JP4328250B2 - Colored curable composition for color filter, color filter and method for producing the same - Google Patents

Description

The present invention relates to a colored curable composition for a color filter containing a nitrogen-containing heterocyclic azo dye, a color filter, and a method for producing the same.

  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, refer to 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 yellow dye and magenta dye are used for the red filter array of the color filter (see, for example, Patent Document 13). However, the pyrazolone azo dyes and xanthene dyes used are insufficient in heat resistance and light resistance. Further, 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 robustness.

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 Japanese Patent Laid-Open No. 2002-14220

  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 and magenta 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, high resolution with high sensitivity, and has a high transmittance characteristics, the hue is good, the color filter heat fastness and light fastness and excellent high stability over time providing use colored curable composition, and, which has a high resolution and high transmittance characteristics, hue of a good heat fastness and light fastness with high color filters, and high productivity of the color filter It aims at providing the manufacturing method of the color filter which enables manufacture, and makes it the subject of this invention to achieve this objective.

In the present invention, various dye compound derivatives having a good hue and high fastness to light and heat have been examined in detail, and a specific nitrogen-containing heterocyclic azo dye has a particularly good hue. And obtaining knowledge that it is useful for improving fastness such as heat resistance and light resistance, and based on this knowledge, a colored curable composition for color filters having the following constitution, a color filter and a method for producing the same are provided. The object has been achieved. Specific means for achieving the above object are as follows.

<1> At least one selected from the dye represented by the following general formula (1), the dye represented by the following general formula (2) and the dye represented by the following general formula (3) , A colored curable composition for a color filter , comprising at least one radiation-sensitive compound . The colored curable composition for a color filter preferably further contains a binder and a polymerizable monomer.

In the general formula (1), R ^a1 represents an aliphatic group, an aryl group, a heterocyclic group, an acyl group, an aliphatic oxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an aliphatic sulfonyl group, an arylsulfonyl group, or It represents a sulfamoyl group, and R ^a2 represents a hydrogen atom or a substituent. X ^a1 represents —CR ^a3 = or a nitrogen atom, and R ^a3 represents a hydrogen atom or a substituent. B represents a coupler-residue. When R ^a1 and R ^a2 and / or X ^a1 represents —CR ^{a3 ═} , R ^a2 and R ^a3 may be bonded to each other to form a 5- to 7-membered ring.

In the general formula (2), A represents a residue of a 5-membered heterocyclic diazo component A-NH ₂ . B ¹ represents represents -CR ¹ = or a nitrogen atom, B ² represents -CR ² = or a nitrogen atom, B ¹ and B ² do not simultaneously represent a nitrogen atom. R ⁵ and R ⁶ are each independently a hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group, or It represents a sulfamoyl group, and R ⁵ and R ⁶ do not represent a hydrogen atom at the same time. G, R ¹ and R ² are each independently a hydrogen atom, halogen atom, aliphatic group, aromatic group, heterocyclic group, cyano group, carboxyl group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, Substituted with acyl group, hydroxy group, alkoxy group, aryloxy group, silyloxy group, acyloxy group, carbamoyloxy group, heterocyclic oxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, alkyl group or aryl group or heterocyclic group Substituted amino group, acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkylsulfonylamino group, arylsulfonylamino group, aryloxycarbonylamino group, nitro group, alkyl O group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group, an alkylsulfinyl group, an arylsulfinyl group, a sulfamoyl group, a sulfo group, or a heterocyclic thio group. R ¹ and R ⁵ and / or R ⁵ and R ⁶ may be bonded to each other to form a 5-membered or 6-membered ring.

In the general formula (3), Rd ₁ , Rd ₂ , Rd ₃ , and Rd ₄ each independently represent a hydrogen atom or an aliphatic group, Rd ₅ represents a sulfo group or a sulfamoyl group, Rd ₆ , Rd ₇ , Rd ₈ , Rd ₉ , and Rd ₁₀ each independently represent a substituent. m, n, p, and q each independently represent an integer of 0 to 3, and r represents an integer of 0 to 4.

  <2> At least one dye represented by the following general formula (1) and at least one selected from a dye represented by the following general formula (2) and a dye represented by the following general formula (3) It is a color filter characterized by including.

In the general formula (1), as described above, R ^a1 represents an aliphatic group, an aryl group, a heterocyclic group, an acyl group, an aliphatic oxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an aliphatic sulfonyl group, An arylsulfonyl group or a sulfamoyl group is represented, and R ^a2 represents a hydrogen atom or a substituent. X ^a1 represents —CR ^a3 = or a nitrogen atom, and R ^a3 represents a hydrogen atom or a substituent. B represents a coupler-residue. When R ^a1 and R ^a2 and / or X ^a1 represents —CR ^{a3 ═} , R ^a2 and R ^a3 may be bonded to each other to form a 5- to 7-membered ring.

In the general formula (2), as described above, A represents a residue of a 5-membered heterocyclic diazo component A-NH ₂ . B ¹ represents represents -CR ¹ = or a nitrogen atom, B ² represents -CR ² = or a nitrogen atom, B ¹ and B ² do not simultaneously represent a nitrogen atom. R ⁵ and R ⁶ are each independently a hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group, or It represents a sulfamoyl group, and R ⁵ and R ⁶ do not represent a hydrogen atom at the same time. G, R ¹ and R ² are each independently a hydrogen atom, halogen atom, aliphatic group, aromatic group, heterocyclic group, cyano group, carboxyl group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, Substituted with acyl group, hydroxy group, alkoxy group, aryloxy group, silyloxy group, acyloxy group, carbamoyloxy group, heterocyclic oxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, alkyl group or aryl group or heterocyclic group Substituted amino group, acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkylsulfonylamino group, arylsulfonylamino group, aryloxycarbonylamino group, nitro group, alkyl O group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group, an alkylsulfinyl group, an arylsulfinyl group, a sulfamoyl group, a sulfo group, or a heterocyclic thio group. R ¹ and R ⁵ and / or R ⁵ and R ⁶ may be bonded to each other to form a 5-membered or 6-membered ring.

In the general formula (3), as described above, Rd ₁ , Rd ₂ , Rd ₃ , and Rd ₄ each independently represent a hydrogen atom or an aliphatic group, and Rd ₅ represents a sulfo group or a sulfamoyl group. , Rd ₆ , Rd ₇ , Rd ₈ , Rd ₉ , and Rd ₁₀ each independently represent a substituent. m, n, p, and q each independently represent an integer of 0 to 3, and r represents an integer of 0 to 4.

<3> A color filter comprising a step of applying a colored curable composition for a color filter according to <1> above onto a support, exposing through a mask, and developing to form a pattern image. It is a manufacturing method.
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, a colored curable composition for a color filter having high sensitivity, high resolution, high transmittance, good hue, high heat fastness and light fastness, and excellent temporal stability, and Provided are a color filter having high resolution and high transmittance characteristics, good hue, high heat fastness and high light fastness, and a method for producing a color filter capable of producing the color filter with high productivity. can do.

Hereinafter, the colored curable composition for a color filter of the present invention, the color filter, and the production method thereof will be described in detail.
[Colored curable composition for color filter ]
The colored curable composition for a color filter of the present invention includes, as a pigment, at least one compound represented by the following general formula (1), a compound represented by the following general formula (2), and the following general formula (3). at least one and in than the compound represented by the selected (hereinafter, also collectively called "dye according to the present invention".), further comprises at least one radiation-sensitive compound, preferably a binder and weight polymerizable monomer Comprising. 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; dye which concerns on this invention) represented by following General formula (1). This dye exhibits a good hue, does not precipitate over time when it is in the state of a liquid preparation or a coated film, and has excellent stability, and particularly has resistance to heat and light.

  The “aliphatic” in the general formula (1) is linear, branched, or cyclic, and may be saturated or unsaturated. For example, alkyl, alkenyl, cycloalkyl, cyclo It includes alkenyl and may be unsubstituted or substituted with a substituent. Further, “aryl” in the general formula (1) 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. The “heterocycle” in the general formula (1) is one in which the heterocycle portion has a heteroatom (for example, a nitrogen atom, a sulfur atom, or an 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 general formula (1) 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, 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 sulfonamido group, arylsulfonamido group, heterocyclic sulfonamido group, amino group, aliphatic amino group, arylamino group, heterocyclic amino group, aliphatic oxy Carbonylamino group, aryloxycarbonylamino group Heterocyclic 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), R ^a1 represents an aliphatic group, an aryl group, a heterocyclic group, an acyl group, an aliphatic oxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an aliphatic sulfonyl group, an arylsulfonyl group, or Represents a sulfamoyl group.

The aliphatic group represented by R ^a1 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 aryl group represented by R ^a1 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 heterocyclic group represented by R ^a1 may be a saturated or unsaturated ring group, and is preferably a heterocyclic group having 3 to 15 carbon atoms in total. For example, 3-pyridyl group, 2-pyridyl group, 2-pyrimidinyl group, 2-pyrazinyl group and the like can be mentioned.
The acyl group represented by R ^a1 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 R ^a1 may be unsubstituted or substituted, may be a saturated group or an unsaturated group, and is 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 R ^a1 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 R ^a1 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 R ^a1 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 R ^a1 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-butylphenylsulfonyl group, 4-toluenesulfonyl group, 2-toluenesulfonyl group and the like can be mentioned.
The sulfamoyl group represented by R ^a1 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.

Among the above, R ^a1 is preferably an aliphatic group, an aryl group, or a heterocyclic group, more preferably an aryl group or a heterocyclic group, from the viewpoint of more effectively achieving the effects of the present invention. In the case of an aryl group, it is most preferable.

In the general formula (1), R ^a2 represents a hydrogen atom or a substituent. X ^a1 represents —CR ^a3 = or a nitrogen atom, and R ^a3 represents a hydrogen atom or a substituent.
The substituent represented by R ^a2 or R ^a3 may be any group as long as it is a group that can be substituted as described in the above-mentioned “Substituent” section. Of these, R ^a2 and R ^a3 are each preferably the following groups from the viewpoint of more effectively achieving the effects of the present invention. That is,
R ^a2 is a hydrogen atom, aliphatic group, aryl group, acyloxy group, acylamino group, aliphatic oxy group, aliphatic sulfonyloxy group, arylsulfonyloxy group, aliphatic sulfonamido group, arylsulfonamido group, amino group, When representing an aliphatic amino group, arylamino group, aliphatic oxycarbonylamino group, aryloxycarbonylamino group, heterocyclic oxycarbonylamino group, hydroxy group, cyano group, sulfo group, carbamoylamino group, sulfamoylamino group More preferably, it represents a hydrogen atom, an aliphatic group, an aryl group, an acyloxy group, an aliphatic oxy group, or an aliphatic sulfonyloxy group, and most preferably a hydrogen atom or an aliphatic group.

R ^a3 is an aliphatic group, aryl group, acyl group, acylamino group, aliphatic oxycarbonyl group, aryloxycarbonyl group, carbamoyl group, aliphatic sulfonyl group, arylsulfonyl group, heterocyclic sulfonyl group, aliphatic sulfonyl group An oxy group, an arylsulfonyloxy group, an aliphatic sulfonamido group, an arylsulfonamido group, a cyano group, and a carboxyl group are preferable, and X ^a1 is preferably selected from —CR ^a3 = and nitrogen atom. R ^a3 is more preferably an acyl group, an aliphatic oxycarbonyl group, an aliphatic sulfonyl group, an arylsulfonyl group, a cyano group, or a carboxyl group, and X ^a1 is selected from —CR ^{a3 ═} and nitrogen atom It is more preferable that Furthermore, R ^a3 is most preferably an aliphatic oxycarbonyl group, an aliphatic sulfonyl group, or a cyano group, and X ^a1 is most preferably selected from —CR ^a3 = and a nitrogen atom.

In the general formula (1), B represents a coupler residue.
The coupler residue represented by B is not particularly limited as long as it is a group capable of coupling with a diazonium salt, and examples thereof include a hydrocarbon ring group, a heterocyclic group, and a substituted methylene group. This B is a coupler in which the dye represented by the general formula (1) may constitute either a non-dissociation dye or a dissociation dye (a dye containing a group that becomes alkaline and dissociates and becomes a target hue). Residue. More specifically, groups represented by the following (B-1) to (B-13) are exemplified.

In the (B-1) to (B-13), R ^{a6 to} R ^a47 each represents a hydrogen atom or a substituent. The substituent here is the group described in the above-mentioned “Substituent” section, and may be any group that can be substituted. Preferred substituents include aliphatic groups, aryl groups, heterocyclic groups, acyl groups. Group, acylamino group, aliphatic oxy group, aliphatic oxycarbonyl group, carbamoyl group, sulfamoyl group, aliphatic sulfonamido group, arylsulfonamido group, amino group, aliphatic amino group, hydroxy group, cyano group, sulfo group, It is a carboxyl group.

^{R a6 ~R a14, R a15 ~R} a17, R a45 ~R adjacent two groups of ^a47, and R ^a19 and R ^a20, R ^a21 and R ^a22, R ^a23 and R ^a24, R ^a29 and R ^a30, R ^a31 and R ^a32, R ^a33 and R ^a34, and R ^a35 and R ^a36 is a hydrocarbon ring of 5-membered ring to 7-membered ring together as possible, it may form a heterocyclic ring.

Further, (B-9) in the Q ^a1, Q ^a3 in (B-11) Q ^a2, and in (B-12) is required to form each 5-membered ring to 7-membered ring together with the nitrogen atom Represents a non-metallic atomic group.

Among the above, R ^a6 and R ^a8 , R ^a11 and R ^a13 , R ^a15 and R ^a17 and R ^a18 , R ^a19 and R ^a22 , R ^a24 and R ^a25 , from the viewpoint of more effectively ^achieving the effects of the present invention. R ^a26 and R ^a27 and R ^a28, each of the at least one hydroxy group, preferably if a substituted amino group, may represent a substituted amino group are more preferable. Similarly, R ^a31 preferably represents an aliphatic group or an aromatic group, more preferably an aliphatic group, from the viewpoint of more effectively achieving the effects of the present invention. Similarly, R ^a32 is preferably a hydroxy group, R ^a39 preferably ^represents a hydroxy group or an optionally substituted amino group, and R ^a39 is substituted from the viewpoint of more effectively ^achieving the effects of the present invention. More preferably, it represents a good amino group.

  From the viewpoint of achieving the effects of the present invention particularly effectively, B preferably represents (B-1), (B-3), (B-6), or (B-7).

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

In the general formula ^{(1-1), R a1, R} a2, X a1, and R ^a3 has the same meaning as ^{R a1, R a2, X a1} , and R ^a3 in the above general formula (1), The same applies to each preferred embodiment.
In general formula (1-1), B ^a1 represents —CR ^a4 = or a nitrogen atom, B ^a2 represents —CR ^a5 = or a nitrogen atom, and B ^a1 and B ^a2 do not represent a nitrogen atom at the same time. R ^a4 and R ^a5 represent a hydrogen atom or a substituent. In the general formula (1-1), R ^a1 and R ^a2 , R ^a2 and R ^a3 , R ^a4 and R ^a5 , and R ^a5 and G ^a2 are bonded to each other to form a 5-membered ring to a 7-membered ring. Also good.

The substituent represented by R ^a4 or R ^a5 is the group described in the above-mentioned “Substituent” section and may be any group that can be substituted. R ^a4 and R ^a5 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 formula (1-1), B ^a1 is a -CR ^a4 =, B ^a2 preferably may represent -CR ^a5 = or a nitrogen atom, B ^a1 is a -CR ^a4 =, B ^a2 is -CR ^a5 = Is more preferable. When B ^a1 represents -CR ^a4 = and B ^a2 represents -CR ^a5 =, it is most preferable that R ^a4 represents an aliphatic group and R ^a5 represents a hydrogen atom or a cyano group.

In the general formula (1-1), G ^a1 and G ^a2 each independently represent a hydrogen atom or a substituent. The substituent represented by G ^a1 or G ^a2 is the group described in the above-mentioned “Substituent” section and may be any group that can be substituted. G ^a1 and G ^a2 are each a hydrogen atom, an aliphatic group, an aryl group, a heterocyclic group, an acyloxy group, an acylamino group, an aliphatic oxy group, an aryloxy group from the viewpoint of more effectively achieving the effects of the present invention. , Heterocyclic oxy group, aliphatic sulfonamide group, aryl sulfonamide group, heterocyclic sulfonamide group, amino group, aliphatic amino group, arylamino group, heterocyclic amino group, aliphatic oxycarbonylamino group, aryloxycarbonyl Preferably represents an amino group, heterocyclic oxycarbonylamino group, aliphatic thio group, arylthio group, hydroxy group, cyano group, sulfo group, carboxyl group, carbamoylamino group, sulfamoylamino group, halogen atom, hydrogen atom , Aliphatic group, heterocyclic group, acylamino group, aliphatic oxy group, aryl More preferably represents a xy group, an aliphatic sulfonamido group, an arylsulfonamido group, an aliphatic amino group, an arylamino group, a heterocyclic amino group, an aliphatic thio group, an arylthio group, a halogen atom, an aliphatic oxy group, Most preferred is an aliphatic amino group, an arylamino group, or an aliphatic thio group, and an embodiment in which at least one of G ^a1 and G ^a2 represents an aliphatic amino group or an aromatic amino group is preferred.

R ^a1 and R ^a2 , R ^a2 and R ^a3 , R ^a4 and R ^a5 and R ^a5 and G ^a2 are bonded to each other to form a 5- to 7-membered ring (which may be aromatic or non-aromatic, carbon It may be a ring or a heterocyclic ring, and may form a benzene ring, a pyridine ring, etc.).

Furthermore, among the dyes represented by the general formula (1), a dye represented by the following general formula (1-2) is particularly preferable.

In the general formula (1-2), R ^a1 , R ^a2 , R ^a3 , R ^a4 , R ^a5 , X ^a1 , G ^a1 , and G ^a2 are the same as those in the general formula (1) or the general formula (1- It is synonymous with R ^a1 , R ^a2 , R ^a3 , R ^a4 , R ^a5 , X ^a1 , G ^a1 and G ^{a2 in 1)} , and these preferable embodiments are also the same.

In the general formula (1-2), R ^a1 represents an aliphatic group, an aryl group, or a heterocyclic group, and R ^a2 represents a hydrogen atom, an aliphatic group, or aryl from the viewpoint of more effectively achieving the effects of the present invention. Group, acyloxy group, aliphatic oxy group, aliphatic sulfonyloxy group, arylsulfonyloxy group, hydroxy group, cyano group, R ^a3 is an acyl group, aliphatic oxycarbonyl group, aliphatic sulfonyl group, arylsulfonyl group, Represents a cyano group or a carboxyl group, R ^a4 and R ^a5 represent a hydrogen atom, an aliphatic group or a cyano group, and G ^a1 and G ^a2 represent a hydrogen atom, an aliphatic group, a heterocyclic group, an acylamino group or an aliphatic oxy group , Aryloxy group, aliphatic sulfonamido group, arylsulfonamido group, aliphatic amino group, arylamino group, heterocyclic amino group, aliphatic thio group, arylthio group Hydroxy groups, are preferred if a halogen atom, R ^a1 represents an aryl group, R ^a2 represents a hydrogen atom, an aliphatic group, R ^a3 represents an aliphatic oxycarbonyl group, an aliphatic sulfonyl group, a cyano group, Most preferably, R ^a4 represents an aliphatic group, R ⁵ represents a hydrogen atom or a cyano group, and G ^a1 and G ^a2 represent an aliphatic oxy group, an aliphatic amino group, an arylamino group, or an aliphatic thio group. .

When the pigment represented by the general formula (1), (1-1) or (1-2) is a water-soluble dye, any one of B, R ^a1 , R ^a2 , G ^a1 and G ^a2 It is preferable to further have an ionic hydrophilic group as a substituent at the position. Examples of the ionic hydrophilic group as a substituent include a sulfo group, a carboxyl group, and a quaternary ammonium group. As the ionic hydrophilic group, a carboxyl group and a sulfo group are preferable, and a sulfo group is particularly preferable. The carboxyl group and the sulfo group may be in a salt state, and examples of the counter ion forming the salt include an alkali metal ion (for example, sodium ion, potassium ion) and an organic cation (for example, tetramethylguanidinium ion). It is.

  Hereinafter, specific examples (Exemplified Compounds 1 to 102) of the pigment represented by the general formula (1), (1-1), or (1-2) (the dye according to the present invention) are 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) while stirring 93.5 g (0.50 mol) of 3- (2-ethylhexyloxy) propylamine with water. Was gradually added. Thereafter, the mixture was further stirred at 120 ° C. for 4 hours. After the temperature of the resulting 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 layer was washed twice with 200 ml of saturated brine. Subsequently, ethyl acetate was distilled off under reduced pressure, and the resulting viscous liquid was purified by silica gel column chromatography to obtain 45.5 g of compound (B) as a colorless viscous liquid (yield 93.2%). ).

  Separately, 1.5 g (0.022 mol) of sodium nitrite was added to a solution of 2.16 g (0.02 mol) of compound (C) dissolved in 25 ml of phosphoric acid while stirring at 0 ° C. Stir for minutes. To this reaction solution, 9.7 g (0.02 mol) of the compound (B) obtained above was added and stirred at 25 ° C. for 3 hours. 300 ml of water was further added to the obtained reaction solution, and the mixture was stirred for 1 hour, and the precipitated crystals were filtered and washed thoroughly with water. The obtained crystals were dried to obtain 11.0 g of Compound (D) (yield 90.1%).

  Next, 30 ml of dimethylacetamide, 3.0 g of potassium carbonate, and 2.0 g (0.014 mol) of p-fluoronitrobenzene are added to 6.1 g (0.01 mol) of the compound (D), and the mixture is heated at 75 ° C. for 2 hours. Stir. The reaction mixture was poured into a mixture of 100 ml of water and 100 ml of ethyl acetate, and the phases were separated. The ethyl acetate phase was washed twice with 100 ml of saturated brine. Ethyl acetate was distilled off under reduced pressure and the residue was purified by silica gel column chromatography, crystallized with 40 ml of acetonitrile, filtered, washed with 20 ml of cold acetonitrile and dried to give an azo compound [Exemplary Compound 1 (general formula ( 4.8 g (yield 65.9%).

The melting point of the obtained azo compound was measured, and the maximum absorption wavelength (λ _max ) and molar extinction coefficient (ε) of the azo compound in ethyl acetate were measured with a spectrophotometer UV-2400PC (manufactured by Shimadzu Corporation). The melting point was 157 to 158 ° C., the maximum absorption wavelength λ _{max was} 466.9 nm, and ε49,300.
In addition, it can synthesize | combine other exemplary compounds other than the above-mentioned exemplary compound 1 by the method approximated to the above by changing said compound (A) and (C) into a desired compound.

  The colored curable composition of the present invention includes at least a dye represented by the following general formula (2) and / or a dye represented by the general formula (3) together with the dye represented by the general formula (1). Contains one kind.

-Dye represented by general formula (2)-
The coloring matter represented by the following general formula (2) (azo dye; dye according to the present invention) also exhibits a good hue and is stable with no precipitation over time when it is in the form of a liquid preparation or a coated film. It has excellent resistance to heat and light.
Hereinafter, the dye represented by the general formula (2) will be described in detail.

In the formula (2), A represents the residue of A-NH ₂ is a 5-membered heterocyclic diazo component. Examples of heteroatoms 5-membered heterocyclic ring constituting A of this A-NH _2, can be mentioned N, O, and S. A nitrogen-containing 5-membered heterocyclic ring is preferable, and an aliphatic ring, an aromatic ring or another heterocyclic ring may be condensed to the heterocyclic ring.

  Preferable examples of the heterocyclic ring in A include a pyrazole ring, an imidazole ring, a thiazole ring, an isothiazole ring, a thiadiazole ring, a benzothiazole ring, a benzoxazole ring, and a benzoisothiazole ring. Each heterocyclic ring may further have a substituent. Among these, a pyrazole ring, an imidazole ring, an isothiazole ring, a thiadiazole ring, and a benzothiazole ring represented by the following general formulas (a) to (f) are preferable.

R ^{7 to} R ²⁰ in the general formulas (a) to (f) have the same meanings as G, R ¹ , and R ² described later, and preferred embodiments thereof are also the same. Of the general formulas (a) to (f), preferred are the pyrazole ring and isothiazole ring represented by the general formula (a) or (b), and the most preferred is represented by the general formula (a). It is a pyrazole ring.

Wherein B ¹ represents represents -CR ¹ = or a nitrogen atom, wherein B ² represents -CR ² = or a nitrogen atom, B ¹ and B ² do not simultaneously represent a nitrogen atom. That is, -CR ¹ =, -CR ² = is represented, or ^one of B ¹ and B ² represents a nitrogen atom, and the other represents -CR ¹ = or -CR ² =. Among others, B ¹ is -CR ¹ =, which B ¹ is represents a -CR ² = is more preferable.

R ⁵ and R ⁶ are each independently a hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group, Alternatively, it represents a sulfamoyl group, and each group may further have a substituent. Preferred groups represented by R ⁵ and R ⁶ include a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, an alkylsulfonyl group, and an arylsulfonyl group, more preferably a hydrogen atom, An aromatic group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group. Most preferably, they are a hydrogen atom, an aryl group, and a heterocyclic group. An embodiment in which each of these preferable groups further has a substituent is also suitable. However, R ⁵ and R ⁶ are not simultaneously hydrogen atoms.

G, R ¹ and R ² are each independently a hydrogen atom, halogen atom, aliphatic group, aromatic group, heterocyclic group, cyano group, carboxyl group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group , Acyl group, hydroxy group, alkoxy group, aryloxy group, silyloxy group, acyloxy group, carbamoyloxy group, heterocyclic oxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, "alkyl group, aryl group or heterocyclic group Substituted amino group substituted by ", acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkyl and arylsulfonylamino group, nitro group, alkyl and arylthio group, alkyl and aryl Ruhoniru group, alkyl or arylsulfinyl group, a sulfamoyl group, a sulfo group or a heterocyclic thio group, and each group may be further substituted.

  Preferred groups represented by G include a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group, a hydroxy group, an alkoxy group, an aryloxy group, an acyloxy group, a heterocyclic oxy group, an “alkyl group, an aryl group or A substituted amino group substituted with a heterocyclic group ”, an acylamino group, a ureido group, a sulfamoylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, an alkyl and arylthio group, or a heterocyclic thio group, and more A hydrogen atom, a halogen atom, an alkyl group, a hydroxy group, an alkoxy group, an aryloxy group, an acyloxy group, a “substituted amino group substituted with an alkyl group, an aryl group or a heterocyclic group”, or an acylamino group is preferable. Of these, a hydrogen atom, an arylamino group, and an amide group are most preferable. Each group may further have a substituent.

Preferable groups represented by R ¹ and R ² include a hydrogen atom, an alkyl group, an alkoxycarbonyl group, a carboxyl group, a carbamoyl group, or a cyano group. Each group may further have a substituent.
R ¹ and R ⁵ and / or R ⁵ and R ⁶ may be bonded to each other to form a 5-membered ring or a 6-membered ring.

The substituents in the case where each group represented by A, R ¹ , R ² , R ⁵ , R ⁶ , G further has a substituent are the same as those mentioned for G, R ¹ , R ² above. Can be mentioned.

When the coloring matter represented by the general formula (2) is a water-soluble dye, an ionic hydrophilic group as a substituent at any position on A, R ¹ , R ² , R ⁵ , R ⁶ , and G It is preferable to further have a sex group. Examples of the ionic hydrophilic group as a substituent include a sulfo group, a carboxyl group, and a quaternary ammonium group. As the ionic hydrophilic group, a carboxyl group and a sulfo group are preferable, and a sulfo group is particularly preferable. The carboxyl group and the sulfo group may be in a salt state, and examples of the counter ion forming the salt include alkali metal ions (eg, sodium ion, potassium ion) and organic cations (eg, tetramethylguanidinium ion). ) Is included.

Hereinafter, each group which concerns on General formula (2) is demonstrated in detail.
In the general formula (2), examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.

  In the general formula (2), the aliphatic group means an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group, an aralkyl group, and a substituted aralkyl group. The aliphatic group may have a branch or may form a ring. The number of carbon atoms in the aliphatic group is preferably 1-20, and more preferably 1-16. The aryl part of the aralkyl group and the substituted aralkyl group is preferably phenyl or naphthyl, particularly preferably phenyl. Examples of aliphatic groups include methyl, ethyl, butyl, isopropyl, t-butyl, hydroxyethyl, methoxyethyl, cyanoethyl, trifluoromethyl, 3-sulfopropyl, 4-sulfobutyl, cyclohexyl group, benzyl group, 2-phenethyl Groups, vinyl groups, and allyl groups.

  In the general formula (2), the aromatic group means an aryl group and a substituted aryl group. The aryl group is preferably phenyl or naphthyl, particularly preferably phenyl. The aromatic group preferably has 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms. Examples of the aromatic group include phenyl, p-tolyl, p-methoxyphenyl, o-chlorophenyl and m- (3-sulfopropylamino) phenyl.

  In the general formula (2), the heterocyclic group includes a heterocyclic group having a substituent and an unsubstituted heterocyclic group. The heterocyclic ring may be condensed with an aliphatic ring, an aromatic ring or another heterocyclic ring. The heterocyclic group is preferably a 5-membered or 6-membered heterocyclic group. Examples of the substituent include aliphatic groups, halogen atoms, alkyl and arylsulfonyl groups, acyl groups, acylamino groups, sulfamoyl groups, carbamoyl groups, ionic hydrophilic groups and the like. Examples of the heterocyclic group include 2-pyridyl group, 2-thienyl group, 2-thiazolyl group, 2-benzothiazolyl group, 2-benzoxazolyl group and 2-furyl group.

  In the general formula (2), the carbamoyl group includes a carbamoyl group having a substituent and an unsubstituted carbamoyl group. Examples of the substituent include an alkyl group. Examples of the carbamoyl group include a methylcarbamoyl group and a dimethylcarbamoyl group.

  In the general formula (2), the alkoxycarbonyl group includes an alkoxycarbonyl group having a substituent and an unsubstituted alkoxycarbonyl group. As the alkoxycarbonyl group, an alkoxycarbonyl group having 2 to 12 carbon atoms is preferable. Examples of the substituent include an ionic hydrophilic group. Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group.

  In the general formula (2), the aryloxycarbonyl group includes an aryloxycarbonyl group having a substituent and an unsubstituted aryloxycarbonyl group. As the aryloxycarbonyl group, an aryloxycarbonyl group having 7 to 12 carbon atoms is preferable. Substituents include ionic hydrophilic groups. Examples of the aryloxycarbonyl group include a phenoxycarbonyl group.

  In the general formula (2), the acyl group includes an acyl group having a substituent and an unsubstituted acyl group. As the acyl group, an acyl group having 1 to 12 carbon atoms is preferable. Examples of the substituent include an ionic hydrophilic group. Examples of the acyl group include an acetyl group and a benzoyl group.

  In the general formula (2), the alkoxy group includes an alkoxy group having a substituent and an unsubstituted alkoxy group. As an alkoxy group, a C1-C12 alkoxy group is preferable. Examples of the substituent include an alkoxy group, a hydroxyl group, and an ionic hydrophilic group. Examples of the alkoxy group include a methoxy group, an ethoxy group, an isopropoxy group, a methoxyethoxy group, a hydroxyethoxy group, and a 3-carboxypropoxy group.

  In the general formula (2), the aryloxy group includes an aryloxy group having a substituent and an unsubstituted aryloxy group. As the aryloxy group, an aryloxy group having 6 to 12 carbon atoms is preferable. Examples of the substituent include an alkoxy group and an ionic hydrophilic group. Examples of the aryloxy group include a phenoxy group, a p-methoxyphenoxy group, and an o-methoxyphenoxy group.

  In the general formula (2), the acyloxy group includes an acyloxy group having a substituent and an unsubstituted acyloxy group. As the acyloxy group, an acyloxy group having 1 to 12 carbon atoms is preferable. Examples of the substituent include an ionic hydrophilic group. Examples of the acyloxy group include an acetoxy group and a benzoyloxy group.

  In the general formula (2), the carbamoyloxy group includes a carbamoyloxy group having a substituent and an unsubstituted carbamoyloxy group. Examples of the substituent include an alkyl group. Examples of the carbamoyloxy group include an N-methylcarbamoyloxy group.

  In the general formula (2), the substituent of “substituted amino group substituted with an alkyl group, aryl group or heterocyclic group” may further have a substituent. Unsubstituted amino groups are not included. As an alkylamino group, a C1-C6 alkylamino group is preferable. Furthermore, an ionic hydrophilic group is contained in the example of a substituent when it has a substituent. Examples of the alkylamino group include a methylamino group and a diethylamino group. The arylamino group includes an arylamino group having a substituent and an unsubstituted arylamino group. As the arylamino group, an arylamino group having 6 to 12 carbon atoms is preferable. Furthermore, examples of the substituent when having a substituent include a halogen atom and an ionic hydrophilic group. Examples of the arylamino group include an anilino group and a 2-chloroanilino group.

  In the general formula (2), the acylamino group includes an acylamino group having a substituent. The acylamino group is preferably an acylamino group having 2 to 12 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the acylamino group include an acetylamino group, a propionylamino group, a benzoylamino group, an N-phenylacetylamino group, and a 3,5-disulfobenzoylamino group.

  In the general formula (2), the ureido group includes a ureido group having a substituent and an unsubstituted ureido group. The ureido group is preferably a ureido group having 1 to 12 carbon atoms. Examples of the substituent include an alkyl group and an aryl group. Examples of the ureido group include a 3-methylureido group, a 3,3-dimethylureido group, and a 3-phenylureido group.

  In the general formula (2), the sulfamoylamino group includes a sulfamoylamino group having a substituent and an unsubstituted sulfamoylamino group. Examples of the substituent include an alkyl group. Examples of the sulfamoylamino group include an N, N-dipropylsulfamoylamino group.

  In the general formula (2), the alkoxycarbonylamino group includes an alkoxycarbonylamino group having a substituent and an unsubstituted alkoxycarbonylamino group. The alkoxycarbonylamino group is preferably an alkoxycarbonylamino group having 2 to 12 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the alkoxycarbonylamino group include an ethoxycarbonylamino group.

  In the general formula (2), the aryloxycarbonylamino group includes an aryloxycarbonylamino group having a substituent and an unsubstituted aryloxycarbonylamino group. As the aryloxycarbonylamino group, an aryloxycarbonylamino group having 7 to 12 carbon atoms is preferable. Examples of the substituent include an ionic hydrophilic group. Examples of the aryloxycarbonylamino group include a phenoxycarbonylamino group.

  In the general formula (2), the alkylsulfonylamino group and the arylsulfonylamino group include an alkyl and arylsulfonylamino group having a substituent, and an unsubstituted alkyl and arylsulfonylamino group. As the sulfonylamino group, a sulfonylamino group having 1 to 12 carbon atoms is preferable. Examples of the substituent include an ionic hydrophilic group. Examples of the sulfonylamino group include a methanesulfonylamino group, an N-phenylmethanesulfonylamino group, a benzenesulfonylamino group, and a 3-carboxybenzenesulfonylamino group.

  In the general formula (2), the alkylthio group, arylthio group and heterocyclic thio group include an alkylthio group having a substituent, an arylthio group and a heterocyclic thio group and an unsubstituted alkylthio group, an arylthio group and a heterocyclic thio group. It is. As the alkylthio group, arylthio group and heterocyclic thio group, those having 1 to 12 carbon atoms are preferred. Examples of the substituent include an ionic hydrophilic group. Examples of the alkyl, aryl or heterocyclic thio group include a methylthio group, a phenylthio group, and a 2-pyridylthio group.

  In the general formula (2), examples of the alkylsulfonyl group and the arylsulfonyl group include a methanesulfonyl group and a phenylsulfonyl group, respectively. Examples of the alkylsulfinyl group and the arylsulfinyl group include a methanesulfinyl group and a phenylsulfinyl group, respectively.

  In the general formula (2), the sulfamoyl group includes a sulfamoyl group having a substituent and an unsubstituted sulfamoyl group. Examples of the substituent include an alkyl group. Examples of the sulfamoyl group include a dimethylsulfamoyl group and a di- (2-hydroxyethyl) sulfamoyl group.

  Specific examples of the dye represented by the general formula (2) (Exemplary compounds a-1 to a-36, b-1 to b-8, c-1 to c-5, d-1 to d-5) , E-1 to e-5, f-1 to f-33, and g- (1) to g- (68)). However, the present invention is not limited to these.

Next, a synthesis example of the dye represented by the general formula (2) will be described in detail.
[Synthesis Example 1]: Synthesis of Exemplary Compound a-1

<Synthesis of Intermediate (a-1a)>
8 g (48.7 mmol) of 5-amino-3-tert-butyl-4-cyanopyrazole (1), 15 ml of concentrated hydrochloric acid, and 50 ml of water were stirred at an internal temperature of 5 ° C., and 3.36 g (48.7 mmol) of sodium nitrite was stirred. ) Was added in portions over 10 minutes. After stirring for 10 minutes, 50 g of AcONa (sodium acetate), 50 ml of DMF (dimethylformamide) and 50 ml of ethyl acetate were added to 21.3 g (40.6 mmol) of the coupling component (2), and the mixture was stirred. The diazonium salt that had been cooled to 5 ° C. was added over 10 minutes. After the addition of the diazonium salt, the reaction solution was further stirred for 30 minutes, and then 300 ml of saturated brine was added to precipitate the precipitated crystals [intermediate (a-1a)]. The yield was 24.2 g and the yield was 85%.

<Synthesis of Exemplified Compound a-1>
To 14.0 g (20 mmol) of the obtained intermediate (a-1a), 4.4 g (26 mmol) of a heterylating agent (3), 2.8 g of potassium carbonate, and 50 ml of DMAc (dimethylacetamide) were added at 100 ° C. Heated and stirred for 1 hour. After completion of the reaction, the reaction mixture was cooled to room temperature, 200 ml of saturated brine was added, and the precipitated crude crystals [Exemplary Compound a-1] were separated by filtration. Further, this crude crystal was recrystallized from acetonitrile. The yield was 16.7 g and the yield was 80%. Further, the synthesized crude crystal (Exemplary Compound a-1) had a maximum absorption wavelength λmax = 545 nm (DMF solution) and m / z (posi) = 834.

[Synthesis Example 2]: Synthesis of Exemplified Compound b-1

  1 g of compound (b-1a) was dispersed in 3.8 ml of a mixed solvent of acetic acid / propionic acid = 2/3 (v / v), cooled to 0 ° C., and then nitrosylsulfuric acid (41% containing liquid) was added to this dispersion. 2.21 g was gradually added and stirred for 1 hour to obtain a diazo solution. On the other hand, 1.05 g of compound (b-1b) was dissolved in a mixed solvent of 14 ml of dimethylformamide and 6 ml of ethyl acetate, and 2.5 g of sodium acetate was further added and cooled to 0 ° C. to obtain a suspension. The above diazo solution was gradually added dropwise to the resulting suspension, and the reaction was further continued for 2 hours after the completion of the addition. After completion of the reaction, water was added and the precipitated crystals were filtered and purified by silica gel column chromatography to obtain 750 mg of a crystalline product [Exemplary Compound b-1]. The yield was 57.7% and the maximum absorption wavelength λmax was 545 nm.

[Synthesis Example 3]: Synthesis of Exemplified Compound b-6

  1 g of compound (b-6a) was dispersed in 3.8 ml of a mixed solvent of acetic acid / propionic acid = 2/3 (v / v), cooled to 0 ° C., and then nitrosylsulfuric acid (41% containing liquid) was added to this dispersion. 2.21 g was gradually added and stirred for 1 hour to obtain a diazo solution. On the other hand, 1.0 g of compound (b-6b) was dissolved in a mixed solvent of 15 ml of dimethylformamide and 5 ml of ethyl acetate, 2.5 g of sodium acetate was further added, and the mixture was cooled to 0 ° C. to obtain a suspension. The above diazo solution was gradually added dropwise to the resulting suspension, and the reaction was further continued for 2 hours after the completion of the addition. After completion of the reaction, water was added and the precipitated crystals were filtered to obtain crude crystals. The crude crystals were further dissolved in 10 ml of dimethylformamide, 560 mg of potassium carbonate and 1.3 g of 2-chlorobenzothiazole (b-6c) were added, and the mixture was reacted at 110 ° C. for 1 hour. After completion of the reaction, water was added, and the precipitated crude crystals were separated by filtration and purified by silica gel column chromatography to obtain 700 mg of a crystalline product [Exemplary Compound b-6]. The yield was 58.6% and the maximum absorption wavelength λmax was 550 nm.

-Dye represented by general formula (3)-
The coloring matter represented by the following general formula (3) (the dye according to the present invention) also exhibits a good hue and is excellent in stability with no precipitation over time when it is in the form of a liquid preparation or a coated film. Especially resistant to heat and light.
Hereinafter, the dye represented by the general formula (3) will be described in detail.

In the general formula (3), Rd ₁ , Rd ₂ , Rd ₃ , and Rd ₄ each independently represent a hydrogen atom or an aliphatic group, Rd ₅ independently represents a sulfo group or a sulfamoyl group, Rd ₆ , Rd ₇ , Rd ₈ , Rd ₉ , and Rd ₁₀ each independently represent a substituent. Moreover, m, n, p, and q represent the integer of 0-3, r represents the integer of 0-4.

In the general formula (3), the aliphatic group may be unsubstituted or substituted, may be saturated or unsaturated, and is preferably an aliphatic group having 1 to 20 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.
In the general formula (3), the sulfamoyl group may be unsubstituted or substituted, and is preferably a sulfamoyl group having 0 to 20 carbon atoms in total, for example, an N-methylsulfamoyl group, N, N— Examples thereof include a diethyl sulfamoyl group, an N-allyl sulfamoyl group, and an N-aryl sulfamoyl group.
In the general formula (3), the substituent is preferably a group mentioned in the section of “substituent” in the general formula (1) described above, an aliphatic group, an acylamino group, a carboxyl group, an aliphatic oxy group, an aliphatic group. An oxycarbonyl group, a carbamoyl group, a sulfo group and a sulfamoyl group are preferred.

  The dye represented by the general formula (3) may be a salt when a carboxyl group or a sulfo group is present, for example, an alkali metal salt such as sodium salt or potassium salt, or an organic salt such as triethylamine. There may be.

  Hereinafter, specific examples (Exemplified Compounds H-1 to H-5) of the pigment represented by the general formula (3) (the dye according to the invention) are shown. However, the present invention is not limited to these.

  Among the above, at least one of the dyes represented by the general formula (1) and at least one of the dyes represented by the general formula (2) are effective in that the effects of the present invention can be effectively achieved. The aspect comprised combining is more preferable. The dye according to the present invention described above can be used in combination with other acid dyes, salts of other acid dyes with metals or nitrogen-containing compounds, derivatives of other acid dyes, and the like.

  The concentration of the dye according to the present invention in the colored curable composition varies depending on the molecular weight and the molar extinction coefficient, but is preferably 0.5 to 80% by mass based on the total solid components of the composition. -60% by mass is more preferred, and 0.5-50% by mass is particularly preferred.

-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 phosphate ester site, a quaternary ammonium salt site, an ethyleneoxy chain, a propyleneoxy chain, a sulfonic acid or its salt site, a morpholinylethyl group 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, alkali-soluble phenol resin can also be used as a binder in 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 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-
In the present invention, the coloring matter (dye) represented by the general formula described above is used, and the curing reaction of the film proceeds to a higher degree than before, and a film having good curability can be obtained. However, it is also possible to obtain a more highly cured film by 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-
Colored curable composition for a color filter of the present invention, it contains at least one 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 compound that is the halomethyloxadiazole compound include 2-halomethyl-5-vinyl-1,3,4-oxadiazole compounds described in JP-B-57-6096, 2-trichloromethyl, and the like. -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 Japanese Patent Publication No. 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 JP-B-51-48516, etc., 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, 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 about 2 to 50% by mass and 2 to 30%, respectively, based on the total solid content added to the organic solvent. It is preferable to dissolve at a ratio of about mass%. Moreover, each content of the said naphthoquinone diazide compound and the said pigment | dye normally has the ratio of about 2-30 mass% and about 2-50 mass%, respectively with respect to the solution which melt | dissolved the said binder and the crosslinking agent.

-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, and camphoric 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, 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 colored curable composition of the present invention described above is used. The color filter of the present invention uses the colored curable composition of the present invention, and the colored curable composition is applied on a support by a coating method such as spin coating, cast coating, roll coating, and the like. It can be most suitably configured by forming a physical 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-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) Co., Ltd .; photopolymerization initiator)... 0.58 parts were mixed and dissolved to prepare a resist solution.

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 (general formula (1)) which is a dye according to the present invention ) 0.40 g and the aforementioned exemplified compound a-1 (pigment represented by the general formula (2)) 0.35 g are mixed and dissolved to prepare a dye resist solution (colored curable composition). Product [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 red pattern suitable as a red pixel 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 6)
In Example 1, “3) Preparation of dye resist solution”, a red pattern was formed in the same manner as in Example 1 except that the dye according to the present invention was changed (but equimolar) as shown in Table 1 below. Further, the same evaluation was performed. The evaluation results are shown in Table 1 below.

(Example 7)
In Example 1, except that “3) Preparation of dye resist solution” was changed as follows, a red pattern was formed in the same manner as in Example 1, and the same evaluation was performed. The evaluation results are shown in Table 1 below.
-Preparation of dye resist solution (colored curable composition [negative type])-
9.4 g of the resist solution obtained in the above 1), 0.30 g of the exemplified compound 1 (the dye represented by the general formula (1)) as the dye according to the present invention, 0.3 g of the exemplified compound f- 25 (dye represented by the general formula (2)) 0.35 g and the above-described exemplified compound g- (1) (dye represented by the general formula (2)) 0.10 g were mixed and dissolved. A dye resist solution (colored curable composition [negative type] solution) was prepared.

(Examples 8 to 10)
In Example 7, “Preparation of dye resist solution”, a red pattern was formed in the same manner as in Example 7, except that the dye according to the present invention was changed as shown in Table 1 below (but equimolar). Further, the same evaluation was performed. The evaluation results are shown in Table 1 below.

(Comparative Examples 1-2)
A comparative yellow pattern was obtained in the same manner as in Example 1 except that the dye according to the present invention was changed as shown in Table 1 below (but equimolar) in “3) Preparation of dye resist solution” in Example 1. 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, the dye represented by the general formula (1), the dye represented by the general formula (2) and / or the dye represented by the general formula (3) described above as the dye. In the combined examples, as compared with the comparative examples using other dyes in combination, all of the colored curable compositions prepared in the form of a solution are excellent in storage stability, and this colored curable composition is used. The red pattern thus formed exhibited good 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)
-Exemplified compound 3 of dye according to the present invention 0.5 part (colorant represented by formula (1))
-Exemplified compound g- (1) of the dye according to the present invention 1.0 part (colorant represented by formula (2))

-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 attached with a stirrer, a reflux condenser, and a thermometer under a nitrogen stream. 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, the 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.

Claims (4)

At least one selected from the following formula (1), at least one selected from the following formula (2) and the following formula (3) , and radiation sensitivity A colored curable composition for a color filter , comprising at least one compound .

[In General Formula (1), R ^a1 represents an aliphatic group, an aryl group, a heterocyclic group, an acyl group, an aliphatic oxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an aliphatic sulfonyl group, an arylsulfonyl group, or It represents a sulfamoyl group, and R ^a2 represents a hydrogen atom or a substituent. X ^a1 represents —CR ^a3 = or a nitrogen atom, and R ^a3 represents a hydrogen atom or a substituent. B represents a coupler-residue. When R ^a1 and R ^a2 and / or X ^a1 represents —CR ^{a3 ═} , R ^a2 and R ^a3 may be bonded to each other to form a 5- to 7-membered ring. ]

In [the formula (2), A represents a residue of a 5-membered heterocyclic diazo component A-NH _2. B ¹ represents represents -CR ¹ = or a nitrogen atom, B ² represents -CR ² = or a nitrogen atom, B ¹ and B ² do not simultaneously represent a nitrogen atom. R ⁵ and R ⁶ are each independently a hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group, or It represents a sulfamoyl group, and R ⁵ and R ⁶ do not represent a hydrogen atom at the same time. G, R ¹ and R ² are each independently a hydrogen atom, halogen atom, aliphatic group, aromatic group, heterocyclic group, cyano group, carboxyl group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, Substituted with acyl group, hydroxy group, alkoxy group, aryloxy group, silyloxy group, acyloxy group, carbamoyloxy group, heterocyclic oxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, alkyl group or aryl group or heterocyclic group Substituted amino group, acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkylsulfonylamino group, arylsulfonylamino group, aryloxycarbonylamino group, nitro group, alkyl O group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group, an alkylsulfinyl group, an arylsulfinyl group, a sulfamoyl group, a sulfo group, or a heterocyclic thio group. R ¹ and R ⁵ and / or R ⁵ and R ⁶ may be bonded to each other to form a 5-membered or 6-membered ring. ]

[In General Formula (3), Rd ₁ , Rd ₂ , Rd ₃ , and Rd ₄ each independently represent a hydrogen atom or an aliphatic group, Rd ₅ represents a sulfo group or a sulfamoyl group, Rd ₆ , Rd ₇ , Rd ₈ , Rd ₉ , and Rd ₁₀ each independently represent a substituent. m, n, p, and q each independently represent an integer of 0 to 3, and r represents an integer of 0 to 4. ] The colored curable composition for a color filter according to claim 1, further comprising a binder and a polymerizable monomer. Including at least one kind of a dye represented by the following general formula (1), and at least one kind selected from a dye represented by the following general formula (2) and a dye represented by the following general formula (3). Characteristic color filter.

[In General Formula (1), R ^a1 represents an aliphatic group, an aryl group, a heterocyclic group, an acyl group, an aliphatic oxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an aliphatic sulfonyl group, an arylsulfonyl group, or It represents a sulfamoyl group, and R ^a2 represents a hydrogen atom or a substituent. X ^a1 represents —CR ^a3 = or a nitrogen atom, and R ^a3 represents a hydrogen atom or a substituent. B represents a coupler-residue. When R ^a1 and R ^a2 and / or X ^a1 represents —CR ^{a3 ═} , R ^a2 and R ^a3 may be bonded to each other to form a 5- to 7-membered ring. ]

In [the formula (2), A represents a residue of a 5-membered heterocyclic diazo component A-NH _2. B ¹ represents represents -CR ¹ = or a nitrogen atom, B ² represents -CR ² = or a nitrogen atom, B ¹ and B ² do not simultaneously represent a nitrogen atom. R ⁵ and R ⁶ are each independently a hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group, or It represents a sulfamoyl group, and R ⁵ and R ⁶ do not represent a hydrogen atom at the same time. G, R ¹ and R ² are each independently a hydrogen atom, halogen atom, aliphatic group, aromatic group, heterocyclic group, cyano group, carboxyl group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, Substituted with acyl group, hydroxy group, alkoxy group, aryloxy group, silyloxy group, acyloxy group, carbamoyloxy group, heterocyclic oxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, alkyl group or aryl group or heterocyclic group Substituted amino group, acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkylsulfonylamino group, arylsulfonylamino group, aryloxycarbonylamino group, nitro group, alkyl O group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group, an alkylsulfinyl group, an arylsulfinyl group, a sulfamoyl group, a sulfo group, or a heterocyclic thio group. R ¹ and R ⁵ and / or R ⁵ and R ⁶ may be bonded to each other to form a 5-membered or 6-membered ring. ]

[In General Formula (3), Rd ₁ , Rd ₂ , Rd ₃ , and Rd ₄ each independently represent a hydrogen atom or an aliphatic group, Rd ₅ represents a sulfo group or a sulfamoyl group, Rd ₆ , Rd ₇ , Rd ₈ , Rd ₉ , and Rd ₁₀ each independently represent a substituent. m, n, p, and q each independently represent an integer of 0 to 3, and r represents an integer of 0 to 4. ] A color filter comprising a step of applying a colored curable composition for a color filter according to claim 1 or 2 onto a support, exposing through a mask, and developing to form a pattern image. Production method.