, Irgacure 784, Irgacure 651, Irgacure 184, Irgacure 500, Irgacure 1000) manufactured by Ciba Geigy Irgacure 149, Irgacure 819, Irgacure 261, etc.), Darocur series (eg Darocur 1173, etc.),

4,4′-bis (diethylamino) -benzophenone, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 2-benzyl-2-dimethylamino-4- Morpholinobyrophenone, 2,2-dimethoxy-2-phenylacetophenone, 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazolyl dimer 2- (o-methoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-dimethoxyphenyl) -4 , 5-Diphenylimidazolyl dimer, 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer , 2-(p-methyl) -4,5-diphenyl imidazolyl dimer, benzoin isopropyl ether, etc. are also useful.

  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 polykettle aldonyl compound described in US Pat. No. 2,367,660, the α described in US Pat. Nos. 2,367,661 and 2,367,670 Carbonyl compounds, acyloin ethers described in US Pat. No. 2,448,828, aromatic acyloin compounds substituted with α-hydrocarbons described in US Pat. No. 2,722,512, US Polynuclear quinone compounds described in Patent Nos. 3,046,127 and 2,951,758, and triallylimidazole dimer / p-aminophenyl ketone described in US Pat. No. 3,549,367. Combinations, benzothiazole compounds / trihalomethyl-s-triazine compounds described in JP-B 51-48516, and the like can be mentioned.

  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. 1-20 mass% is especially preferable. 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, benzoin, 9-fluorenone, 2-chloro-9-fluorenone, 2-methyl-9-fluorenone, 9-anthrone, 2-bromo-9-anthrone, 2-ethyl-9. Anthrone, 9,10-anthraquinone, 2-ethyl-9,10-anthraquinone, 2-t-butyl-9,10-anthraquinone, 2,6-dichloro-9,10-anthraquinone, xanthone, 2-methylxanthone, 2-methoxyxanthone, 2-ethoxyxanthone, thioxanthone, 2,4-diethylthioxanthone, acridone, 10-butyl-2-chloroacridone, benzyl, dibenzalacetone, p- (dimethylamino) phenylstyryl ketone, p- (Dimethylamino) phenyl-p-methyls Rilketone, benzophenone, p- (dimethylamino) benzophenone (or Michler's ketone), p- (diethylamino) benzophenone, benzoanthrone, benzothiazole compounds described in Japanese Patent Publication No. 51-48516, tinuvin 1130, 400, etc. Is mentioned.

  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, a naphthoquinone diazide compound suitable for a positive structure will be described. The naphthoquinonediazide compound is a compound having at least one o-quinonediazide group, 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, a phenol compound described in general formula (I) in JP-A-2-84650 and JP-A-3-49437. .

  In addition, when the colored curable composition is constituted as a positive type, the binder and the crosslinking agent are usually about 2 to 50% by mass and about 2 to 30% by mass, respectively, of the total solid content added to the solvent. It is preferable to dissolve at a ratio of In addition, the contents of the naphthoquinone diazide compound and the dye are preferably about 2 to 30% by mass and about 2 to 50% by mass, respectively, with respect to the mass of the solution in which the binder and the crosslinking agent are dissolved. .

-Solvent-
In preparing the colored curable composition of the present invention, a solvent can generally be contained. The solvent is 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, Methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc .;

3-oxypropionic acid alkyl esters such as methyl 3-oxypropionate and ethyl 3-oxypropionate, such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy Ethyl propionate, etc .; 2-oxypropionic acid alkyl esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, such as methyl 2-methoxypropionate, 2-methoxypropion Acid ethyl, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, 2-methoxy- 2-methylpropio Methyl acid, 2-ethoxy-2-methylpropionic acid ethyl, etc; methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc .;

Ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether, propylene glycol methyl Ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, etc .; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc .; aromatic hydrocarbons such as toluene, xylene, etc. Preferably mentioned .

  Among these, 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 methyl 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, for example, aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid; oxalic acid, malonic acid, succinic acid, Aliphatic dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid; Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, camphoric acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, Aromatic polycarboxylic acids such as trimesic acid, melophanoic acid, pyromellitic acid; phenylacetic acid Hydratropic acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetic acid, coumaric acid, other carboxylic acids such as umbellic acid.

  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.), a printing ink, and an inkjet ink. And can be suitably used as a production application for paints and the like.

<< 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 produced 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 ( 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. In addition, 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.

  In the production of a color filter, in the case of a negative type, the image forming step (and a curing step if necessary) is repeated according to a desired number of hues. In the case of a positive type, the image forming step and post-baking are performed. By repeating according to the desired number of hues, a color filter configured with a desired number of hues can be produced.

Examples of the support include soda glass, Pyrex (R) glass, and quartz glass used for liquid crystal display elements and the like, a transparent conductive film attached thereto, a photoelectric conversion element substrate used for an imaging element, and the like. For example, a silicon substrate, a complementary metal oxide semiconductor (CMOS), or the like can be given. These supports may be formed with 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, any developer may be used as long as it has a composition that dissolves the uncured portion of the colored curable composition of the present invention but does not dissolve the cured portion. it can. Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used. As said organic solvent, the above-mentioned solvent used for preparation of the colored curable composition of this invention can be mentioned.

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

  The color filter of the present invention can be used for a solid-state image pickup 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 having more than 1 million pixels. The color filter of the present invention can be used as, for example, a color filter disposed between a light receiving portion of each pixel constituting a CCD and a microlens for condensing light.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. Unless otherwise specified, “part” is based on mass.

(Example 1)
1) Preparation of resist solution (negative type)
Propylene glycol monomethyl ether acetate 5.20 parts (PGMEA)
-Ethyl lactate (EL)-52.6 parts-Binder-30.5 parts [Benzyl methacrylate / methacrylic acid / methacrylic acid-2-hydroxyethyl copolymer (copolymerization ratio [molar ratio] = 60) / 20/20) 41% EL solution]
Dipentaerythritol hexaacrylate 10.2 parts Polymerization inhibitor (p-methoxyphenol) 0.006 parts Fluorosurfactant 0.80 parts TAZ-107 (Midori Chemical) (Manufactured by company; photopolymerization initiator)..

2) Production of glass substrate with undercoat layer A glass substrate (Corning 1737) was ultrasonically washed with 0.5% NaOH water, followed by washing with water and dehydration baking (200 ° C./20 minutes). Next, the resist solution obtained in 1) above was applied onto 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 form a cured film (undercoat layer). .

3) Preparation of dye resist solution (colored curable composition [negative type]) 9.4 g of the resist solution obtained in the above 1) and the exemplified compound (1) described above which is an azo dye according to the present invention [general formula Dye represented by (1)] 0.75 g was mixed and dissolved to prepare a dye resist solution (colored curable composition [negative type] solution).

4) Exposure and development of dye resist solution (image formation)
The dye resist solution obtained in 3) above was applied on the undercoat layer of the glass substrate with an 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.
Then, using an exposure apparatus, the coating film was irradiated at a wavelength of 365 nm through a mask having a line width of 20 μm with an exposure amount of 500 mJ / cm ² . After irradiation, development was performed using a developer CD-2000 (manufactured by Fuji Film Arch Co., Ltd.) at 25 ° C. for 40 seconds. Then, after rinsing with running water for 30 seconds, spray drying was performed.
As described above, a yellow pattern suitable as a yellow color constituting the color filter was obtained.

5) Evaluation The storage stability of the dye resist solution prepared above over time, and the heat resistance and light resistance of the coating film coated on the glass substrate using the dye resist solution were evaluated as follows. The evaluation results are shown in Table 1 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.
X: Precipitation was recognized.

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

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

(Examples 2 to 10)
In Example 1, “3) Preparation of dye resist solution”, a yellow pattern was formed in the same manner as in Example 1, except that the azo dye according to the present invention was changed as shown in Table 1 below (but equimolar). A similar evaluation was made. The evaluation results are shown in Table 1 below.

(Comparative Examples 1-2)
In Example 1, “3) Preparation of dye resist solution”, a comparative yellow was prepared in the same manner as in Example 1 except that the azo dye according to the present invention was changed as shown in Table 1 below (but equimolar). A pattern was formed and the same evaluation was performed. The evaluation results are shown in Table 1 below together with the results of the examples.

  As shown in Table 1 above, in the examples using the azo dyes according to the present invention, all of the colored curable compositions prepared in a solution state are stable in storage as compared with the comparative examples using other dyes. The yellow pattern formed using this colored curable composition was excellent in heat resistance and light resistance.

(Example 11)
1) Preparation of colored curable composition [positive type] The following compositions were mixed and dissolved to prepare a solution-like colored curable composition [positive type].
・ Ethyl lactate (EL): 30 parts ・ Resin P-1: 3.0 parts ・ Naphthoquinonediazide 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 (fluorine-based surfactant; Dainippon Ink and Chemicals, Inc.) Industrial)
-Illustrative compound of azo dye according to the present invention (3) 1.5 parts (colorant represented by general formula (1))

-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. A polymerization amount of a polymerization initiator V-65 (manufactured by Wako Pure Chemical Industries, Ltd.) was added at 65 ° C. and stirred for 10 hours. The obtained resin solution was added dropwise to 20 L (liter) 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 P-1. When this molecular weight was measured by GPC, the weight average molecular weight Mw = 28,000 and the 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 into a large amount of water with stirring. Precipitated naphthoquinone diazide sulfonic acid ester was collected by suction filtration and vacuum dried at 40 ° C. for 24 hours to obtain photosensitive naphthoquinone diazide compound N-1.

2) 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 yellow pattern, and then this pattern was heated at 180 ° C. for 5 minutes (post-baking). The formed yellow pattern showed a good rectangular profile.

  Subsequently, when the storage stability of the dye resist solution prepared above and the heat resistance and light resistance of the coating film coated on the glass substrate using the dye resist solution were evaluated in the same manner as in Example 1, As in the case of the negative type, storage stability, light resistance, and heat resistance were all good.

(Examples 12 to 21)
Except having replaced the glass substrate of Examples 1-10 with the silicon wafer substrate, operation similar to Example 1-10 was performed and the coating film was coated on the silicon wafer substrate. Next, a 2 μm square pattern is exposed at an exposure amount of 500 mj / cm ² using an i-line reduction projection exposure apparatus, and a developer obtained by diluting CD-2000 (manufactured by Fuji Film Arch) to 60% is used. Developed at 23 ° C. for 60 seconds. Subsequently, after rinsing with running water for 30 seconds, spray drying was performed. As described above, a pattern suitable as a CCD color filter having a substantially square cross section and a good profile could be obtained.

(Examples 22 to 24)
According to the method described in Example 1 of JP-A-2002-14223, C.I.Solvent Yellow 162 described herein is converted to an equimolar amount of the azo dye (Exemplary Compound (2), (7 ), (11); a positive composition is obtained in the same manner as in the method described in Example 1 of JP-A No. 2002-14223 except that it is replaced with a dye represented by the general formula (1). It was. Using the obtained composition, a yellow filter layer was formed in the same manner as in Example 1 of the publication, and the heat resistance and light resistance were evaluated in the same manner as in Example 1 described above. A trend similar to the results shown was observed.

Claims (3)

The coloring curable composition characterized by including the pigment | dye represented by following General formula (1).
[In General Formula (1), X represents a sulfur atom or —N (—Q ¹ ) —, Q represents a nonmetallic atom group necessary for forming a 5-membered heterocyclic ring together with X, The heterocycle may be condensed. Q ¹ represents a hydrogen atom, aliphatic group, heterocyclic group, aryl group, acyl group, aliphatic oxycarbonyl group, aryloxycarbonyl group, carbamoyl group, aliphatic sulfonyl group, arylsulfonyl group, or sulfamoyl group. B ¹ represents —CR ⁴ ═ or a nitrogen atom, B ² represents —CR ⁵ ═ or a nitrogen atom, and B ¹ and B ² do not represent a nitrogen atom at the same time. R ⁴ and R ⁵ each independently represents a hydrogen atom or a substituent. G ¹ and G ² each independently represent a substituent. However, G ² is not a group linked by a nitrogen atom. R ⁴ and R ⁵ and / or R ⁵ and G ² may be bonded to each other to form a 5- to 7-membered hydrocarbon ring or a 5- to 7-membered heterocyclic ring. ] The color filter characterized by including the pigment | dye represented by following General formula (1).
[In General Formula (1), X represents a sulfur atom or —N (—Q ¹ ) —, Q represents a nonmetallic atom group necessary for forming a 5-membered heterocyclic ring together with X, The heterocycle may be condensed. Q ¹ represents a hydrogen atom, aliphatic group, heterocyclic group, aryl group, acyl group, aliphatic oxycarbonyl group, aryloxycarbonyl group, carbamoyl group, aliphatic sulfonyl group, arylsulfonyl group, or sulfamoyl group. B ¹ represents —CR ⁴ ═ or a nitrogen atom, B ² represents —CR ⁵ ═ or a nitrogen atom, and B ¹ and B ² do not represent a nitrogen atom at the same time. R ⁴ and R ⁵ each independently represents a hydrogen atom or a substituent. G ¹ and G ² each independently represent a substituent. However, G ² is not a group linked by a nitrogen atom. R ⁴ and R ⁵ and / or R ⁵ and G ² may be bonded to each other to form a 5- to 7-membered hydrocarbon ring or a 5- to 7-membered heterocyclic ring. ]   A method for producing a color filter, comprising: applying a colored curable composition according to claim 1 onto a support, exposing the film through a mask, and developing to form a pattern image.