JP2008058683A - Dye-containing negative curable composition, color filter and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a dye-containing negative curable composition excellent in temporal stability after prepared and showing a small variation in pattern line width due to variation in exposure energy, a color filter excellent in hue and resolution and having a good pattern profile, and a method for producing a color filter by which the above color filter can be produced with high productivity (high cost performance). <P>SOLUTION: The dye-containing negative curable composition comprises (A) at least two organic-solvent soluble dyes selected from a heterocyclic azo compound, a phthalocyanine compound and an azomethine compound, (B) at least one oxime photopolymerization initiator, (C) at least one radical polymerizable monomer and (D) at least one organic solvent, wherein the moisture content of the composition is <1 mass% relative to the total amount of the composition. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a dye-containing negative curable composition suitable for forming a color filter used in a liquid crystal display device or a solid-state imaging device, a dye-containing color filter, and a method for producing the same.

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

  Among these, the pigment dispersion method is a method for producing a color filter by a photolithography method using a colored radiation-sensitive composition in which a pigment is dispersed in various photosensitive compositions, and the pigment is used as a colorant. Therefore, it has the advantage of being stable to light, heat, and the like. Further, since patterning is performed by a photolithography method, it has been widely used as a suitable method for manufacturing a color filter for a large-screen, high-definition color display with high positional accuracy.

  When producing a color filter by a pigment dispersion method, a radiation sensitive composition is applied on a glass substrate with a spin coater or a roll coater and dried to form a coating film, and then this coating film is subjected to pattern exposure and development. A colored filter is formed, and a color filter is obtained by repeating this operation for each color according to the desired number of hues. As such a pigment dispersion method, there is one in which an example using a negative photosensitive composition in which a photopolymerizable monomer and a photopolymerization initiator are used in combination with an alkali-soluble resin is described (for example, Patent Documents 1 to 5). reference).

  On the other hand, in recent years, there has been a demand for higher definition in color filters for solid-state imaging devices. However, it is difficult to further improve the resolution with conventional pigment dispersion systems, and there are problems such as color unevenness caused by coarse particles of the pigment, so that it is used for applications that require fine patterns such as solid-state imaging devices. Was not suitable.

In view of such a problem, a technique using an organic solvent-soluble dye (hereinafter sometimes simply referred to as “dye”) instead of a pigment has been proposed. (For example, refer to Patent Document 7).
As a colored photosensitive resin composition containing a dye, a technique has been proposed in which the moisture content in the composition is reduced to a specific range or less to suppress the separation of micropatterns after development and the occurrence of biting shapes between the pattern and the substrate. (For example, refer to Patent Document 6).
Moreover, the composition containing dye has the problem that light resistance is generally inferior compared with a pigment. As a method for improving light resistance, a technique of adding an alcohol-soluble Ni, Co metal compound or a transition metal complex to a vitreous colored filter has been proposed (for example, see Patent Documents 8 to 10).
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 2003-295427 A JP-A-2005-99488 Japanese Patent No. 2986796 Japanese Patent Laid-Open No. 11-223720 JP 2004-295116 A

However, even with the above technique, the stability over time after the composition is formed and the variation in the pattern line width due to the variation in exposure dose cannot be satisfied. In particular, when a transition metal complex is added to the composition, the above problem becomes remarkable.
In addition, unlike the case of the semiconductor manufacturing use, in the case of the production of the color filter for the solid-state imaging device, a film thickness of 1.5 μm or less is required, and it is necessary to add a large amount of dye in the curable composition. is there. In this case, the above problem becomes more prominent.

This invention is made | formed in view of the above, and makes it a subject to achieve the following objective.
That is, the present invention is a dye-containing negative curable composition having excellent temporal stability after composition preparation and having a small ratio of pattern line width variation due to exposure dose variation, and excellent in hue and resolution, and having a pattern shape. It is an object of the present invention to provide a good color filter and a method for producing a color filter capable of producing the color filter with high productivity (high cost performance).

  This invention achieves the said subject with the composition which combined specific dye and photoinitiator, and specified the water content, The concrete means is as follows.

<1> (A) at least two organic solvent-soluble dyes selected from heterocyclic azo compounds, phthalocyanine compounds, and azomethine compounds; (B) at least one oxime photopolymerization initiator; and (C) A dye-containing negative curable composition comprising at least one radical polymerizable monomer and (D) at least one organic solvent, wherein the water content of the composition is 1% by mass relative to the total amount of the composition Dye-containing negative curable composition characterized by being less than.
<2> The above-mentioned <1>, wherein the at least two organic solvent-soluble dyes are selected from a nitrogen-containing heterocyclic azo compound, an organic group-substituted phthalocyanine compound, and a nitrogen-containing heterocyclic azomethine compound. > The dye-containing negative curable composition of>.

<3> The at least two organic solvent-soluble dyes are selected from pyrazole azo compounds, pyridone azo compounds, pyridine azo compounds, pyrimidine azo compounds, sulfur-containing organic group-substituted phthalocyanine compounds, and pyrazolotriazole-containing azomethine compounds. The dye-containing negative curable composition as described in <1> or <2> above,
<4> Further, (E) a transition metal complex having a maximum molar extinction coefficient ε in the visible light region smaller than the molar extinction coefficient ε of the organic solvent-soluble dye, The dye-containing negative curable composition according to any one of <3>.

<5> The at least two kinds of organic solvent-soluble dyes include at least one selected from the following (1) to (3). A dye-containing negative curable composition.
(1) Two types of pyrazole azo compounds and pyridone azo compounds (2) Two types of sulfur-containing organic group-substituted phthalocyanines and pyrazole azo compounds (3) Two of sulfur-containing organic group-substituted phthalocyanines and pyrazolotriazole-containing azomethine compounds seed

<6> The dye-containing negative curable composition according to any one of <1> to <5>, wherein at least one of the organic solvent-soluble dye (A) includes an acidic group. .
<7> The dye-containing negative curable composition according to any one of <1> to <6>, wherein at least two of the (A) organic solvent-soluble dyes contain an acidic group.

<8> The ratio (B / C) of the total mass of the photopolymerization initiator including the (B) oxime photopolymerization initiator to the total mass of the (C) radical polymerizable monomer is 0.25 or more and 0.75. The dye-containing negative curable composition according to any one of <1> to <7>, which is the following.
<9> The content of the (B) oxime-based photopolymerization initiator is 9% by mass or more in the total solid content of the composition, according to any one of <1> to <8>, The dye-containing negative curable composition as described.

<10> The content of the (B) oxime-based photopolymerization initiator is 12% by mass or more based on the total solid content of the composition, according to any one of the above items <1> to <9> The dye-containing negative curable composition as described.
<11> The organic solvent-soluble dye (A) is 40% by mass to 95% by mass in the total solid content of the composition, according to any one of <1> to <10>, A dye-containing negative curable composition.

<12> The organic solvent-soluble dye (A) is 45% by mass or more and 90% by mass or less in the total solid content of the composition, according to any one of <1> to <11>, A dye-containing negative curable composition.
<13> The dye-containing negative type according to any one of <1> to <12>, further comprising a photopolymerization initiator other than the (B) oxime-based photopolymerization initiator. Curable composition.

<14> The dye-containing negative curable composition according to any one of <1> to <13>, further comprising a resin.
<15> The dye-containing negative curable composition according to any one of <1> to <14>, further comprising a surfactant.

<16> The <D>, wherein the organic solvent (D) is at least one of cyclohexanone, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and ethyl 3-ethoxypropionate. The dye-containing negative curable composition according to any one of <15>.

<17> The dye-containing negative curable composition <18> according to <16>, wherein the organic solvent (D) is at least one of propylene glycol monomethyl ether and ethyl 3-ethoxypropionate. > A color filter comprising the dye-containing negative curable composition according to any one of <1> to <17>.

<19> A color filter having one or more colored regions on a support, wherein at least one color of the colored region is at least one of the following (1) to (3) as an organic solvent-soluble dye: Dye-containing negative curing comprising 1 and (B) at least one oxime-based photopolymerization initiator and having a water content of less than 1% by weight based on the total amount of the composition A color filter formed using an adhesive composition.
(1) Two types of pyrazole azo compounds and pyridone azo compounds (2) Two types of sulfur-containing organic group-substituted phthalocyanines and pyrazole azo compounds (3) Two of sulfur-containing organic group-substituted phthalocyanines and pyrazolotriazole-containing azomethine compounds seed

<20> A step of applying the dye-containing negative curable composition according to any one of <1> to <17> onto a support, exposing the film through a mask, and developing to form a pattern. A method for producing a color filter, characterized by comprising at least once.

  According to the present invention, the dye-containing negative curable composition having excellent temporal stability due to the reduction of insoluble matter after the composition is created and the pattern line width variation ratio due to exposure dose variation is small, and excellent in hue and resolving power. It is possible to provide a color filter having a good pattern shape and a color filter manufacturing method capable of producing the color filter with high productivity (high cost performance).

  Hereinafter, the dye-containing negative curable composition, the color filter, and the production method thereof of the present invention will be described in detail.

<< Dye-containing negative curable composition >>
The dye-containing negative curable composition of the present invention (hereinafter sometimes referred to as “the composition of the present invention”) is selected from (A) a heterocyclic azo compound, a phthalocyanine compound, and an azomethine compound. At least two organic solvent-soluble dyes, (B) at least one oxime photopolymerization initiator, (C) at least one radical polymerizable monomer, and (D) at least one organic solvent, and The water content of the composition is less than 1% by mass relative to the total amount of the composition.
Moreover, it is preferable to contain resin (binder) and surfactant, and may contain a crosslinking agent, a photosensitizer, a sensitizer, a photo-acid generator etc. as needed.

(A) Organic solvent-soluble dye The composition of the present invention contains at least two kinds selected from (A) a heterocyclic azo compound, a phthalocyanine compound, and an azomethine compound as the organic solvent-soluble dye. These dyes are effective in combination with the oxime photopolymerization initiator described later in order to reduce the rate of pattern line width variation due to temporal stability and exposure amount variation.
The at least two organic solvent-soluble dyes are preferably selected from nitrogen-containing heterocyclic azo compounds, organic group-substituted phthalocyanine compounds, and nitrogen-containing heterocyclic azomethine compounds, pyrazole azo compounds, More preferably selected from pyridone azo compounds, pyridine azo compounds, pyrimidine azo compounds, sulfur-containing organic group-substituted phthalocyanine compounds, and pyrazolotriazole-containing azomethine compounds, at least (1) pyrazole azo compounds and pyridone azo compounds Any one selected from (2) two types of (2) sulfur-containing organic group-substituted phthalocyanines and pyrazole azo compounds, and (3) two types of sulfur-containing organic group-substituted phthalocyanines and pyrazolotriazole-containing azomethine compounds. It is more preferable that one be included.

Moreover, it is preferable that at least 1 type of organic-solvent soluble dye contains an acidic group, and also it is preferable that at least 2 types of organic-solvent soluble dye contain an acidic group. These acidic groups can be contained at any position of the organic solvent-soluble dye. Here, the acidic group is not limited as long as it is a functional group that can be dissociated with respect to an alkaline aqueous solution, and specific examples include sulfonic acid, carboxylic acid, phenolic hydroxyl group, sulfonamide, and phosphoric acid. It is done. Moreover, these acidic groups may be a salt of a metal having a valence of 2 or more, and examples of the metal include magnesium, calcium, strontium, barium, zinc, aluminum, nickel, copper, cobalt, and iron. It is done.
Hereinafter, the components of the composition of the present invention will be described in detail.

[Heterocyclic azo compound]
A heterocyclic azo compound is a compound in which an azo group (—N═N—) is directly connected to a heterocyclic ring.
Here, the heterocyclic ring has a hetero atom (for example, nitrogen atom, sulfur atom, oxygen atom) in the ring. Either a saturated ring or an unsaturated ring may be used, but an unsaturated ring is preferable. Further, it may be either a single ring or a condensed ring, and may be unsubstituted or substituted with a substituent.

  Specific examples of the heterocyclic ring include furan, pyrrole, pyrazole, pyrazoline, imidazole, oxazole, thiazole, triazole, pyran, pyridine, pyrimidine, pyrazine, triazine, pyridone, isothiazole, thiadiazole, benzothiazole, benzoxazole, benzoisothiazole. Etc. Among these, a heterocyclic ring containing a nitrogen atom in the ring (a nitrogen-containing heterocyclic ring) is preferable, and among them, pyrazole, pyridone, pyridine, and pyrimidine are preferable.

  Specific examples of the heterocyclic azo compound are shown below. However, the present invention is not limited to these specific examples.

-Heterocyclic azo compound (1)-
Examples of the heterocyclic azo compound include pyridone azo dyes represented by the following general formula (A). This dye simultaneously satisfies high light resistance and high heat resistance, which are not found in conventional azo compounds, and can be freely dissolved in water or an organic solvent when necessary.
The pyridone azo dye represented by formula (A) includes tautomers.

In the general formula (A), R ^a01 , R ^a03 and R ^a04 are each independently a hydrogen atom, an alkyl group having 1 to 21 carbon atoms, an alkenyl group having 2 to 21 carbon atoms, or an aryl group having 6 to 21 carbon atoms. , An aralkyl group having 7 to 21 carbon atoms, or a “substituent having a hetero atom”, and at least one of R ^a01 , R ^a03 and R ^a04 is a substituent having a hetero atom. R ^a03 and R ^a04 may form a heterocyclic ring together with the nitrogen atom bonded ^thereto . R ^a02 represents an alkyl group having 1 to 10 carbon atoms, a methoxymethyl group, or a trifluoromethyl group.

Examples of the pyridone azo dye represented by the general formula (A) include: (1) the R ^a01 is a substituent having a hetero atom, and the R ^a03 and R ^a04 are each independently a hydrogen atom, carbon number 1 An embodiment representing an alkyl group of ˜21, an alkenyl group of 2 to 21 carbon atoms, an aryl group of 6 to 21 carbon atoms, or an aralkyl group of 7 to 21 carbon atoms, (2) at least one of R ^a03 and R ^a04 is “ R ^a01 is a hydrogen atom, an alkyl group having 1 to 21 carbon atoms, an alkenyl group having 2 to 21 carbon atoms, an aryl group having 6 to 21 carbon atoms, or an aryl group having 7 to 21 carbon atoms. An embodiment representing an aralkyl group can be preferably exemplified.

In the general formula (A), R ^a01 , R ^a03 and R ^a04 each independently ^represent a hydrogen atom, an alkyl group having 1 to 21 carbon atoms, an alkenyl group having 2 to 21 carbon atoms, or an aryl group having 6 to 21 carbon atoms. , An aralkyl group having 7 to 21 carbon atoms, or a “substituent having a hetero atom”. However, at least one of R ^a01 , R ^a03 and R ^a04 is a substituent having a hetero atom.

First, the case where the group represented by R ^a01 is a substituent having a hetero atom will be described.
The “substituent having a hetero atom” represented by R ^a01 is not particularly limited as long as it is derived from an amine having a hetero atom (for example, a nitrogen atom, a sulfur atom, or an oxygen atom) that can be used for the synthesis of a pyridone ring. Not. R ^a01 may be unsubstituted or may further have a substituent.

As the “substituent having a hetero atom” represented by R ^a01 , a substituent having about 3 to 50 total atoms is preferable from the viewpoint of color valence, a substituent having 3 to 40 total atoms is more preferable, A substituent having a number of 3 to 30 is particularly preferable, and a substituent having a total number of 3 to 30 having at least one of a nitrogen atom, a sulfur atom and an oxygen atom is most preferable.

The “substituent having a hetero atom” represented by R ^a01 can be introduced, for example, by closing an amide compound obtained by the reaction of a cyanoacetate with a primary amine on a pyridone ring. For this reason, examples of the “substituent having a heteroatom” represented by R ^a01 include a group derived from a primary amine containing a heteroatom described in “Aldrich structure index”. .

Specific examples of the “substituent having a hetero atom” represented by R ^a01 include 2-methoxyethyl group, 3-methoxypropyl group, 3-ethoxypropyl group, 3-butoxypropyl group, 2-methoxy. -1-methyl-ethyl group, tetrahydrofurfuryl group, hydroxyethyl group, hydroxypropyl group, 4-hydroxybutyl group, 2-hydroxy-1-methyl-ethyl group, hydroxyethoxyethyl group, 3-N-morpholinopropyl group 2-N-morpholinoethyl group, 3-N-pyrrolidinonylpropyl group, 2-dimethylaminoethyl group, 3-dimethylaminopropyl group, 3-diethylaminopropyl group, 2-N-pyrrolidinylethyl group, 2 -(N-methyl-2-pyrrolidinyl) ethyl group, 2-N-piperidinylethyl group, 3- (2-methyl-N -Piperidinyl) propyl group, 3-isopropoxypropyl group, and the like.

Among these, as the “substituent having a hetero atom” represented by R ^a01 , 3-methoxypropyl group, 3-ethoxypropyl group, 2-methoxy-1-methyl-ethyl group, tetrahydrofurfuryl group, hydroxy Ethyl group, hydroxypropyl group, 4-hydroxybutyl group, 2-hydroxy-1-methyl-ethyl group, hydroxyethoxyethyl group, 3-N-morpholinopropyl group, 2-N-morpholinoethyl group, 3-N-pyrrole Dinonylpropyl group, 2-dimethylaminoethyl group, 3-dimethylaminopropyl group, 3-diethylaminopropyl group, 2-N-pyrrolidinylethyl group, 2- (N-methyl-2-pyrrolidinyl) ethyl group, 2 -N-piperidinylethyl group, 3- (2-methyl-N-piperidinyl) propyl group, 3-isopropoxyp More preferred are propyl groups, among which 3-methoxypropyl group, 2-methoxy-1-methyl-ethyl group, tetrahydrofurfuryl group, hydroxyethyl group, hydroxypropyl group, 4-hydroxybutyl group, hydroxyethoxy Ethyl group, 3-N-morpholinopropyl group, 2-N-morpholinoethyl group, 3-N-pyrrolidinonylpropyl group, 3-dimethylaminopropyl group, 3-diethylaminopropyl group, 2- (N-methyl-2) -Pyrrolidinyl) ethyl group, 2-N-piperidinylethyl group, 3- (2-methyl-N-piperidinyl) propyl group, 3-isopropoxypropyl group and the like are more preferable.

Furthermore, among these, the “substituent having a hetero atom” represented by R ^a01 includes a 3-methoxypropyl group, a tetrahydrofurfuryl group, a hydroxypropyl group, a 4-hydroxybutyl group, a hydroxyethoxyethyl group, 3 -N-morpholinopropyl group, 2-N-morpholinoethyl group, 3-N-pyrrolidinonylpropyl group, 3-dimethylaminopropyl group, 2- (N-methyl-2-pyrrolidinyl) ethyl group, 2-N- A piperidinylethyl group, 3- (2-methyl-N-piperidinyl) propyl group, 3-isopropoxypropyl group, and the like are particularly preferable.

When R ^a03 and / or R ^{a04 represents a} “substituent having a heteroatom”, the “substituent having a heteroatom” represented by R ^a03 and / or R ^a04 includes, for example, a corresponding sulfonamide As long as it is a group derived from an amine having a heteroatom (for example, a nitrogen atom, a sulfur atom, or an oxygen atom) that can be used in the synthesis of the above, there is no particular limitation. R ^a03 and / or R ^a04 may be unsubstituted or may further have a substituent.

The “substituent having a hetero atom” represented by R ^a03 and / or R ^a04 is preferably a group having about 3 to 50 total atoms in terms of color valence, and more preferably a group having 3 to 40 total atoms. A group having 3 to 30 total atoms is particularly preferable, and a group having 3 to 30 total atoms having at least one of a nitrogen atom, a sulfur atom and an oxygen atom is most preferable.

The “substituent having a hetero atom” represented by R ^a03 and R ^a04 can be introduced, for example, by reaction of nitrobenzenesulfonyl chloride with a primary or secondary amine. Examples of the “substituent having a heteroatom” represented by R ^a03 and / or R ^a04 include groups derived from primary or secondary amines containing heteroatoms described in the Aldrich Structure Index, and these And derivatives thereof.

Specific examples of the “substituent having a hetero atom” represented by R ^a03 and R ^a04 include a 2-methoxyethyl group, a 3-methoxypropyl group, a 3-ethoxypropyl group, a 3-butoxypropyl group, 2-methoxy-1-methyl-ethyl group, tetrahydrofurfuryl group, 2-hydroxyethyl group, 2-hydroxypropyl group, 4-hydroxybutyl group, 2-hydroxy-1-methyl-ethyl group, hydroxyethoxyethyl group, 3-N-morpholinopropyl group, 2-N-morpholinoethyl group, 3-N-pyrrolidinonylpropyl group, 2-dimethylaminoethyl group, 3-dimethylaminopropyl group, 3-diethylaminopropyl group, 2-N- Pyrrolidinylethyl group, 2- (N-methyl-2-pyrrolidinyl) ethyl group, 2-N-piperidinylethyl group, -(2-methyl-N-piperidinyl) propyl group, 3-isopropoxypropyl group, diethylaminoethyl group, 2,2-dimethoxyethyl group, 1,3-dioxolan-2-yl-methyl group, 3-hydroxypropyl group , 2-mercaptoethyl group, and the like.

Among these, as the “substituent having a hetero atom” represented by R ^a03 and R ^a04 , 3-methoxypropyl group, 3-ethoxypropyl group, 2-methoxy-1-methyl-ethyl group, tetrahydrofurfuryl Group, 2-hydroxyethyl group, 2-hydroxypropyl group, 4-hydroxybutyl group, 2-hydroxy-1-methyl-ethyl group, hydroxyethoxyethyl group, 3-N-morpholinopropyl group, 2-N-morpholinoethyl Group, 3-N-pyrrolidinonylpropyl group, 2-dimethylaminoethyl group, 3-dimethylaminopropyl group, 3-diethylaminopropyl group, 2-N-pyrrolidinylethyl group, 2- (N-methyl-2) -Pyrrolidinyl) ethyl group, 2-N-piperidinylethyl group, 3- (2-methyl-N-piperidinyl) propyl group 3-isopropoxypropyl group, diethylaminoethyl group, 2,2-dimethoxyethyl group, 1,3-dioxolan-2-yl-methyl group, 3-hydroxypropyl group, 2-mercaptoethyl group, and the like are preferable. Among them, 3-methoxypropyl group, 2-methoxy-1-methyl-ethyl group, tetrahydrofurfuryl group, 2-hydroxyethyl group, 2-hydroxypropyl group, 4-hydroxybutyl group, hydroxyethoxyethyl group, 3-N -Morpholinopropyl group, 2-N-morpholinoethyl group, 3-N-pyrrolidinonylpropyl group, 3-dimethylaminopropyl group, 3-diethylaminopropyl group, 2- (N-methyl-2-pyrrolidinyl) ethyl group, 2-N-piperidinylethyl group, 3- (2-methyl-N-piperidinyl) propyl , 3-isopropoxypropyl group, diethylaminoethyl group, 2,2-dimethoxyethyl group, 1,3-dioxolan-2-yl - methyl group, 3-hydroxypropyl group, 2-mercaptoethyl group, etc. are more preferable.

Furthermore, among these, as the “substituent having a hetero atom” represented by R ^a03 and R ^a04 , 3-methoxypropyl group, tetrahydrofurfuryl group, 2-hydroxypropyl group, 4-hydroxybutyl group, hydroxyethoxy Ethyl group, 3-N-morpholinopropyl group, 2-N-morpholinoethyl group, 3-N-pyrrolidinonylpropyl group, 3-dimethylaminopropyl group, 2- (N-methyl-2-pyrrolidinyl) ethyl group, 2-N-piperidinylethyl group, 3- (2-methyl-N-piperidinyl) propyl group, 3-isopropoxypropyl group, diethylaminoethyl group, 2,2-dimethoxyethyl group, 1,3-dioxolane-2 Particularly preferred are -yl-methyl group, 3-hydroxypropyl group, 2-mercaptoethyl group and the like.

In the general formula (A), when R ^a01 , R ^a03 or R ^a04 is a group not containing a hetero atom, R ^a01 , R ^a03 and R ^a04 are each independently a hydrogen atom, an alkyl having 1 to 21 carbon atoms. Group, an alkenyl group having 2 to 21 carbon atoms, an aryl group having 6 to 21 carbon atoms, or an aralkyl group having 7 to 21 carbon atoms, and R ^a03 and R ^{a04 represent a} heterocyclic ring together with a nitrogen atom bonded thereto. It may be formed. R ^a01 , R ^a03 or R ^a04 may further have a substituent.

The alkyl group having 1 to 21 carbon atoms represented by R ^a01 , R ^a03 or R ^a04 may be unsubstituted or may have a substituent. As an alkyl group, a C1-C15 alkyl group is preferable and a C1-C10 alkyl group is still more preferable.
The alkyl group having 1 to 21 carbon atoms represented by R ^a01 , R ^a03 or R ^a04 may be any of a linear, branched, or cyclic alkyl group, such as a methyl group, an ethyl group, or n-propyl. Group, n-butyl group, n-amyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group Group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosanyl group, i-propyl group, sec-butyl group, i-butyl Group, t-butyl group, 1-methylbutyl group, 1-ethylpropyl group, 2-methylbutyl group, i-amyl group, neopentyl group, 1,2-dimethylpropyl group, 1,1-dimethyl Rupropyl group, t-amyl group, 1,3-dimethylbutyl group, 3,3-dimethylbutyl group,

2-ethylbutyl group, 2-ethyl-2-methylpropyl group, linear or branched heptyl group, 1-methylheptyl group, 2-ethylhexyl group, 1,5-dimethylhexyl group, t-octyl group, branched nonyl Group, branched decyl group, branched undecyl group, branched dodecyl group, branched tridecyl group, branched tetradecyl group, branched pentadecyl group, branched hexadecyl group, branched heptadecyl group, branched octadecyl group, linear or Branched nonadecyl group, linear or branched eicosanyl group, cyclopropyl group, cyclopropylmethyl group, cyclobutyl group, cyclobutylmethyl group, cyclopentyl group, cyclohexyl group, cyclohexylmethyl group, cycloheptyl group, cyclooctyl group, cyclohexylpropyl Group, cyclododecyl group, Rubornyl group, bornyl group, cis-miltanyl group, isopinocanphenyl group, noradamantyl group, adamantyl group, adamantylmethyl group, 1- (1-adamantyl) ethyl group, 3,5-dimethyladamantyl group, quinuclidinyl group, cyclopentyl Preferred examples include an ethyl group and a bicyclooctyl group.

Among these, examples of the alkyl group having 1 to 21 carbon atoms represented by R ^a01 , R ^a03 or R ^a04 include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-amyl group, an n- Hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, i-propyl, sec- Butyl, i-butyl, t-butyl, 1-methylbutyl, 1-ethylpropyl, 2-methylbutyl, i-amyl, neopentyl, 1,2-dimethylpropyl, 1,1-dimethyl Propyl group, t-amyl group, 1,3-dimethylbutyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, 2-ethyl-2-methylpropyl group, linear or branched heptyl group, 1-methyl group Tylheptyl group, 2-ethylhexyl group, 1,5-dimethylhexyl group, t-octyl group, branched nonyl group, branched decyl group, branched undecyl group, branched dodecyl group, branched tridecyl group, branched tetradecyl group , Cyclopropyl group, cyclopropylmethyl group, cyclobutyl group, cyclobutylmethyl group, cyclopentyl group, cyclohexyl group, cyclohexylmethyl group, cycloheptyl group, cyclooctyl group, cyclohexylpropyl group, cyclododecyl group, norbornyl group, bornyl group, Cis-miltanyl group, isopinocanphenyl group, noradamantyl group, adamantyl group, adamantylmethyl group, 1- (1-adamantyl) ethyl group, 3,5-dimethyladamantyl group, quinuclidinyl group, cyclopentylethyl group, biphenyl Cyclooctyl group is more preferable.

Furthermore, among the above, the alkyl group having 1 to 21 carbon atoms represented by R ^a01 , R ^a03 or R ^a04 includes a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-amyl group. N-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, i-propyl group, sec-butyl group, i-butyl group, t-butyl group, 1-methylbutyl group 1-ethylpropyl group, 2-methylbutyl group, i-amyl group, neopentyl group, 1,2-dimethylpropyl group, 1,1-dimethylpropyl group, t-amyl group, 1,3-dimethylbutyl group, 3 , 3-dimethylbutyl group, 2-ethylbutyl group, 2-ethyl-2-methylpropyl group, linear or branched heptyl group, 1-methylheptyl group, 2-ethylhexyl group, 1,5-dimethylhexyl group T-octyl group, branched nonyl group, branched decyl group, cyclopropyl group, cyclopropylmethyl group, cyclobutyl group, cyclobutylmethyl group, cyclopentyl group, cyclohexyl group, cyclohexylmethyl group, cycloheptyl group, cyclooctyl group Cyclohexylpropyl group, cyclododecyl group, norbornyl group, bornyl group, noradamantyl group, adamantyl group, adamantylmethyl group, 1- (1-adamantyl) ethyl group, 3,5-dimethyladamantyl group, cyclopentylethyl group, bicyclooctyl The group is particularly preferred.

Of the alkyl groups having 1 to 21 carbon atoms represented by R ^a01 , R ^a03 or R ^a04 listed above, from the viewpoint of improving heat resistance, an ethyl group, an n-propyl group, an n-butyl group, n-amyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, i-propyl group, sec-butyl group, i-butyl group, t-butyl group, 1-methylbutyl group, 1-ethylpropyl group, 2-methylbutyl group, i-amyl group, neopentyl group, 1,2-dimethylpropyl group, 1,1-dimethylpropyl group, t-amyl group, 1,3-dimethyl Butyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, 2-ethyl-2-methylpropyl group, branched heptyl group, 1-methylheptyl group, 2-ethylhexyl group, 1,5-dimethylhexyl Group, t-octyl group, branched nonyl group, branched decyl group, cyclopropyl group, cyclopropylmethyl group, cyclobutyl group, cyclobutylmethyl group, cyclopentyl group, cyclohexyl group, cyclohexylmethyl group, cycloheptyl group, cyclo Octyl group, cyclohexylpropyl group, cyclododecyl group, norbornyl group, bornyl group, noradamantyl group, adamantyl group, adamantylmethyl group, 1- (1-adamantyl) ethyl group, 3,5-dimethyladamantyl group, cyclopentylethyl group, A branched alkyl group such as a bicyclooctyl group or a cyclic alkyl group is particularly preferred.

  Of the alkyl groups exemplified above, an alkyl group substituted with fluorine is also particularly suitable. Examples of the fluorine-substituted alkyl group include trifluoromethyl group, trifluoroethyl group, pentafluoroethyl group, heptafluoropropyl group, nonafluorobutyl group, tridecafluorohexyl group, pentadecafluoroheptyl group, heptadecafluorooctyl group , Tridecafluorooctyl group, nonadecafluorononyl group, heptadecafluorodecyl group and perfluorodecyl group are preferable, among which trifluoromethyl group, pentafluoroethyl group, heptafluoropropyl group, nonafluorobutyl group, trideca A fluorohexyl group and a pentadecafluoroheptyl group are more preferable, and a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a nonafluorobutyl group, and a tridecafluorohexyl group are particularly preferable.

The alkenyl group having 2 to 21 carbon atoms represented by R ^a01 , R ^a03 or R ^a04 may be unsubstituted or may have a substituent. The alkenyl group is preferably an alkenyl group having 2 to 15 carbon atoms, and more preferably an alkenyl group having 2 to 10 carbon atoms.

Examples of the alkenyl group having 2 to 21 carbon atoms represented by R ^a01 , R ^a03 or R ^a04 include a vinyl group, an isopropenyl group, a 2-propenyl group, a 2-methyl-propenyl group, and 1-methyl-1 -Propenyl group, 1-butenyl group, 3-butenyl group, 1-methyl-1-butenyl group, 1,1-dimethyl-3-butenyl group, 1-pentenyl group, 2-pentenyl group, 1-ethyl-1- Pentenyl group, 1-hexenyl group, 1-heptenyl group, 2,6-dimethyl-5-heptenyl group, 9-decenyl group, 1-cyclopentenyl group, 2-cyclopentenylmethyl group, cyclohexenyl group, 1-methyl- 2-cyclohexenyl group, 1,4-dihydro-2-methylphenyl group, octenyl group, citronellyl group, oleyl group, geranyl group, farnesyl group, 2- Preferred examples include (1-cyclohexenyl) ethyl group.

Among them, examples of the alkenyl group having 2 to 21 carbon atoms represented by R ^a01 , R ^a03 or R ^a04 include a vinyl group, an isopropenyl group, a 2-propenyl group, a 2-methyl-propenyl group, and 1-methyl- 1-propenyl group, 1-butenyl group, 3-butenyl group, 1-methyl-1-butenyl group, 1,1-dimethyl-3-butenyl group, 1-pentenyl group, 2-pentenyl group, 1-ethyl-1 -Pentenyl group, 1-hexenyl group, 1-heptenyl group, 1-cyclopentenyl group, 2-cyclopentenylmethyl group, cyclohexenyl group, 1-methyl-2-cyclohexenyl group, 1,4-dihydro-2-methyl A phenyl group is more preferable, and further a vinyl group, isopropenyl group, 2-propenyl group, 2-methyl-propenyl group, 1-methyl-1-propenyl group, 1 -Butenyl group, 3-butenyl group, 1-methyl-1-butenyl group, 1,1-dimethyl-3-butenyl group, 1-pentenyl group, 2-pentenyl group, 1-ethyl-1-pentenyl group, 1- A hexenyl group, 1-cyclopentenyl group, 2-cyclopentenylmethyl group, cyclohexenyl group, 1-methyl-2-cyclohexenyl group, and 1,4-dihydro-2-methylphenyl group are particularly preferable.

The aryl group having 6 to 21 carbon atoms represented by R ^a01 , R ^a03 or R ^a04 may be unsubstituted or may have a substituent. As the aryl group, an aryl group having 6 to 15 carbon atoms is preferable, and an aryl group having 6 to 10 carbon atoms is more preferable.

Examples of the aryl group having 6 to 21 carbon atoms represented by R ^a01 , R ^a03 or R ^a04 include, for example, phenyl group, naphthyl group, biphenylenyl group, acenaphthenyl group, fluorenyl group, anthracenyl group, anthraquinonyl group, pyrenyl Preferred examples thereof include a phenyl group, a naphthyl group, a biphenylenyl group, an acenaphthenyl group, a fluorenyl group, and an anthracenyl group, and a phenyl group, a naphthyl group, a biphenylenyl group, and a fluorenyl group are particularly preferable.

The aralkyl group having 7 to 21 carbon atoms represented by R ^a01 , R ^a03 or R ^a04 may be unsubstituted or may have a substituent. As the aralkyl group, an aralkyl group having 7 to 15 carbon atoms is preferable, and an aralkyl group having 7 to 10 carbon atoms is more preferable.

Examples of the aralkyl group having 7 to 21 carbon atoms represented by R ^a01 , R ^a03 or R ^a04 include, for example, benzyl group, diphenylmethyl group, 1,2-diphenylethyl group, phenyl-cyclopentylmethyl group, α-methyl. Benzyl group, phenylethyl group, α-methyl-phenylethyl group, β-methyl-phenylethyl group, 3-phenylpropyl group, 3,3-diphenylpropyl group, 4-phenylbutyl group, naphthylmethyl group, styryl group, Preferred examples include cinnamyl group, fluorenyl group, 1-benzocyclobutenyl group, 1,2,3,4-tetrahydronaphthyl group, indanyl group, piperonyl group, pyrenemethyl group and the like.

Among these, examples of the aralkyl group having 7 to 21 carbon atoms represented by R ^a01 , R ^a03 or R ^a04 include benzyl group, phenyl-cyclopentylmethyl group, α-methylbenzyl group, phenylethyl group, α-methyl- Phenylethyl, β-methyl-phenylethyl, 3-phenylpropyl, 4-phenylbutyl, styryl, cinnamyl, fluorenyl, 1-benzocyclobutenyl, 1,2,3,4-tetrahydro A naphthyl group is more preferable, and a benzyl group, an α-methylbenzyl group, a phenylethyl group, an α-methyl-phenylethyl group, a β-methyl-phenylethyl group, a 3-phenylpropyl group, a styryl group, a cinnamyl group, and a fluorenyl group. Group, 1-benzocyclobutenyl group, 1,2,3,4-tetrahydronaphthyl group are particularly preferred. That's right.

The group represented by R ^a01 , R ^a03 or R ^a04 may contain an ether group, and for example, a tetrahydrofurfuryl group, a 2,5-dihydro-2,5-dimethoxyfurfuryl group and the like are preferable.

As described above, R ^a03 and R ^a04 may form a heterocyclic ring together with the nitrogen atom bonded ^thereto . Examples of the heterocyclic ring in this case include 2-methylaziridine ring, azetidine ring, pyrrolidine ring, 3-pyrroline ring, piperidine ring, 1,2,3,6-tetrahydropyridine ring, hexamethyleneimine ring, piperazine ring, 1,3,3-trimethyl-6-azabicyclo [3.2.1] octane ring, decahydroquinoline ring, oxazolidine ring, morpholine ring, thiazolidine ring, thiomorpholine ring, indoline ring, isoindoline ring, 1,2, Preferred are 3,4-tetrahydrocarbazole ring, 1,2,3,4-tetrahydroquinoline ring, 1,2,3,4-tetrahydroisoquinoline ring, iminodibenzyl ring, phenoxazine ring, phenothiazine ring, phenazine ring, etc. It is.

  Among these, pyrrolidine ring, 3-pyrroline ring, piperidine ring, 1,2,3,6-tetrahydropyridine ring, hexamethyleneimine ring, piperazine ring, decahydroquinoline ring, oxazolidine ring, morpholine ring, thiazolidine ring, thio A morpholine ring is more preferable, and further a pyrrolidine ring, a 3-pyrroline ring, a piperidine ring, a 1,2,3,6-tetrahydropyridine ring, a piperazine ring, a decahydroquinoline ring, an oxazolidine ring, a morpholine ring, a thiazolidine ring, a thiol A morpholine ring is particularly preferred.

When the group represented by R ^a01 , R ^a03 or R ^a04 and the heterocyclic ring formed by R ^a03 and R ^a04 and a nitrogen atom have a substituent, the substituent includes an acyl group, an acylamino group , Acylaminocarbonylamino group, aralkylaminocarbonylamino group, arylaminocarbonylamino group, methacryloylaminocarbonylamino group, alkoxycarbonyl group, trifluoromethyl group, fluoro group, chloro group, bromo group, iodo group, hydroxy group, nitro Group, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group, Vinyl group, methoxy group, ethoxy group, butoxy group, isopropoxy group, t-butoxy , Cyclohexyloxy group, a vinyloxy group, a methylthio group, an ethylthio group, a pyrrolidinyl group, a piperidinyl group, a piperazinyl group, an amino group, dimethylamino group, diethylamino group, a phenyl group, -SO ₃ M group, -COOM group (M represents a hydrogen atom Represents a cation composed of a metal atom or a nitrogen-containing compound).

Among the substituents, acyl group (particularly acetyl group), acylamino group, acylaminocarbonylamino group, alkoxycarbonyl group, trifluoromethyl group, fluoro group, chloro group, bromo group, hydroxy group, nitro group, methyl group, Ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, pentyl, hexyl, vinyl, methoxy, ethoxy, butoxy , isopropoxy, t-butoxy group, cyclohexyloxy group, a vinyloxy group, a methylthio group, an ethylthio group, a pyrrolidinyl group, a piperidinyl group, a piperazinyl group, an amino group, dimethylamino group, diethylamino group, a phenyl group, -SO ₃ M group , -COOM group (wherein M is a hydrogen atom, a metal atom or a nitrogen-containing compound) More preferably, an acyl group (particularly an acetyl group), an acylamino group, an acylaminocarbonylamino group, an alkoxycarbonyl group, a trifluoromethyl group, a fluoro group, a chloro group, a bromo group, a hydroxy group, Nitro group, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, hexyl group, vinyl group, methoxy group, ethoxy group, isopropoxy group, cyclohexyloxy group, a vinyloxy group, a methylthio group, an ethylthio group, a pyrrolidinyl group, a piperidinyl group, a piperazinyl group, an amino group, dimethylamino group, diethylamino group, a phenyl group, -SO ₃ M group, -COOM group (M represents a hydrogen atom, Represents a cation composed of a metal atom or a nitrogen-containing compound).
Further, the above substituents may be further substituted with the same substituent multiple times.

  In particular, when the substituent is a group having an active hydrogen such as a hydroxy group or an amino group, the substituent is reacted with various acid chlorides, acid anhydrides, halides or various isocyanates to produce acetyl groups, acyl Group, (meth) acryloyl group, alkylaminocarbonyl group, arylaminocarbonyl group (for example, butylaminocarbonyl group, phenylaminocarbonyl group and the like), alkyl group, aralkyl group and the like.

The alkyl group, alkenyl group, aryl group, aralkyl group represented by R ^a01 , R ^a03 or R ^a04 , and the heterocyclic ring formed by R ^a03 and R ^a04 and a nitrogen atom are further ^represented by R ^a01 , R It may be substituted with each group represented by ^a03 or R ^a04 .

From the viewpoint of color value (ε / Mw), the formula weight of the group represented by R ^a01 , R ^a03 or R ^a04 is preferably 500 or less, and 400 or less in total of R ^a01 , R ^a03 and R ^a04. Is more preferable, and 300 or less is particularly preferable. When R ^a03 and R ^a04 have a substituent, the number of the substituent that R ^a03 and R ^a04 each have is preferably 0 to 4, more preferably 0 to 3, and particularly preferably 0 to 2.

The group represented by R ^a01 , R ^a03 or R ^a04 and the —SO ₃ M group exemplified as the substituent when the heterocyclic ring formed by R ^a03 and R ^a04 and a nitrogen atom has a substituent. M in the —COOM group represents a cation composed of a hydrogen atom, a cation of a metal atom, or a nitrogen-containing compound. Further, the M includes a cation of H, Li, Na, K, Rb, Cs, Ag, Mg, Ca, Sr, Ba, Zn, Al, Ni, Cu, Co, or Fe, or a nitrogen-containing compound. A cation is preferred, a cation of H, Na, K, Rb, Cs, Ag, Mg, Ca, Sr, Ba, Zn, Al, Cu, or Fe, or a cation comprising a nitrogen-containing compound is more preferred, and H, Na, K, Mg, Ca, Ba, Sr, Zn, Al, Cu, or Fe cations, or cations made of nitrogen-containing compounds are particularly preferred.

  The cation composed of the nitrogen-containing compound represented by M is selected in consideration of all of the solubility in organic solvents and water, salt formation, the absorbance and color value of the dye, the heat resistance and light resistance of the colorant, and the like. be able to. When a cation composed of a nitrogen-containing compound is selected only from the viewpoint of absorbance and color value, the nitrogen-containing compound preferably has a molecular weight as low as possible. Among them, those having a molecular weight of 300 or less are preferred, and those having a molecular weight of 280 or less are further preferred. Those having a molecular weight of 250 or less are particularly preferred.

  Hereinafter, specific examples of the nitrogen-containing compound forming “a cation comprising a nitrogen-containing compound” will be given. However, the present invention is not limited to these. The cation here refers to a cation that is obtained by protonating the following nitrogen-containing compound.

In the general formula (A), R ^a02 represents an alkyl group having 1 to 10 carbon atoms, a methoxymethyl group, or a trifluoromethyl group. As the alkyl group represented by R ^a02 , an alkyl group having 1 to 5 carbon atoms is preferable. R ^a02 may be unsubstituted or may further have a substituent.

As R ^a02 , specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a t-butyl group, a methoxymethyl group, and a trifluoromethyl group are preferable, and among them, a methyl group, an ethyl group, and an isopropyl group T-butyl group, methoxymethyl group and trifluoromethyl group are more preferable, and methyl group, isopropyl group, methoxymethyl group and trifluoromethyl group are particularly preferable.

When R ^a02 has a substituent, the substituent is preferably a halogen atom, an alkyl group, or an alkenyl group. Among them, a chlorine atom, a fluorine atom, a methyl group, an ethyl group, a propyl group, a butyl group, A 2-butenyl group is more preferable, and a chlorine atom, a methyl group, an ethyl group, a propyl group, a butyl group, and a 2-butenyl group are particularly preferable.

The pyridone azo dye represented by the general formula (A) may be bonded at the R ^a01 , R ^a03 and R ^a04 portions, and may have two or more dye skeletons.

  Hereinafter, specific examples [Exemplary Compounds A2-1 to A2-24] of the pyridone azo dye represented by the general formula (A) will be listed. However, the present invention is not limited to these. In addition, tautomers of the following specific examples are also suitable.

The pyridone azo dye represented by the general formula (A) is generally synthesized by, for example, a method in which a nitrobenzene derivative having a desired substituent is reduced and then diazotized, and a pyridone compound having the desired substituent is added thereto. can do.
In addition, various compounds included in the general formula (A) can be synthesized in the same manner by appropriately changing desired substituents of the nitrobenzene derivative and the pyridone compound.

-Heterocyclic azo compound (2)-
Other heterocyclic azo compounds include azo dyes represented by the following general formula (B).

In general formula (B), A represents a 5-membered heterocyclic ring. The 5-membered heterocyclic ring is the residue of the diazo component “A-NH ₂ ”. Examples of heteroatoms contained in the 5-membered heterocycle include N, O, and S. As the 5-membered heterocyclic ring, a nitrogen-containing 5-membered heterocyclic ring is preferable. The 5-membered heterocyclic ring may be condensed with an aliphatic ring, an aromatic ring or another heterocyclic ring.
Preferable examples of A include pyrazole ring, imidazole ring, thiazole ring, isothiazole ring, thiadiazole ring, benzothiazole ring, benzoxazole ring, and benzoisothiazole ring. The above A may further have a substituent. As A, the pyrazole ring, imidazole ring, isothiazole ring, thiadiazole ring or benzothiazole ring represented by the following (a) to (f) is particularly preferable.

In the above (a) to (f), R ^{b09 to} R ^b22 represent the same substituents as G, R ^b01 and R ^b02 in the general formula (B) described later.
Among the above (a) to (f), as A, the pyrazole ring and the isothiazole ring represented by (a), (a ′) and (b) are preferable, and the pyrazole ring represented by (a) is More preferably, it is a pyrazole ring represented by (a) and R ^b11 is particularly preferably a 5-membered monocyclic heterocycle.

In the general formula (B), B ^b1 and B ^b2 represent —CR ^b01 = and —CR ^b02 =, respectively, or one of them represents a nitrogen atom and the other represents —CR ^b01 = or —CR ^b02 =. As the ^{B b1} and ^{B b2,} which each represent a ^{-CR b01} = and ^{-CR bO2} = are preferable. R ^b01 and R ^b02 will be described later.
In the general formula (B), R ^b05 and R ^b06 are each independently a hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl. Represents a group, an arylsulfonyl group, or a sulfamoyl group, and each group may further have a substituent.

R ^b05 and R ^b06 are preferably a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, an alkylsulfonyl group and an arylsulfonyl group, and a hydrogen atom, an aromatic group, a heterocyclic group, an acyl group, An alkylsulfonyl group and an arylsulfonyl group are more preferable, and a hydrogen atom, an aromatic group, and a heterocyclic group are particularly preferable. However, R ^b05 and R ^b06 are not simultaneously hydrogen atoms. Each group may further have a substituent.

In the general formula (B), G, R ^b01 and R ^b02 each independently represent a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group, a heterocyclic group, a cyano group, a carboxyl group, a carbamoyl group, or an 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, aromatic An amino group substituted with an aromatic group or a heterocyclic group; acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkylsulfonylamino group, arylsulfonylamino group, nitro group, alkylthio Group, arylthio Group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, an alkylsulfinyl group, an arylsulfinyl group, a sulfamoyl group, or represents a sulfo group, each group may be further substituted.

  As G, 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 aromatic group or a heterocyclic group is substituted. An amino group; an acylamino group, a ureido group, a sulfamoylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, an alkylthio group, an arylthio group, and a heterocyclic thio group, preferably a hydrogen atom, a halogen atom, an alkyl group, a hydroxy group Group, alkoxy group, aryloxy group, acyloxy group; amino group substituted with alkyl group, aromatic group or heterocyclic group; or acylamino group is more preferable, and among them, hydrogen atom, arylamino group, and acylamino group are most preferable. . Each group may further have a substituent.

R ^b01 and R ^b02 are preferably a hydrogen atom, an alkyl group, an alkoxycarbonyl group, a carboxyl group, a carbamoyl group and a cyano group. Each group may further have a substituent.

R ^b02 and R ^b05 , and R ^b05 and R ^b06 may combine to form a 5- to 6-membered ring. Examples of the 5- to 6-membered ring include a pyridine ring, a pyrrole ring, a pyrazole ring, an imidazole ring, and a triazole ring.
In the general formula (B), when each of the substituents represented by A, R ^b01 , R ^b02 , R ^b05 , R ^b06 and G further has a substituent, the substituent includes the above G, R ^b01 and R ^The substituents exemplified for ^b02 can be mentioned.

When the coloring matter represented by the general formula (B) is a water-soluble dye, an ionic hydrophilic group as a substituent is further ^added to any of A, R ^b01 , R ^b02 , R ^b05 , R ^b06 , and G. It is preferable to have. Examples of the ionic hydrophilic group as the substituent include a sulfo group, a carboxyl group, and a quaternary ammonium group. As the ionic hydrophilic group, a sulfo group and a carboxyl group are preferable, and a sulfo group is particularly preferable. The sulfo group and the carboxyl group may be in a salt state. Examples of counter ions that form the salt include alkali metal ions (for example, sodium ions, potassium ions) and organic cations (for example, tetramethylguanidinium ions).

  Specific examples (A1-1 to A1-24) of the pigment represented by the general formula (B) are shown below, but the dye used in the present invention is not limited to the following examples.

-Heterocyclic azo compound (3)-
Other heterocyclic azo compounds include azo dyes represented by the following general formula (C). This azo dye has a good hue, does not precipitate over time when it is in the form of a liquid preparation or a coated film, has excellent storage stability, and is particularly fast against heat and light. Furthermore, when a pattern is formed with the liquid preparation prepared using this pigment | dye, a favorable rectangular pattern shape is obtained and the residual film in the pattern non-formation area | region can be reduced.

In general formula (C), R ^c01 represents a heterocyclic group, and R ^c02 represents a hydrogen atom or a substituent. X ^c01 represents ^—N═ or —C (R ^c03 ) ^═ , and R ^c03 represents a hydrogen atom or a substituent. When X ^c01 is —C (R ^c03 ) ^═ , R ^c02 and R ^c03 may be bonded to each other to form a 5-membered, 6-membered, or 7-membered ring. R ^c04 represents a hydrogen atom or a substituent. R ^c05 and R ^c06 are each independently a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an aryl A sulfonyl group or a sulfamoyl group is represented. The R ^c05 and ^{R c06,} 5-membered may be bonded to each other to form a 6-membered, or 7-membered ring. R ^c07 represents a hydrogen atom or a substituent.

  The term “heterocyclic group” in formula (C) means that the heterocyclic moiety has a heteroatom (eg, nitrogen atom, sulfur atom, oxygen atom) in the ring. It may be a saturated ring, may be a monocyclic ring or a condensed ring, may be unsubstituted or may have a substituent. For example, tetrahydrofuranyl group, dihydrofuranyl group, dihydrofuranyl group, tetrahydropyranyl group, dihydropyranyl group, oxocanyl group, dioxanyl group, tetrahydrothiophenyl group, dithianyl group, pyrrolidinyl group, pyrrolinyl group, tetrahydropyridinyl Group, piperazinyl group, homopiperazinyl group, piperidinyl group, pyrrolyl group, furyl group, thiophenyl group, benzopyrrolyl group, benzofuryl group, benzothiophenyl group, pyrazolyl group, isoxazolyl group, isothiazolyl group, indazolyl group, benzoisoxazolyl group, Benzoisothiazolyl, imidazolyl, oxazolyl, thiazolyl, benzoimidazolyl, benzoxazolyl, benzothiazolyl, pyridyl, quinolinyl, isoquinolinyl, pyrida Nyl, pyrimidinyl, pyrazinyl, cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, acridinyl, phenanthridinyl, phthalazinyl, carbazolyl, uracil, dithiouracil, carbolinyl, purinyl, thiadiazolyl Group etc. can be mentioned, These may be unsubstituted or may have a substituent.

In addition, the “substituent” in the general formula (C) may be any group that can be substituted, for example, an alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, acyl group, acyloxy group, acylamino group. , Alkyloxy group, alkenyloxy group, alkynyloxy group, aryloxy group, heterocyclic oxy group, alkyloxycarbonyl group, alkenyloxycarbonyl group, alkynyloxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, carbamoyl group Alkylsulfonyl group, alkenylsulfonyl group, alkynylsulfonyl group, arylsulfonyl group, heterocyclic sulfonyl group, alkylsulfonyloxy group, alkenylsulfonyloxy group, alkynylsulfonyloxy group, arylsulfonyloxy group, Telocyclic sulfonyloxy group, sulfamoyl group, alkylsulfonamide group, alkenylsulfonamide group, alkynylsulfonamide group, arylsulfonamide group, heterocyclic sulfonamido group, amino group, alkylamino group, alkenylamino group, alkynylamino group, Arylamino group, heterocyclic amino group, alkyloxycarbonylamino group, alkenyloxycarbonylamino group, alkynyloxycarbonylamino group, aryloxycarbonylamino group, heterocyclic oxycarbonylamino group, alkylsulfinyl group, alkenylsulfinyl group, alkynylsulfinyl Group, arylsulfinyl group, alkylthio group, alkenylthio group, alkynylthio group, arylthio group, hydroxy group, cyano group, sulfo group, carbo Sil group, alkyloxyamino group, alkenyloxyamino group, alkynyloxyamino group, aryloxyamino group, carbamoylamino group, sulfamoylamino group, halogen atom, sulfamoylcarbamoyl group, carbamoylsulfamoyl group, dialkyloxy A phosphinyl group, dialkenyloxyphosphinyl group, dialkynyloxyphosphinyl group, diaryloxyphosphinyl group and the like can be mentioned.
Further, the “aryl group” in the present specification may be a single ring or a condensed ring, and may be unsubstituted or may have a substituent (the substituent described above). It is good (when it has two or more substituents, these substituents may be the same or different).

Hereinafter, R ^{c01 to} R ^c07 and X ^c01 in the general formula (C) will be described in detail.
R ^c01 in the general formula (C) represents a heterocyclic group. Preferably, it is a C1-C36 heterocyclic group, More preferably, it is a C2-C24 heterocyclic group. For example, pyrrolyl group, furyl group, thiophenyl group, benzopyrrolyl group, benzofuryl group, benzothiophenyl group, pyrazolyl group, isoxazolyl group, isothiazolyl group, indazolyl group, benzisoxazolyl group, benzoisothiazolyl group, imidazolyl group, Oxazolyl group, thiazolyl group, benzimidazolyl group, benzoxazolyl group, benzothiazolyl group, pyridyl group, quinolinyl group, isoquinolinyl group, pyridazinyl group, pyrimidinyl group, pyrazinyl group, cinnolinyl group, phthalazinyl group, quinazolinyl group, quinoxalinyl group , Phenanthridinyl group, phthalazinyl group, carbazolyl group, carbolinyl group, purinyl group, triazolyl group, oxadiazolyl group, thiadiazolyl group, among them, 3-pyrazolyl 4-pyrazolyl group, 2-imidazolyl group, 4-imidazolyl group, 5-imidazolyl group, 2-oxazolyl group, 2-thiazolyl group, 2-benzoimidazolyl group, 2-benzoxazolyl group, 2-benzothiazolyl group, 2 -Pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-quinolinyl group, 4-quinolinyl group, 1-isoquinolinyl group, 3-isoquinolinyl group, 3-pyridazinyl group, 4-pyridazinyl group, 2-pyrimidinyl group, 4 -Pyrimidinyl group, 5-pyrimidinyl group, 2-pyrazinyl group, 2-purinyl group, 6-purinyl group, 8-purinyl group, 3-triazolyl group, 5-triazolyl group, 3-oxadiazolyl group, 5-oxadiazolyl group, 3 -A thiadiazolyl group and a 5-thiadiazolyl group are more preferable.

When the heterocyclic group represented by R ^c01 is a substitutable group, it may be substituted with the substituent described in the section “Substituent” of the general formula (C) described above. When substituted with the above substituents, these substituents may be the same or different. The following groups are preferable from the viewpoint of more effectively achieving the effects of the present invention.

  That is, a halogen atom (for example, fluorine, chlorine, bromine), an alkyl group (preferably a linear, branched or cyclic alkyl group having 1 to 48 carbon atoms, for example, methyl, ethyl, propyl, isopropyl, butyl , T-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, dodecyl, hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, 1-norbornyl, 1-adamantyl), an alkenyl group (preferably an alkenyl group having 2 to 48 carbon atoms) For example, vinyl, aryl, 3-buten-1-yl), an aryl group (preferably an aryl group having 6 to 48 carbon atoms, such as phenyl or naphthyl), a heterocyclic group (preferably having 1 to 32 carbon atoms). A heterocyclic group such as 2-thienyl, 4-pyridyl, 2-furyl, 2-pyridyl Dinyl, 1-pyridyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, benzotriazol-1-yl), silyl group (preferably a silyl group having 3 to 38 carbon atoms, for example, trimethylsilyl, triethylsilyl, tributylsilyl) , T-butyldimethylsilyl, t-hexyldimethylsilyl), hydroxyl group, cyano group, nitro group, alkoxy group (preferably an alkoxy group having 1 to 48 carbon atoms such as methoxy, ethoxy, 1-butoxy, 2- Butoxy, isopropoxy, t-butoxy, dodecyloxy, cycloalkyloxy groups (eg, cyclopentyloxy, cyclohexyloxy)), aryloxy groups (preferably aryloxy groups having 6 to 48 carbon atoms, such as phenoxy, 1- Naphthoxy), heterocyclic ring Group (preferably a heterocyclic oxy group having from 1 to 32 carbon atoms, e.g., 1-phenyl-5-oxy, 2-tetrahydropyranyloxy),

A silyloxy group (preferably a silyloxy group having 1 to 32 carbon atoms, for example, trimethylsilyloxy, t-butyldimethylsilyloxy, diphenylmethylsilyloxy), an acyloxy group (preferably an acyloxy group having 2 to 48 carbon atoms, for example, Acetoxy, pivaloyloxy, benzoyloxy, dodecanoyloxy), an alkoxycarbonyloxy group (preferably an alkoxycarbonyloxy group having 2 to 48 carbon atoms, such as ethoxycarbonyloxy, t-butoxycarbonyloxy, cycloalkyloxycarbonyloxy group ( For example, cyclohexyloxycarbonyloxy)), aryloxycarbonyloxy group (preferably an aryloxycarbonyloxy group having 7 to 32 carbon atoms, such as phenoxycarbonyloxy group). ), A carbamoyloxy group (preferably a carbamoyloxy group having 1 to 48 carbon atoms such as N, N-dimethylcarbamoyloxy, N-butylcarbamoyloxy, N-phenylcarbamoyloxy, N-ethyl-N-phenylcarbamoyloxy). ), A sulfamoyloxy group (preferably a sulfamoyloxy group having 1 to 32 carbon atoms, such as N, N-diethylsulfamoyloxy, N-propylsulfamoyloxy), an alkylsulfonyloxy group (preferably Is an alkylsulfonyloxy group having 1 to 38 carbon atoms, such as methylsulfonyloxy, hexadecylsulfonyloxy, cyclohexylsulfonyloxy), arylsulfonyloxy group (preferably an arylsulfonyloxy group having 6 to 32 carbon atoms, Feni Sulfonyloxy)

An acyl group (preferably an acyl group having 1 to 48 carbon atoms such as formyl, acetyl, pivaloyl, benzoyl, tetradecanoyl, cyclohexanoyl), an alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 48 carbon atoms). , For example, methoxycarbonyl, ethoxycarbonyl, octadecyloxycarbonyl, cyclohexyloxycarbonyl), aryloxycarbonyl group (preferably an aryloxycarbonyl group having 7 to 32 carbon atoms, such as phenoxycarbonyl), carbamoyl group (preferably carbon number) 1 to 48 carbamoyl groups such as carbamoyl, N, N-diethylcarbamoyl, n-ethyl-N-octylcarbamoyl, N, N-dibutylcarbamoyl, N-propylcarbamoyl, N-phenylcarbyl Moyl, N-methyl N-phenylcarbamoyl, N, N-dicyclohexylcarbamoyl), amino group (preferably an amino group having 32 or less carbon atoms, such as amino, methylamino, N, N-dibutylamino, tetradecyl) Amino, 2-ethylhexylamino, cyclohexylamino), anilino group (preferably an anilino group having 6 to 32 carbon atoms, such as anilino, N-methylanilino), a heterocyclic amino group (preferably a heterogeneous group having 1 to 32 carbon atoms). A ring amino group such as 4-pyridylamino), a carbonamido group (preferably a carbonamido group having 1 to 32 carbon atoms such as acetamide, benzamide, pivaloylamide, cyclohexaneamide, adamantylamino, 2-ethylhexanamide, However, perfluoroalkylcarbonyl Mino groups are excluded), ureido groups (preferably ureido groups having 1 to 32 carbon atoms, such as ureido, N, N-dimethylureido, N-phenylureido), imide groups (preferably imide groups having 10 or less carbon atoms). And, for example, N-succinimide, N-phthalimide),

Alkoxycarbonylamino group (preferably an alkoxycarbonylamino group having 2 to 48 carbon atoms, for example, methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, octadecyloxycarbonylamino, cyclohexyloxycarbonylamino), aryloxycarbonylamino A group (preferably an aryloxycarbonylamino group having 7 to 32 carbon atoms, for example, phenoxycarbonylamino), an azo group (preferably an azo group having 1 to 32 carbon atoms, for example, phenylazo, 3-pyrazolylazo), alkylthio A group (preferably an alkylthio group having 1 to 48 carbon atoms such as methylthio, ethylthio, octylthio, cyclohexylthio), an arylthio group (preferably an arylthio group having 6 to 48 carbon atoms, Phenylthio), a heterocyclic thio group (preferably a heterocyclic thio group having 1 to 32 carbon atoms, such as 2-benzothiazolylthio, 2-pyridylthio, 1-phenyltetrazolylthio), an alkylsulfinyl group (preferably Is an alkylsulfinyl group having 1 to 32 carbon atoms such as dodecanesulfinyl), an arylsulfinyl group (preferably an arylsulfinyl group having 6 to 32 carbon atoms such as phenylsulfinyl), an alkylsulfonyl group (preferably having 1 carbon atom) -48 alkylsulfonyl groups such as methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, isopropylsulfonyl, 2-ethylhexylsulfonyl, hexadecylsulfonyl, octylsulfonyl, cyclohexylsulfonyl),

An arylsulfonyl group (preferably an arylsulfonyl group having 6 to 48 carbon atoms, for example, phenylsulfonyl, 1-naphthylsulfonyl), a sulfamoyl group (preferably a sulfamoyl group having 32 or less carbon atoms, for example, sulfamoyl, N, N- Dipropylsulfamoyl, N-ethyl-N-dodecylsulfamoyl, N-ethyl-N-phenylsulfamoyl, N-cyclohexylsulfamoyl), sulfo group, phosphonyl group (preferably phosphonyl having 1 to 32 carbon atoms) Groups such as phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl), phosphinoylamino groups (preferably phosphinoylamino groups having 1 to 32 carbon atoms such as diethoxyphosphinoylamino, dioctyl Oxyphosphinoylamino) .
When these substituents are further substitutable groups, they may be substituted with the groups described in the “Substituent” section of the general formula (C) described above. When substituted with two or more substituents, the substituents may be the same or different.

In the general formula (C), R ^c02 represents a hydrogen atom or a substituent. X ^c01 represents ^—N═ or —C (R ^c03 ) ^═ , and R ^c03 represents a hydrogen atom or a substituent. When X ^c01 is —C (R ^c03 ) ^═ , R ^c02 and R ^c03 may be bonded to each other to form a 5-membered, 6-membered, or 7-membered ring.
The substituents represented by R ^c02 and R ^c03 are each independently synonymous with the group described in the “Substituent” section of General Formula (C) described above.
When the substituent represented by R ^c02 or R ^c03 is a further substitutable group, it may be substituted with the group described in the “Substituent” section of the general formula (C) described above. When substituted with two or more substituents, the substituents may be the same or different.

R ^c02 and R ^c03 are each preferably the following groups from the viewpoint of more effectively ^achieving the effects of the present invention. That is,
R ^c02 includes a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an acyloxy group, an acylamino group, an alkyloxy group, an alkenyloxy group, an alkynyloxy group, an alkylsulfonyloxy group, an ^{alkenylsulfonyloxy} group, and an ^{alkynylsulfonyl} group. Oxy group, arylsulfonyloxy group, alkylsulfonamide group, alkenylsulfonamide group, alkynylsulfonamide group, arylsulfonamide group, amino group, alkylamino group, alkenylamino group, alkynylamino group, arylamino group, alkyloxycarbonyl Amino group, alkenyloxycarbonylamino group, alkynyloxycarbonylamino group, aryloxycarbonylamino group, heterocyclic oxycarbonylamino group, hydroxy group , A cyano group, a sulfo group, a carbamoylamino group, and a sulfamoylamino group, preferably a hydrogen atom, alkyl group, alkenyl group, alkynyl group, cyano group, aryl group, acyloxy group, alkyloxy group, alkenyloxy group , An alkynyloxy group, an alkylsulfonyloxy group, an alkenylsulfonyloxy group, and an alkynylsulfonyloxy group are more preferable, and a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, and a cyano group are most preferable.

R ^c03 includes an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an acyl group, an acylamino group, an alkyloxycarbonylamino group, an alkenyloxycarbonylamino group, an alkynyloxycarbonylamino group, an aryloxycarbonyl group, and a carbamoyl group. , Alkylsulfonyl group, alkenylsulfonyl group, alkynylsulfonyl group, arylsulfonyl group, heterocansulfonyl group, alkylsulfonyloxy group, alkenylsulfonyloxy group, alkynylsulfonyloxy group, arylsulfonyloxy group, alkylsulfonamide group, alkenylsulfonamide group, alkynyl sulfonamido group, an aryl sulfonamide group, a cyano group, a carboxyl group are preferred, -C when X ^c01 are representing these (R ⁰³⁾ = and if selected from N = are preferred. Further, R ^c03 includes an acyl group, an alkyloxycarbonylamino group, an alkenyloxycarbonylamino group, an alkynyloxycarbonylamino group, an alkylsulfonyl group, an ^{alkenylsulfonyl} group, an ^{alkynylsulfonyl} group, an arylsulfonyl group, a cyano group, and a carboxyl group. More preferably, X ^c01 is more preferably selected from -C (R ^c03 ) = and N = in the case of representing them. Further, R ^c03 is most preferably an alkyloxycarbonylamino group, an alkenyloxycarbonylamino group, an alkynyloxycarbonylamino group, an alkylsulfonyl group, an ^{alkenylsulfonyl} group, an ^{alkynylsulfonyl} group, or a cyano group, and ^Xc01 represents Most preferably, it is selected from -C (R ^c03 ) = and N =.

The substituents represented by R ^c04 and R ^c07 are groups described in the “Substituent” section of the general formula (C) described above, and may be any groups that can be substituted. In the case where R ^c04 and R ^c07 are substitutable groups, they may have the substituents described in the section “Substituent” of the general formula (C) described above, and two or more In the case of having a substituent, these substituents may be the same or different.
R ^c04 and R ^c07 are each a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an acyl group, an acyloxy group, an acylamino group, from the viewpoint of more effectively ^achieving the effects of the present invention. Alkyloxy group, alkenyloxy group, alkynyloxy group, aryloxy group, heterocyclic oxy group, alkyloxycarbonyl group, alkenyloxycarbonyl group, alkynyloxycarbonyl group, carbamoyl group, sulfamoyl group, alkylsulfonamide group, alkenylsulfonamide Group, alkynylsulfonamide group, arylsulfonamide group, heterocyclic sulfonamide group, amino group, alkylamino group, alkenylamino group, alkynylamino group, arylamino group, heterocyclic amino group, alkyloxycarbonyl Mino group, alkenyloxycarbonylamino group, alkynyloxycarbonylamino group, aryloxycarbonylamino group, heterocyclic oxycarbonylamino group, alkylthio group, alkenylthio group, alkynylthio group, arylthio group, heterocyclic thio group, hydroxy group, Preferably represents a cyano group, a sulfo group, a carboxyl group, a carbamoylamino group, a sulfamoylamino group, a halogen atom, a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a heterocyclic group, an acylamino group, an alkyloxy group, Alkenyloxy group, alkynyloxy group, aryloxy group, alkylsulfonamide group, alkenylsulfonamide group, alkynylsulfonamide group, arylsulfonamide group, alkylamino group, alkenylamino group, More preferably, it represents a quinylamino group, an arylamino group, a heterocyclic amino group, an alkylthio group, an alkenylthio group, an alkynylthio group, an arylthio group or a halogen atom, an alkyloxy group, an alkenyloxy group, an alkylamino group, an alkenylamino group , Arylamino group, heterocyclic amino group, and alkylthio group are most preferable.

Wherein R ^c05 and R ^c06 are each independently a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, An arylsulfonyl group or a sulfamoyl group is represented. When R ^c05 and R ^c06 are substitutable group may have a substituent as described in the section on the "substituent" of the above-mentioned general formula (C), 2 or more substituents When having a group, these substituents may be the same or different. ^Furthermore, 5-membered to bond with ^{R c05} and ^{R c06} are each other to form a 6-membered, or 7-membered ring.
R ^c05 and R ^c06 are each a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, from the viewpoint of more effectively ^achieving the effects of the present invention. Or a sulfamoyl group, preferably a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkylsulfonyl group or an arylsulfonyl group, more preferably a hydrogen atom, an alkyl group, an aryl group or a heterocyclic ring. The group is most preferably an alkylsulfonyl group.
^Examples of the 5-membered, 6-membered or 7-membered ring formed by combining R ^c05 and R ^c06 with each other include, for example, a piperidinyl group, pyrrolidinyl group, azepanyl group, morpholinyl group and the like which may have a substituent. And a piperidinyl group and a pyrrolidinyl group are preferable.

  The dye represented by the general formula (C) is preferably a dye represented by the following general formula (C2).

In general formula (C2), R ^c01 , R ^c02 , R ^c05 and R ^c06 have the same ^{meanings as those} in general formula (C), and the preferred embodiments thereof are also the same. In general formula (C2), R ^c08 , R ^c09 , R ^c10 and R ^c11 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonyl group. Represents a group, an aryloxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, or a sulfamoyl group. When R ^c05 and R ^c06 are substitutable group may have a substituent as described in the section on the "substituent" of the aforementioned general formula (C), 2 or more substituents When having a group, these substituents may be the same or different. ^Furthermore, 5-membered to bond with ^{R c05} and ^{R c06} are each other to form a 6-membered, or 7-membered ring. R ^c08 , R ^c09 , R ^c10 and R ^c11 are each a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, a carbamoyl group, an alkylsulfonyl group from the viewpoint of more effectively ^achieving the effects of the present invention. Group, an arylsulfonyl group, or a sulfamoyl group is preferable, and a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkylsulfonyl group, or an arylsulfonyl group is more preferable, and a hydrogen atom, an alkyl group is preferable. , Aryl group, heterocyclic group, and alkylsulfonyl group are most preferable. When R ^c08 , R ^c09 , R ^c10 and R ^c11 are substitutable groups, they have the substituents described in the section “Substituents” of the general formula (C) described above. In the case of having two or more substituents, these substituents may be the same or different.

More preferably, in the general formula (C2), R ^c01 is a 3-pyrazolyl group, a 4-pyrazolyl group, a 2-imidazolyl group, a 4-imidazolyl group, a 5-imidazolyl group, a 2-oxazolyl group, a 2-thiazolyl group, 2-benzoimidazolyl group, 2-benzoxazolyl group, 2-benzothiazolyl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-quinolinyl group, 4-quinolinyl group, 1-isoquinolinyl group, 3- Isoquinolinyl group, 3-pyridazinyl group, 4-pyridazinyl group, 2-pyrimidinyl group, 4-pyrimidinyl group, 5-pyrimidinyl group, 2-pyrazinyl group, 2-purinyl group, 6-purinyl group, 8-purinyl group, 3- Triazolyl group, 5-triazolyl group, 3-oxadiazolyl group, 5-oxadiazolyl group, 3-thiadiazolyl group, Or 5-thiadiazolyl group;
R ^c02 is a hydrogen atom, alkyl group, alkenyl group, alkynyl group, cyano group, aryl group, acyloxy group, alkyloxy group, alkenyloxy group, alkynyloxy group, alkylsulfonyloxy group, alkenylsulfonyloxy group, or alkynylsulfonyl An oxy group;
^{R c05, R c06, R c08} , R c09, R c10 and ^{R c11} are each independently a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group , A carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, or a sulfamoyl group.

More preferably, in the general formula (C2), R ^c01 represents a 3-pyrazolyl group, a 4-pyrazolyl group, a 2-imidazolyl group, a 4-imidazolyl group, a 5-imidazolyl group, a 2-oxazolyl group, a 2-thiazolyl group, 2-benzoimidazolyl group, 2-benzoxazolyl group, 2-benzothiazolyl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-quinolinyl group, 4-quinolinyl group, 1-isoquinolinyl group, 3- Isoquinolinyl group, 3-pyridazinyl group, 4-pyridazinyl group, 2-pyrimidinyl group, 4-pyrimidinyl group, 5-pyrimidinyl group, 2-pyrazinyl group, 2-purinyl group, 6-purinyl group, 8-purinyl group, 3- Triazolyl group, 5-triazolyl group, 3-oxadiazolyl group, 5-oxadiazolyl group, 3-thiadiazolyl group, 5-thiadiazolyl group;
R ^c02 is a hydrogen atom, alkyl group, alkenyl group, cyano group, acyloxy group, alkyloxy group, alkylsulfonyloxy group;
^{R c05, R c06, R c08} , R c09, R c10 and ^{R c11} are each independently a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group , A carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, or a sulfamoyl group.

Most preferably, in the general formula (C2), R ^c01 is a 3-pyrazolyl group, a 4-pyrazolyl group, a 2-imidazolyl group, a 4-imidazolyl group, a 5-imidazolyl group, a 2-oxazolyl group, a 2-thiazolyl group, 2-benzoimidazolyl group, 2-benzoxazolyl group, 2-benzothiazolyl group, 3-pyridazinyl group, 4-pyridazinyl group, 2-pyrimidinyl group, 4-pyrimidinyl group, 5-pyrimidinyl group, 2-pyrazinyl group, 3 -Triazolyl group, 5-triazolyl group, 3-oxadiazolyl group, 5-oxadiazolyl group, 3-thiadiazolyl group, 5-thiadiazolyl group;
R ^c02 is a hydrogen atom, an alkyl group, or a cyano group;
^{R c05, R c06, R c08} , R c09, R c10, and ^{R c11,} a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, an arylsulfonyl group, or a sulfamoyl group And a dye represented by

In the present invention, the dye represented by the general formula (C) or (C2) may form a salt with a cation composed of a metal ion or a nitrogen-containing compound via R ^{c01 to} R ^c11 . When the metal ion is a divalent or higher valent metal ion, it has two or more (may be the same or different) dyes represented by the general formula (C) or (C2). ^{Alternatively} , a bond may be formed via any of R ^{c01 to} R ^c11 to form a bis body, a tris body, or a multimer. The metal ion at this time is not limited as long as it is a cationic ion that forms a salt with the anion moiety contained in the substituent of the dye represented by formula (C) or (C2). Preferred metal ions include Li, Na, K, Rb, Cs, Ag, Mg, Ca, Sr, Ba, Zn, Al, Ni, Cu, Co, and Fe.
Examples of the nitrogen-containing compound include compounds described on pages 12 to 20 of JP-A-2005-99658.

  The nitrogen-containing compound / acid dye molar ratio (hereinafter represented by n) in the salt of the dye represented by the general formula (C) or (C2) and the cation composed of the nitrogen-containing compound is represented by the formula (C) or It is a value that determines the molar ratio between the dye molecule represented by (C2) and the nitrogen-containing compound that is a counter ion, and the salt-forming conditions of the dye-amine compound represented by the general formula (C) or (C2) You can choose freely. Specifically, a numerical value between 0 <n ≦ 5 of the number of functional groups of the acid in the dye represented by the general formula (C) or (C2) is practically used, and is dissolved in an organic solvent or a developer. It is selected in consideration of all necessary performances such as properties, salt-forming properties, absorbance, interaction with other components in the curable composition, light resistance, heat resistance and the like. From the standpoint of absorbance only, n is preferably a value between 0 <n ≦ 4.5, more preferably a value between 0 <n ≦ 4, and 0 <n ≦ 3. It is particularly preferred to take a numerical value between 5.

  Next, specific examples [Exemplary compounds A3-1 to A3-24] of the dye represented by the general formula (C) or (C2) are shown. However, the present invention is not limited to these.

  Next, as a synthesis example of the azo dye represented by the general formula (C), a case where the above exemplary compound (1) is synthesized will be described based on the following reaction scheme A as an example. However, the present invention is not limited to this.

[Synthesis Example]: Synthesis of Exemplary Compound A3-1

(1) Synthesis of Compound B After adding 50.0 g (0.273 mol) of Compound A dropwise to 61.0 g (0.684 mol) of 2-amino-1-methoxypropane, the mixture was heated to 75 ° C. and stirred. To this solution, 76 ml (0.545 mol) of triethylamine was added dropwise. After completion of dropping, the mixture was heated and stirred at 105 to 115 ° C. for 7.5 hours. After completion of the reaction, the reaction solution was cooled to room temperature and extracted by adding 300 ml of water and 300 ml of ethyl acetate. The ethyl acetate solution was washed with water and dried over anhydrous magnesium sulfate. The ethyl acetate solution was concentrated under reduced pressure and purified by silica gel column chromatography (eluent: n-hexane / ethyl acetate = 10/1). Compound B70.0g (yield: 88.8%) was obtained. As compound A, “2,4,6-trichloropyrimidine” manufactured by Sigma-Aldrich was used.

(2) Synthesis of Compound C 53.9 g (0.605 mol) of methoxypropylamine was added to 70.0 g (0.242 mol) of Compound B obtained by the above method, and the external temperature was 160 ° C. to 170 ° C. for 29 hours. Heated and stirred. After completion of the reaction, the reaction solution was cooled to room temperature and extracted by adding 400 ml of water and 400 ml of ethyl acetate. The ethyl acetate solution was washed with water and dried over anhydrous magnesium sulfate. The ethyl acetate solution was concentrated under reduced pressure and purified by silica gel column chromatography (eluent: n-hexane / ethyl acetate = 3/1). 51.8 g (yield: 62.8%) of compound C was obtained.

(3) Synthesis of Compound E A solution of 5.00 g (0.046 mol) of Compound (D) in 56.0 ml of phosphoric acid was stirred at 0 ° C., and 3.51 g (0.051) of sodium nitrite was stirred under stirring. Mol) was added and stirred for 1 hour. To the reaction solution was added a solution of compound (C) 15.3 g (0.045 mol) in acetic acid 5.0 ml, and the mixture was stirred at 25 ° C. for 3 hours. After adding 500 ml of ethyl acetate and 500 ml of water to the reaction solution, the reaction solution was neutralized with sodium bicarbonate. The organic layer was sufficiently washed with water and the solvent was distilled off. After 200 ml of ethyl acetate was added to the residue and dissolved, 600 ml of n-hexane was added to remove the precipitated sticky solid, and 600 ml of n-hexane was further added to the filtrate to separate the precipitated yellow solid. The obtained crystals were dried to obtain 19.0 g of compound (E) (yield 89.1%).

(4) Synthesis of Exemplified Compound A3-1 Compound (E) 3.8 g (0.0083 mol) was added to 20 ml of dimethylacetamide, 2.18 g (0.0259 mol) of sodium bicarbonate, 2.10 g of 2-chlorobenzothiazole ( 0.0124 mol) and 2.0 ml of distilled water were added, and the mixture was stirred at 90 to 95 ° C. for 15 hours. After completion of the reaction, the reaction solution was cooled to room temperature and extracted by adding 400 ml of water and 400 ml of ethyl acetate. The ethyl acetate solution was washed twice with 300 ml of saturated brine, then washed with water and dried over anhydrous magnesium sulfate. The ethyl acetate solution was concentrated under reduced pressure and purified by silica gel column chromatography (eluent: n-hexane / ethyl acetate = 3/1). After dissolving in 100 ml of ethyl acetate, 400 ml of n-hexane was added. The precipitated solid was collected by filtration, washed with 100 ml of n-hexane, and dried to obtain 4.2 g of Exemplified Compound A3-1 as yellow crystals (yield 85.7%).

  About the obtained exemplary compound A3-1, the melting point was measured, and the maximum absorption wavelength (λmax) in ethyl acetate and the molar absorption coefficient (ε) were measured with a spectrophotometer UV-3100PC (manufactured by Shimadzu Corporation). As a result, the melting point was 132 ° C. to 133 ° C., the maximum absorption wavelength λmax = 437.1 nm, and ε = 46250.

[Phthalocyanine compounds]
The phthalocyanine compound is preferably a phthalocyanine compound substituted with an organic group. Details will be described below.
~ Phthalocyanine compound (1) ~
As the phthalocyanine compound, a compound represented by the general formula (C1) described in JP-A-2006-133508 is preferable. The description of the substituents in the formula, and preferred examples and synthesis examples thereof are also the same.

  Hereinafter, specific examples (exemplary compounds A4-1 to A4-13, A-14 to A-19) of the phthalocyanine compound (1) are shown. However, the present invention is not limited to these.

~ Phthalocyanine compound (2) ~
Examples of other phthalocyanine compounds include tetraazaporphyrin compounds represented by the following general formula (β). This compound is an organic solvent-soluble dye having a good molar extinction coefficient ε and color value, and simultaneously satisfies unprecedented high light resistance and high heat resistance, and easily dissolves in water or a solvent as required. It is a compound that can.

In the general formula (β), ring A ^d01 , ring A ^d02 , ring A ^d03 , and ring A ^d04 each independently ^{represent the following} aromatic ring, the direction of the condensed ring, and the substitution of the substituent bonded thereto: There are many isomers depending on the position.

Further, at least one of the ring A ^d01 , the ring A ^d02 , the ring A ^d03 , and the ring A ^{d04 represents} the ^following aromatic ring.

  Specifically, as the basic skeleton of the general formula (β), there are five types of structures of the following formulas (3) to (7). Furthermore, regioisomerism in which the position of N is different due to the difference in the condensation direction of the pyridine ring. There is a body. Furthermore, isomers having different substitution positions of substituents such as bromine also exist.

In the general formula (β), R ^d01 and R ^d02 each independently ^represent a hydrogen atom or a substituted or unsubstituted alkyl group. However, R ^d01 and R ^d02 do not represent a hydrogen atom at the same time. Moreover, m represents an integer of 1 to 8, and n represents an integer of 1 to 4.

The unsubstituted alkyl group represented by R ^d01 or R ^d02 is preferably an alkyl group having 1 to 12 carbon atoms, such as a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl. Group, n-hexyl group, 2-ethylhexyl group, n-octyl group, n-dodecyl group and the like, and straight chain or branched alkyl groups such as 4 to 12 carbon atoms are preferable. .

The substituted alkyl group represented by R ^d01 or R ^d02 is preferably a substituted alkyl group containing an oxygen atom in at least one form of an ether bond, a carbonyl bond, and an ester bond, and particularly an oxygen atom in the at least one form. A linear, branched, or cyclic substituted alkyl group having 1 to 4 carbon atoms and having 2 to 12 carbon atoms is preferred. For example, methoxymethyl group, ethoxymethyl group, butoxymethyl group, methoxyethyl group, ethoxyethyl group, 3-methoxypropyl group, 3-ethoxypropyl group, 3-butoxypropyl group, methoxyethoxyethyl group, ethoxyethoxyethyl group, Butoxyethoxyethyl group, methoxyethoxyethoxyethyl group, ethoxyethoxyethoxyethyl group, butoxyethoxyethoxyethyl group, acetylmethyl group, acetylethyl group, propionylmethyl group, propionylethyl group, tetrahydrofurfuryloxymethyl group, 2,2- Dimethyl-1,3-dioxolane-4-methoxymethyl group, 2- (1,3-dioxolane) ethoxymethyl group, 2- (1,3-dioxane) ethoxymethyl group, methoxycarbonylmethyl group, ethoxycarbonyl group Group,

Propoxycarbonylethyl group, butoxycarbonylethyl group, pentoxycarbonylbutyl group, 1- (butoxymethyl) ethyl group, 1- (methoxymethyl) propyl group, 1- (ethoxymethyl) propyl group, 1- (butoxymethyl) propyl 1- (2-methoxy-ethoxy-methyl) propyl group, 1- (2-ethoxy-ethoxy-methyl) propyl group, 1- (2-methoxy-2-ethoxy-2-ethoxymethyl) ethyl group, 1 -(2-ethoxy-2-ethoxy-2-ethoxymethyl) ethyl group, 1- (2-butoxy-2-ethoxy-2-ethoxymethyl) ethyl group, 1- (2-methoxy-2-ethoxy-2-) Ethoxymethyl) propyl group, 1- (2-ethoxy-2-ethoxy-2-ethoxymethyl) propyl group, 1- (2-propoxy) 2-ethoxy-2-ethoxymethyl) propyl group, 1- (2-butoxy-2-ethoxy-2-ethoxymethyl) propyl group, 1- (2-methoxy-2-ethoxy-2-ethoxymethyl) butyl group, 1- (2-ethoxy-2-ethoxy-2-ethoxymethyl) butyl group, 1- (2-propoxy-2-ethoxy-2-ethoxymethyl) butyl group,

1- (2-methoxy-2-ethoxy-2-ethoxymethyl) pentyl group, 1- (2-ethoxy-2-ethoxy-2-ethoxymethyl) pentyl group, 1- (2-methoxy-2-ethoxy-2) -Ethoxy-2-ethoxymethyl) ethyl group, 1- (2-ethoxy-2-ethoxy-2-ethoxy-2-ethoxymethyl) ethyl group, 1- (2-methoxy-2-ethoxy-2-ethoxy-2) -Ethoxymethyl) propyl group, 1- (2-ethoxy-2-ethoxy-2-ethoxy-2-ethoxymethyl) propyl group, 1- (2-methoxy-2-ethoxy-2-ethoxy-2-ethoxymethyl) Butyl group, 1- (2-methoxy-2-ethoxy-2-ethoxy-2-ethoxyethyl) ethyl group, 1- (2-ethoxy-2-ethoxy-2-ethoxy-2-ethoxye) L) ethyl group, 1- (2-methoxy-2-ethoxy-2-ethoxy-2-ethoxyethyl) propyl group, 1,1-di (methoxymethyl) methyl group, 1,1-di (ethoxymethyl) methyl Group, 1,1-di (propoxymethyl) methyl group, 1,1-di (butoxymethyl) methyl group, 1,1-di (2-methoxy-ethoxymethyl) methyl group, 1,1-di (2- Examples include ethoxy-ethoxymethyl) methyl group, 1,1-di (2-propoxy-ethoxymethyl) methyl group, and 1,1-di (2-butoxy-ethoxymethyl) methyl group.

As the ^{R d01} and ^{R d02,} each independently, a hydrogen atom (provided ^{that the R d01} and ^{R d02} represents a hydrogen atom at the same time no.), An unsubstituted alkyl group or "oxygen atom of ether bond, a carbonyl A preferred embodiment is a substituted alkyl group containing at least one form of a bond and an ester bond.

Among the above, R ^d01 and R ^d02 are each independently a hydrogen atom (provided that R ^d01 and R ^d02 do not simultaneously represent a hydrogen atom), an unsubstituted alkyl group having 1 to 12 carbon atoms, or An embodiment in which “a substituted alkyl group having 2 to 12 carbon atoms containing 1 to 4 oxygen atoms in at least one of an ether bond, a carbonyl bond, and an ester bond” is particularly preferable, and among them, R ^d01 and R ^d02 An embodiment in which at least one is “a substituted alkyl group having 2 to 12 carbon atoms containing 1 to 4 oxygen atoms in the form of at least one of an ether bond, a carbonyl bond, and an ester bond” has a solubility in a polar organic solvent. It is preferable at a high point.

Further, an embodiment in which at least one of R ^d01 and R ^d02 is a substituted alkyl group having 2 to 12 carbon atoms containing 1 to 4 oxygen atoms in at least one of an ether bond, a carbonyl bond, and an ester bond is preferable. In particular, a tetraazaporphyrin compound in which at least one of R ^d01 and R ^d02 is a substituted alkyl group represented by the following formula (β ² ) is preferable.

In the formula (β ² ), R ^d03 and R ^d04 each independently ^represent a hydrogen atom, an unsubstituted alkyl group, or an “alkyl group containing an oxygen atom in at least one form of an ether bond, a carbonyl bond, and an ester bond”. Represents an alkylcarbonyl group or an alkoxycarbonyl group. However, at least one of R ^d03 and R ^{d04 represents} an “alkyl group containing an oxygen atom in at least one form of an ether bond, a carbonyl bond, and an ester bond”, an alkylcarbonyl group, or an alkoxycarbonyl group.

The unsubstituted alkyl group represented by R ^d03 or R ^d04 is preferably an alkyl group having 1 to 8 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, or a pentyl group. Hexyl group, octyl group and the like.

The “substituted alkyl group containing an oxygen atom in at least one form of an ether bond, a carbonyl bond, and an ester bond” ^represented by R ^d03 or R ^d04 has 2 to 10 carbon atoms containing 1 to 4 oxygen atoms. A substituted alkyl group is preferred. For example, methoxymethyl group, ethoxymethyl group, propoxymethyl group, butoxymethyl group, methoxyethoxymethyl group, ethoxyethoxymethyl group, propoxyethoxymethyl group, butoxyethoxymethyl group, methoxyethoxyethoxymethyl group, ethoxyethoxyethoxymethyl group, Propoxyethoxyethoxymethyl group, butoxyethoxyethoxymethyl group, methoxyethoxyethoxyethoxymethyl group, ethoxyethoxyethoxyethoxymethyl group, propoxyethoxyethoxyethoxymethyl group, butoxyethoxyethoxyethoxymethyl group, acetylmethyl group, propionylmethyl group, tetrahydrofur Furyloxymethyl group, 2,2-dimethyl-1,3-dioxolane-4-methoxymethyl group, 2- (1,3-dioxolane) Kishimechiru group, 2- (1,3-dioxane) ethoxymethyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, propoxycarbonylmethyl group, butoxycarbonylmethyl group, pentoxycarbonyl methyl group and the like.

As the alkylcarbonyl group and alkoxycarbonyl group represented by R ^d03 or R ^d04 , an alkylcarbonyl group having 2 to 10 carbon atoms and an alkoxycarbonyl group having 2 to 10 carbon atoms are preferable. Examples include acetyl group, propionyl group, propylcarbonyl group, methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, pentoxycarbonyl group and the like.

  In the general formula (β), m represents an integer of 1 to 8, among which an integer of 1 to 6 is preferable, and an integer of 1 to 4 is particularly preferable in terms of high absorbance. N represents an integer of 1 to 4, preferably 2 or 3, and particularly preferably 2.

  The tetraazaporphyrin compound represented by the general formula (β) includes a part or all of these many isomers.

  Hereinafter, specific examples [specific examples A5-1 to A5-38] of the tetraazaporphyrin compound represented by the general formula (β) will be shown. The present invention is not limited to these specific examples.

-Method for producing tetraazaporphyrin compound represented by general formula (β)-
Hereinafter, a method for producing the tetraazaporphyrin compound represented by the general formula (β) will be described. The outline of a typical manufacturing method is as follows.
(1) Reaction of a mixture appropriately selected from the group of phthalic acid, bromo-substituted phthalic acid, pyridine-2,3-dicarboxylic acid, and bromo-substituted pyridine-2,3-dicarboxylic acid to produce a bromo-substituted tetraazaporphyrin compound The basic skeleton is manufactured.
(2) Next, this is chlorosulfonylated.
(3) It is obtained by reacting an amine with the obtained chlorosulfonylated bromo-substituted tetraazaporphyrin and amidating it.

  As another synthesis method, a mixture of phthalic acid and pyridine-2,3-dicarboxylic acid is reacted to synthesize a tetraazaporphyrin compound, chlorsulfonylated, amidated, and then brominated, or a tetraazaporphyrin compound is synthesized. It can also be obtained by bromination, chlorosulfonylation, and amidation.

Next, the above manufacturing method will be described in more detail.
(1) is a process for forming a bromo-substituted tetraazaporphyrin ring. Methods for forming a tetraazaporphyrin ring include phthalic acid, bromo-substituted phthalic acid, pyridine-2,3-dicarboxylic acid, and bromo-substituted pyridine. A mixture appropriately selected from the group consisting of -2,3-dicarboxylic acid and copper powder, copper oxide or copper salt, in the presence of ammonia gas, ammonium compound or urea, ammonium molybdate as a catalyst, It is obtained by heating to 120 to 300 ° C. in a solvent-free or solvent such as tetralin, 1-chloronaphthalene, nitrobenzene, trichlorobenzene, and DMI.

  A mixture of phthalic acid (A), bromo-substituted phthalic acid (B), pyridine-2,3-dicarboxylic acid (C), and bromo-substituted pyridine-2,3-dicarboxylic acid (D) used in the method for forming a ring The component ratio (molar ratio) of each component in (A) + (B) :( C) + (D) is preferably 3.5: 0.5 to 0: 4, more preferably 3: 1 to 0.5: 3.5, more preferably 3: 1 to 1: 3, and (A) + (C) :( B) + (D) is 3.5: 0.5 to It is preferably 0: 4, more preferably 3: 1 to 0.5: 3.5, and even more preferably 3: 1 to 1: 3.

  Further, in place of phthalic acid, bromo-substituted phthalic acid, pyridine-2,3-dicarboxylic acid, or bromo-substituted pyridine-2,3-dicarboxylic acid, dicyano compounds or acid anhydrides thereof can be used.

  Specific examples of the bromo-substituted phthalic acid include 3-bromophthalic acid, 4-bromophthalic acid, 3,4,5,6-tetrabromophthalic acid and the like. Specific examples of the bromo-substituted pyridine-2,3-dicarboxylic acid include 5-bromopyridine-2,3-dicarboxylic acid, 6-bromopyridine-2,3-dicarboxylic acid and the like.

(2) is a chlorosulfonylation step in which chlorosulfonylation is performed, and the bromo-substituted tetraazaporphyrin compound obtained in the step (1) is reduced to 20 ° C. or less in 5 to 20 times the mass of chlorosulfonic acid. Add in small portions to keep. After stirring at the same temperature for 1 hour, the mixture is reacted at 155 to 160 ° C. for 4 hours. It cools to 80 degreeC and it dripped over 1-2 hours, keeping 2-5 times mass thionyl chloride of a tetraaza porphyrin compound at 70-80 degreeC. The mixture is further stirred at the same temperature for 2 to 10 hours, cooled to 15 to 20 ° C., and stirred at the same temperature for 12 hours. This reaction solution was discharged little by little into ice water having a mass of 50 to 200 times the amount of chlorosulfonic acid used, and the precipitate was filtered off and washed with ice water until neutral, and the sulfonyl of a bromo-substituted tetraazaporphyrin compound was obtained. A chloride body is obtained.
The reaction conditions described above are mainly those for obtaining tetrasulfonyl chloride, but when obtaining mono-, di- or tri-substituted sulfonyl chlorides, it is possible to make the reaction conditions in chlorosulfonic acid more gentle. . That is, it can be achieved by lowering the reaction temperature or shortening the reaction time.

(3) is a sulfonamidation step in which amidation is carried out. The sulfonyl chloride form of the bromo-substituted tetraazaporphyrin compound obtained in the step (2) is suspended in ice water, and NHR ^d01 R ^d02 ( In the formula, R ^d01 and R ^d02 are synonymous with R ^d01 and R ^d02 in the general formula (β).) An organic amine compound (2 to 8-fold molar ratio of the bromo-substituted tetraazaporphyrin compound) It is dropped while keeping the temperature at 15 ° C. or lower. After dropping, the tetraazaporphyrin compound represented by the general formula (β) is obtained by stirring at 20 to 30 ° C. for 15 to 24 hours, filtering, washing with water, and drying.

  In many cases, the product obtained as described above is a mixture of a plurality of isomers as described above, but the mixture is also within the scope of the present invention. Can play.

  In the case of a mixture, it can be purified by a conventional purification method such as recrystallization with an organic solvent such as ethyl acetate, acetone or methanol, or further purification using column chromatography, if necessary. Compounds can also be obtained.

[Azomethine compounds]
The azomethine compound is preferably a compound in which a heterocycle is directly linked. The hetero ring is the same as the hetero ring in the section of the heterocyclic azo compound, and preferred examples and specific examples are also the same.
~ Azomethine compound (1) ~
Examples of the azomethine compound include azomethine dyes represented by the following general formula (γ). This dye has excellent stability with no precipitation over time when it is in the form of a liquid preparation or a coated film, has excellent resistance to heat and light, and developability that suppresses development residues. is there.

In the general formula (γ), R ^e01 represents a hydrogen atom or a substituent, R ^e02 , R ^e03 , R ^e04 , and R ^e05 each independently represent a hydrogen atom or a substituent, and R ^e06 and R ^{e06 e07} each independently represents an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group. Za and Zb each independently represent ^—N═ or —C (R ^d08 ) ^═ , and R ^d08 represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group. R ^e02 and R ^e03 , R ^e03 and R ^e06 , R ^e04 and R ^e05 , R ^e05 and R ^e07 , and R ^e06 and R ^e07 are bonded to each other to form a 5-membered, 6-membered or 7-membered ring. May be.
Hereinafter, R ^{e01 to} R ^e07 , Za and Zb in the general formula (γ) will be described in detail.

In the general formula (γ), R ^e01 represents a hydrogen atom or a substituent. The substituent represented by ^Re01 is a halogen atom (for example, a fluorine atom, a chlorine atom or a bromine atom), an alkyl group (preferably an alkyl group having 1 to 48 carbon atoms, more preferably a linear or branched chain having 1 to 18 carbon atoms). A chain or cyclic alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, dodecyl, hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, 1 -Norbornyl, 1-adamantyl, etc.), an alkenyl group (preferably an alkenyl group having 2 to 48 carbon atoms, more preferably 2 to 18 carbon atoms, such as vinyl, allyl, 3-buten-1-yl, etc. An aryl group (preferably having 6 to 48 carbon atoms, more preferably 6 to 12 carbon atoms). An aryl group such as phenyl and naphthyl), a heterocyclic group (preferably a heterocyclic group having 1 to 32 carbon atoms, more preferably 1 to 12 carbon atoms, such as 2-thienyl, 4- Pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyridyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, benzotriazol-1-yl, etc.), silyl group (preferably having 3 to 38 carbon atoms, More preferably, it is a 3-12 silyl group, for example, trimethylsilyl, triethylsilyl, tributylsilyl, t-butyldimethylsilyl, t-hexyldimethylsilyl, etc.), hydroxyl group, cyano group, nitro group, alkoxy Group (preferably an alkoxy group having 1 to 48 carbon atoms, more preferably 1 to 12 carbon atoms, Butoxy, ethoxy, 1-butoxy, 2-butoxy, isopropoxy, t-butoxy, dodecyloxy, cycloalkyloxy group (e.g. cyclopentyloxy, cyclohexyloxy), and the like.),

An aryloxy group (preferably an aryloxy group having 6 to 48 carbon atoms, more preferably 6 to 12 carbon atoms, such as phenoxy, 1-naphthoxy, etc.), a heterocyclic oxy group (preferably having 1 to 1 carbon atoms). 32, more preferably a heterocyclic oxy group having 1 to 12 such as 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy, and the like, and a silyloxy group (preferably having 1 to 32 carbon atoms). More preferably, it is a silyloxy group having 1 to 12, for example, trimethylsilyloxy, t-butyldimethylsilyloxy, diphenylmethylsilyloxy, etc.), an acyloxy group (preferably having 2 to 48 carbon atoms, more preferably 2 to 12 acyloxy groups such as acetoxy, pivaloyloxy, benzo Yloxy, dodecanoyloxy, and the like.),

An alkoxycarbonyloxy group (preferably an alkoxycarbonyloxy group having 2 to 48 carbon atoms, more preferably 2 to 12 carbon atoms such as ethoxycarbonyloxy, t-butoxycarbonyloxy, cycloalkyloxycarbonyloxy group (for example, cyclohexyloxycarbonyl) Oxy), etc.), an aryloxycarbonyloxy group (preferably an aryloxycarbonyloxy group having 7 to 32 carbon atoms, more preferably 7 to 18 carbon atoms, such as phenoxycarbonyloxy), and carbamoyl. An oxy group (preferably a carbamoyloxy group having 1 to 48 carbon atoms, more preferably 1 to 12 carbon atoms, such as N, N-dimethylcarbamoyloxy, N-butylcarbamoyloxy, N-phenylcarbamoyloxy, -Ethyl-N-phenylcarbamoyloxy, etc.), a sulfamoyloxy group (preferably a sulfamoyloxy group having 1 to 32 carbon atoms, more preferably 1 to 12 carbon atoms, such as N, N- Diethyl sulfamoyloxy, N-propylsulfamoyloxy, etc.).

An alkylsulfonyloxy group (preferably an alkylsulfonyloxy group having 1 to 38 carbon atoms, more preferably 1 to 12 carbon atoms, such as methylsulfonyloxy, hexadecylsulfonyloxy, cyclohexylsulfonyloxy, etc.), arylsulfonyl An oxy group (preferably an arylsulfonyloxy group having 6 to 32 carbon atoms, more preferably 6 to 12 carbon atoms, such as phenylsulfonyloxy), an acyl group (preferably having 1 to 48 carbon atoms, more preferably 1 to 12 acyl groups such as formyl, acetyl, pivaloyl, benzoyl, tetradecanoyl, cyclohexanoyl, etc.), alkoxycarbonyl groups (preferably having 2 to 48 carbon atoms, more preferably 2 to 2 carbon atoms). 12 alkoxycarbonyl groups Yes, for example, methoxycarbonyl, ethoxycarbonyl, octadecyloxycarbonyl, cyclohexyloxycarbonyl, etc.), an aryloxycarbonyl group (preferably an aryloxycarbonyl group having 7 to 32 carbon atoms, more preferably 7 to 12 carbon atoms). For example, phenoxycarbonyl and the like.

A carbamoyl group (preferably a carbamoyl group having 1 to 48 carbon atoms, more preferably 1 to 12 carbon atoms such as carbamoyl, N, N-diethylcarbamoyl, N-ethyl-N-octylcarbamoyl, N, N-dibutylcarbamoyl, N-propylcarbamoyl, N-phenylcarbamoyl, N-methylN-phenylcarbamoyl, N, N-dicyclohexylcarbamoyl, etc.), amino group (preferably having 32 or less carbon atoms, more preferably 12 or less amino groups) Group, for example, amino, methylamino, N, N-dibutylamino, tetradecylamino, 2-ethylhexylamino, cyclohexylamino, etc.), anilino group (preferably having 6 to 32 carbon atoms, more preferably Are 6-12 anilino groups, for example anilino, N Methylanilino and the like), a heterocyclic amino group (preferably a heterocyclic amino group having 1 to 32 carbon atoms, more preferably 1 to 12 carbon atoms, such as 4-pyridylamino), a carbonamido group ( Preferably, it is a carbonamide group having 2 to 48 carbon atoms, more preferably 2 to 12 carbon atoms, and examples thereof include acetamido, benzamide, tetradecanamide, pivaloylamide, cyclohexaneamide, and the like, and ureido groups (preferably having 1 to 1 carbon atoms). 32, more preferably 1 to 12 ureido groups such as ureido, N, N-dimethylureido, N-phenylureido, etc.), imide groups (preferably having 20 or less carbon atoms, more preferably 12 or less imide groups, such as N-succinimide, N-phthalimide, etc. And the like.),

An alkoxycarbonylamino group (preferably an alkoxycarbonylamino group having 2 to 48 carbon atoms, more preferably 2 to 12 carbon atoms, such as methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, octadecyloxycarbonylamino, cyclohexyloxy; Carbonylamino, etc.), an aryloxycarbonylamino group (preferably an aryloxycarbonylamino group having 7 to 32 carbon atoms, more preferably 7 to 12 carbon atoms, such as phenoxycarbonylamino), and sulfone. An amide group (preferably a sulfonamide group having 1 to 48 carbon atoms, more preferably 1 to 12 carbon atoms, such as methanesulfonamide, butanesulfonamide, benzenesulfonamide, hexadecanesulfonamide; , Cyclohexanesulfonamide, etc.), a sulfamoylamino group (preferably a sulfamoylamino group having 1 to 48 carbon atoms, more preferably 1 to 12, such as N, N-dipropylsulfamoyl). Amino, N-ethyl-N-dodecylsulfamoylamino, etc.), an azo group (preferably an azo group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms such as phenylazo and 3-pyrazolyl). Azo, etc.), an alkylthio group (preferably an alkylthio group having 1 to 48 carbon atoms, more preferably 1-12, such as methylthio, ethylthio, octylthio, cyclohexylthio, etc.), an arylthio group. (Preferably an arylthio group having 6 to 48 carbon atoms, more preferably 6 to 12 carbon atoms. And a heterocyclic thio group (preferably a heterocyclic thio group having 1 to 32 carbon atoms, more preferably 1 to 12 carbon atoms such as 2-benzothiazolylthio, 2-pyridylthio, 1- Phenyltetrazolylthio etc.), alkylsulfinyl group (preferably an alkylsulfinyl group having 1 to 32 carbon atoms, more preferably 1 to 12 carbon atoms such as dodecanesulfinyl).

An arylsulfinyl group (preferably an arylsulfinyl group having 6 to 32 carbon atoms, more preferably 6 to 12 carbon atoms such as phenylsulfinyl), an alkylsulfonyl group (preferably having 1 to 48 carbon atoms, more preferably 1 to 12 alkylsulfonyl groups such as methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, isopropylsulfonyl, 2-ethylhexylsulfonyl, hexadecylsulfonyl, octylsulfonyl, cyclohexylsulfonyl and the like. A group (preferably an arylsulfonyl group having 6 to 48 carbon atoms, more preferably 6 to 12 carbon atoms, such as phenylsulfonyl, 1-naphthylsulfonyl, etc.), a sulfamoyl group (preferably Or a sulfamoyl group having 32 or less carbon atoms, more preferably 16 or less, such as sulfamoyl, N, N-dipropylsulfamoyl, N-ethyl-N-dodecylsulfamoyl, N-ethyl-N-phenylsulfuryl. Famoyl, N-cyclohexylsulfamoyl, etc.), sulfo group, phosphonyl group (preferably a phosphonyl group having 1 to 32 carbon atoms, more preferably 1 to 12 carbon atoms such as phenoxyphosphonyl and octyloxy Phosphonyl, phenylphosphonyl, etc.), phosphinoylamino groups (preferably phosphinoylamino groups having 1 to 32 carbon atoms, more preferably 1 to 12 carbon atoms such as diethoxyphosphinoylamino). , Dioctyloxyphosphinoylamino and the like.

When the substituent represented by R ^e01 is a further substitutable group, it may be further substituted with the above R ^e01 , and when it has two or more substituents, those substituents are They may be the same or different.

R ^{e02 to} R ^e05 in the general formula (γ) each independently represent a hydrogen atom or a substituent, and the substituent represented by R ^{e02 to} R ^e05 has the same ^meaning as the substituent represented by R ^e01. The preferred embodiment is also the same. When the substituent represented by R ^{e02 to} R ^e05 is a further substitutable group, it may be substituted with the substituent represented by R ^{e01 or} may be substituted with two or more substituents These substituents may be the same or different.

In the general formula (γ), R ^e06 and R ^e07 each independently represents an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group, and an alkyl group, an alkenyl group represented by R ^e06 or R ^e07 , The aryl group and heterocyclic group have the same ^meanings as the alkyl group, alkenyl group, aryl group, and heterocyclic group described for the substituent represented by R ^e01 , and the preferred ranges thereof are also the same.

When R ^e06 and R ^e07 are further substitutable groups, they may be further substituted with the substituent represented by R ^e01 , and when they are substituted with two or more substituents, The substituents may be the same or different.

In the general formula (γ), Za and Zb each independently represent ^—N═ or —C (R ^d08 ) ^═ , and R ^d08 represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group. Represents.
The alkyl group, alkenyl group, aryl group, or heterocyclic group represented by R ^{d08 has the same meaning} as the alkyl group, alkenyl group, aryl group, or heterocyclic group described in the substituent represented by R ^e01. The same applies to each preferred range. In addition, when the substituent represented by R ^d08 is a further substitutable group, it may be further substituted with the substituent represented by R ^e01 , and is substituted with two or more substituents. In some cases, the substituents may be the same or different.

Among them, Za is preferably -N =, and Zb is preferably -C (R ^d08 ). R ^d08 is preferably an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group. More preferably, it is an embodiment represented by the following general formula (γ2) or general formula (γ3).

In the general formula (γ), R ^e02 and R ^e03 , R ^e03 and R ^e06 , R ^e04 and R ^e05 , R ^e05 and R ^e07 , and R ^e06 and R ^e07 are bonded to each other to form 5 and 6 members, respectively. Or a 7-membered ring. Here, the formed 5-membered, 6-membered, or 7-membered ring may be further substituted with the substituent represented by R ^e01 , and when it is substituted with two or more substituents, These substituents may be the same or different.

Among the azomethine dyes represented by the general formula (γ), an azomethine dye represented by the following general formula (γ2) is preferable. Hereinafter, R ^{e09 to} R ^e14 , R ^{e31 to} R ^e34 , R ^e36 , Zc, and Zd in the general formula (γ2) will be described in detail.

In the general formula (γ2), R ^e09 , R ^e10 , R ^e11 , R ^e12 , R ^e13 , and R ^e14 each independently represent a hydrogen atom or a substituent. The substituents represented by R ^{e09 to} R ^e14 are synonymous with the substituent represented by R ^e01 , and the preferred ranges thereof are the same.

When the substituents represented by R ^{e09 to} R ^e14 are further substitutable groups, they may be further substituted with the substituent represented by R ^e01 and may be substituted with two or more substituents. The substituents may be the same or different.

In the general formula (γ2), R ^e31 represents a hydrogen atom or a substituent, and the substituent represented by R ^e31 has the same ^meaning as the substituent represented by R ^e01 in the general formula (γ), The preferred range is the same. When the substituent represented by R ^e31 is a further substitutable group, it may be further substituted with the substituent represented by R ^e01 , or may be substituted with two or more substituents. These substituents may be the same or different.

In the general formula (γ2), R ^e32 , R ^e33 , and R ^e34 each independently represent a hydrogen atom or a substituent. R ^e32 is a synonymous with ^{R e02} in formula (gamma), preferred embodiments thereof are also the ^{same, R e33} is a synonymous with ^{R e03} in formula (gamma), also a preferred embodiment in ^{and, R e34} is a synonymous with ^{R e04} in formula (gamma), preferred embodiments thereof are also the ^{same, R e36} is a synonymous with ^{R e06} in formula (gamma), the preferred embodiment Is the same.

When R ^{e32 to} R ^e34 are groups that can be further substituted, they may be substituted with a substituent represented by R ^e01 , and when they are substituted with two or more substituents, The substituents may be the same or different.
In the general formula (γ2), R ^e32 and R ^e33 , R ^e33 and R ^e36 , R ^e36 and R ^e09 , and R ^e34 and R ^e14 are bonded to each other to form a 5-membered, 6-membered, or 7-membered ring. May be formed.

  In the general formula (γ2), Zc has the same meaning as Za in the general formula (γ) described above, and its preferred embodiment is also the same, and Zd has the same meaning as Zb in the general formula (γ) described above. And the preferable aspect is also the same.

  Among the azomethine dyes represented by the general formula (γ2), an azomethine dye represented by the following general formula (γ3) is more preferable.

In the general formula ^{(γ3), R e09 ~R e14} , R e31 ~R e34 are respectively synonymous with ^{R e09 ~R e14, R e31 ~R} e34 in the general formula ^{(γ2), R e38} is a hydrogen An atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group is represented.

In the general formula ([gamma] 3), the alkyl group represented by R ^e38, alkenyl group, aryl group, and heterocyclic group, an alkyl group described for the substituent represented by R ^e01, an alkenyl group, an aryl group, And the same as the heterocyclic group, and the preferred embodiments thereof are also the same.
In addition, R ^e38 may be further substituted with the substituent described for R ^e01 , and when it is substituted with two or more substituents, these substituents may be the same or different. Good.

As described above, the azomethine dye represented by the general formula (γ) is preferably an azomethine dye represented by the general formula (γ2), more preferably an azomethine dye represented by the general formula (γ3). It is.
Next, a preferable range of the dye represented by the general formula (γ3) will be described.

In the general formula (γ3), R ^e31 represents an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a hydroxyl group, a cyano group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, a carbamoyloxy group, an acyl group, an alkoxy group. Carbonyl group, aryloxycarbonyl group, carbamoyl group, imide group, azo group, alkylthio group, arylthio group, heterocyclic thio group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfamoyl group, sulfo group, A phosphonyl group or a phosphinoylamino group, wherein R ^e32 , R ^e33 , and R ^e34 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryl Oxy group, Arco Sicarbonyl group, carbamoyl group, amino group, anilino group, carbonamido group, ureido group, alkoxycarbonylamino group, sulfonamido group, sulfamoylamino group, azo group, alkylthio group, arylthio group, heterocyclic thio group, alkyl A sulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, a sulfo group, a phosphonyl group, or a phosphinoylamino group, wherein ^Re36 is an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group; R ^e38 is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group, and R ^{e09 to} R ^e14 are each independently a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group. Certain azomethine dyes are preferred.

More preferably, in the general formula (γ3), R ^e31 is an alkyl group, alkenyl group, aryl group, heterocyclic group, alkoxycarbonyl group, carbamoyl group, imide group, alkylthio group, arylthio group, heterocyclic thio group, alkyl group. A sulfonyl group or an arylsulfonyl group, wherein R ^e32 , R ^e33 , and R ^e34 are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, a carbamoyl group, a carbonamido Group, ureido group, alkoxycarbonylamino group, sulfonamido group, alkylthio group, or arylthio group, R ^e36 is an alkyl group, alkenyl group, aryl group, or heterocyclic group, and R ^e38 is a hydrogen atom, Alkyl group, alkenyl group, a It is a azomethine dye which is a reel group or a heterocyclic group and each of R ^{e09 to} R ^e14 is independently a hydrogen atom or an alkyl group.

More preferably, in the general formula (γ3), R ^e31 is an alkyl group, aryl group, heterocyclic group, alkoxycarbonyl group, carbamoyl group, alkylthio group, arylthio group, alkylsulfonyl group, or arylsulfonyl group, R ^e32 , R ^e33 and R ^e34 are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, a carbamoyl group, a carbonamido group, a ureido group, an alkoxycarbonylamino group, a sulfone. An amide group, an alkylthio group, or an arylthio group, R ^e36 is an alkyl group or an aryl group, R ^e38 is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group; ^{e09 to} R ^e14 are independent of each other And an azomethine dye which is a hydrogen atom or an alkyl group.

More preferably, in the general formula (γ3), R ^e31 is an alkyl group, and R ^e32 , R ^e33 , and R ^e34 are each independently a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group. R ^e36 is an alkyl group, R ^e38 is an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group, and R ^{e09 to} R ^e14 are each independently a hydrogen atom or an alkyl group, It is.

Most preferably, in the general formula (γ3), R ^e31 is a tertiary alkyl group, and R ^e32 , R ^e33 , and R ^e34 are each independently a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group. R ^e36 is an alkyl group, R ^e38 is an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group, R ^e09 and R ^e10 are alkyl groups, and R ^{e11 to} R ^e13 are It is an azomethine dye which is a hydrogen atom and R ^e14 is an alkyl group.

  Hereinafter, specific examples (exemplary dyes A6-1 to A6-29) of the azomethine dyes represented by the general formulas (γ) to (γ3) are shown. However, it is not limited to these.

Next, a synthesis example of the azomethine dye represented by the general formula (γ) will be described with reference to the following reaction scheme A by taking a synthesis example of the exemplified dye A6-29 as an example. However, the present invention is not limited to this, and the exemplified dyes other than the exemplified dye A6-29 can be obtained by a similar method.

<< Synthesis Example >>: Synthesis of Exemplified Dye A6-29

(1) Synthesis of Compound B Compound A (manufactured by Sigma-Aldrich) 94.7 g (0.5 mol), sodium iodide 37.5 g (0.25 mol), and sodium hydrogen carbonate 126 g (1.5 mol) 300 ml of dimethylimidazolidinone was added, and the mixture was heated to 95 ° C. and stirred. To this solution, 90.3 g (0.65 mol) of 3-bromopropanol was added dropwise. After completion of the dropwise addition, the reaction was completed by heating and stirring at 95-100 ° C. for 5 hours. After completion of the reaction, the reaction solution was cooled to room temperature and extracted by adding 600 ml of water and 500 ml of ethyl acetate. Thereafter, this ethyl acetate solution was washed with water and dried over anhydrous magnesium sulfate. The ethyl acetate solution was concentrated under reduced pressure and purified by silica gel column chromatography (eluent: n-hexane / ethyl acetate = 10/1) to obtain 90.5 g (yield: 73.2%) of compound B. .

(2) Synthesis of Compound C Subsequently, 270 ml of methanol was added to 90 g (0.364 mol) of Compound B obtained above, and the mixture was cooled to 5 ° C. and stirred. To this solution, 93.7 ml (1.09 mol) of concentrated hydrochloric acid was added dropwise, and then a solution prepared by dissolving 27.6 g (0.4 mol) of sodium nitrite in 75 ml of water was added dropwise while maintaining at 5 to 10 ° C. After completion of the dropping, the reaction was completed by stirring at 5 to 10 ° C. for 2 hours. After completion of the reaction, 500 ml of ethyl acetate and 1000 ml of water were added. After neutralizing the solution by adding 84 g of sodium hydrogen carbonate little by little, the aqueous phase was removed. The ethyl acetate solution was washed with water and then dried over anhydrous magnesium sulfate. When this ethyl acetate solution was concentrated under reduced pressure, crystals were precipitated. To the precipitated crystals, 200 ml of n-hexane and 200 ml of ethyl acetate were added and stirred to disperse the crystals. The crystals were filtered and dried to obtain 78 g of Compound C (Yield: 77.6%).

(3) Synthesis of Compound E Next, Compound E was synthesized by the method shown in the following scheme.

-Synthesis of Intermediate (M)-
To 112 g (0.9 mol) of 4-methoxyphenol, 600 ml of dimethylacetamide was added and stirred at room temperature. To this solution was added 196 ml of 28% methanol solution of sodium methoxide. After completion of the addition, 190 g (0.97 mol) of 2-bromobutanoic acid ethyl ester was added dropwise to this solution. After completion of the dropwise addition, the mixture was stirred at room temperature for 3 hours to complete the reaction.
To this reaction solution, 1000 ml of water and 1000 ml of ethyl acetate were added and extracted with ethyl acetate. The ethyl acetate solution was washed with brine, and then 250 ml of methanol was added to the residue obtained by distilling off ethyl acetate under reduced pressure, followed by stirring at room temperature. An aqueous solution in which 144 g of sodium hydroxide was dissolved in 1000 ml of water was added to this solution, and then heated to 50 to 55 ° C. and stirred for 2 hours. After completion of the reaction, 340 ml of concentrated hydrochloric acid was added dropwise to the reaction solution to make it acidic. Subsequently, 1000 ml of ethyl acetate was added for extraction, and the ethyl acetate solution was washed with brine and then dried over anhydrous sodium sulfate. The ethyl acetate solution was concentrated under reduced pressure to quantitatively remove the intermediate (M). Obtained.

-Synthesis of Intermediate (N)-
400 ml of toluene was added to 93.1 g (0.433 mol) of the intermediate (M) obtained as described above, and the mixture was heated to 85 to 90 ° C. and stirred. To this was added dropwise 50 ml of thionyl chloride, and the mixture was heated and stirred for 3 hours. After completion of the reaction, toluene and excess thionyl chloride were distilled off under reduced pressure. Then, after cooling to room temperature, 100 ml of ethyl acetate was added to obtain an ethyl acetate solution of intermediate (N). This ethyl acetate solution of intermediate (N) was used in the next step.

-Synthesis of Compound E-
According to the method described in JP-A-2-201443, 5-amino-3-methylpyrazole as a raw material is synthesized by 5-amino-3-tert-butylpyrazole (the method described in Japanese Patent No. 2670943). Intermediate L was obtained instead.
570 ml of 2-propanol was added to 189 g (0.538 mol) of this intermediate L, and the mixture was heated and stirred. Then, 33.6 g (0.673 mol) of hydrazine monohydrate was added dropwise to this solution, and the mixture was heated and stirred for 2 hours. After completion of the reaction, about 400 ml of 2-propanol was distilled off under reduced pressure. To the residue, 420 g of sodium hydrogen carbonate, 1500 ml of water, and 1200 ml of ethyl acetate were added and stirred at room temperature. Subsequently, the ethyl acetate solution of the said intermediate (N) was dripped at this solution, and after completion | finish of dripping, it stirred at room temperature for 2 hours, and also removed the water phase. When this ethyl acetate solution was washed with water, crystals were precipitated. After adding 1200 ml of n-hexane to this dispersion and stirring for 1 hour, the crystals were filtered, washed with water, and dried to obtain 159 g of Compound E (yield: 86.9%).

(4) Synthesis of Illustrative Dye A6-29 To 7.35 g (0.0266 mol) of Compound C obtained above, 50 ml of methanol, 100 ml of ethyl acetate, and 100 ml of water were added, and the mixture was heated to 40 ° C. and stirred. To this solution, 25 g of hydrosulfite soda was added little by little, and after completion of the addition, reaction was carried out at 40 ° C. for 1 hour. After completion of the reaction, the reaction mixture was cooled to room temperature, 100 ml of ethyl acetate and 200 ml of water were added, and the aqueous phase was removed to obtain an ethyl acetate solution containing Compound D. This ethyl acetate solution was used in the next step.
Subsequently, 100 ml of methanol and 200 ml of water were added to 10.0 g (0.0242 mol) of the compound E obtained above and 21 g of sodium hydrogen carbonate, and the mixture was stirred at room temperature. To this solution, the entire amount of the above ethyl acetate solution was added, and an aqueous solution obtained by dissolving 12 g of ammonium persulfate in 100 ml of water was added dropwise. After completion of the dropping, the reaction was performed at room temperature for 1 hour. After completion of the reaction, the aqueous phase was removed, and then the ethyl acetate solution was washed with water and further concentrated under reduced pressure. The residue was purified by silica gel column chromatography (eluent: n-hexane / ethyl acetate = 1/1) to obtain an amorphous exemplified dye A6-29.
As a result of identification using a spectrophotometer UV-2500PC (manufactured by Shimadzu Corporation), the maximum absorption wavelength λ _max in the ethyl acetate solution was 556 nm and the molar absorption coefficient ε was 5,5000.

-Description of substituents-
The “substituent” in the present specification will be described.
In the present specification, the “substituent” represents an arbitrary group regardless of inorganic or organic, and specifically includes a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, a carboxylic acid group, and a sulfonic acid group. , Sulfinic acid group, alkyl group (including linear, branched, and cyclic), alkenyl group (including linear, branched, and cyclic), alkynyl group, aryl group, heterocyclic group, formyl group, or And a group obtained by arbitrarily combining one partial structure selected from the following group (A) and one partial structure selected from an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and a heterocyclic group. It is done.
Group (A): ether group, amino group, thioether group, ketone group, ester group, amide group, urethane group [carbamoyl group -O-CO-N (R)-], urea group [-N (R) -CO -N (R) -], a sulfinyl group [-SO-], a sulfonyl group [-SO ₂ -], a sulfonic acid ester group _[-SO 2 -O-], a sulfonamide group _[-SO 2 -N (R) -], imide group [-CO-N (R) -CO-], sulfonyl amido groups _[-SO 2 -N (R) -CO-], disulfonylimide groups _[-SO 2 -N (R) _{-SO 2-} ]

  R bonded to the nitrogen atom in the group (A) represents any of a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group.

  In the “substituent”, the alkyl group may be linear, branched or cyclic. In the case of a ring, it may be monocyclic or polycyclic. The alkyl group is preferably an alkyl group having 1 to 30 carbon atoms, specifically, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a cyclopentyl group, a cyclohexyl group, or a norbornyl group. And an adamantyl group. Moreover, you may have a substituent further in the arbitrary positions of these alkyl groups, and all the above-mentioned "substituents" are included in the further substituents including said alkyl group itself. In the case of a cyclic alkyl group, a partial structure selected from the above group (A) may be inserted at any position of the carbon-carbon bond constituting the ring.

  In the “substituent”, the alkenyl group may be linear, branched or cyclic. In the case of a ring, it may be monocyclic or polycyclic. The alkenyl group is preferably an alkenyl group having 2 to 20 carbon atoms, specifically, vinyl group, allyl group, 1-methylvinyl group, 3-buten-1-yl group, cyclopentan-2-ene-1 -Yl group, cyclohexane-2-en-1-yl group, cyclohexane-1-en-1-yl group and the like. Further, the alkenyl group may further have a substituent at any position, and the additional substituent includes all of the above-mentioned “substituents”. In the case of a cyclic alkenyl group, a partial structure selected from the above group (A) may be inserted at any position of the carbon-carbon bond constituting the ring.

  In the “substituent”, the alkynyl group is an ethynyl group, but may be substituted by a hydrogen atom of the ethynyl group. The substituents herein include all of the above “substituents”.

  In the “substituent”, the aryl group may be either a single ring or a condensed ring as long as it is an aromatic ring, and is preferably an aryl group having 6 to 30 carbon atoms. Specific examples include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, and a pyrenyl group. Further, the aryl group may further have a substituent at any position, and examples of the further substituent include all of the above-mentioned “substituents”.

  In the “substituent”, the heterocyclic group has a hetero atom (eg, nitrogen atom, sulfur atom, oxygen atom) in the ring, and may be a saturated ring or an unsaturated ring. It may be a single ring or a condensed ring. For example, tetrahydrofuranyl group, dihydrofuranyl group, dihydrofuranyl group, tetrahydropyranyl group, dihydropyranyl group, oxocanyl group, dioxanyl group, tetrahydrothiophenyl group, dithianyl group, pyrrolidinyl group, pyrrolinyl group, tetrahydropyridinyl Group, piperazinyl group, homopiperazinyl group, piperidinyl group, pyrrolyl group, furyl group, thiophenyl group, benzopyrrolyl group, benzofuryl group, benzothiophenyl group, pyrazolyl group, isoxazolyl group, isothiazolyl group, indazolyl group, benzoisoxazolyl group, Benzoisothiazolyl, imidazolyl, oxazolyl, thiazolyl, benzoimidazolyl, benzoxazolyl, benzothiazolyl, pyridyl, quinolinyl, isoquinolinyl, pyrida Nyl, pyrimidinyl, pyrazinyl, cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, acridinyl, phenanthridinyl, phthalazinyl, carbazolyl, uracil, dithiouracil, carbolinyl, purinyl, thiadiazolyl Groups and the like. Further, the heterocyclic group may further have a substituent at any position, and the additional substituent includes all of the above-mentioned “substituents”.

  In addition, the above-mentioned “organic group” refers to an “substituent” containing at least a carbon atom.

-Other organic solvent soluble dyes (A ')-
Furthermore, the organic solvent-soluble dye (A ′) other than the above-mentioned (A) organic solvent-soluble dye that can be contained in the composition of the present invention will be described.
Further, other organic solvent-soluble dyes that may be included are not particularly limited, and conventionally known dyes for color filters can be used. For example, Japanese Patent Application Laid-Open No. 64-90403, Japanese Patent Application Laid-Open No. 64-91102, Japanese Patent Application Laid-Open No. 1-94301, Japanese Patent Application Laid-Open No. 6-11614, No. 2592207, US Pat. No. 4,808,501. Specification, US Pat. No. 5,667,920, US Pat. No. 5,059,500, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115 The dyes described in JP-A-6-194828 can be used.

  The chemical structure includes azo dyes other than the above, triphenylmethane, anthraquinone, benzylidene, oxonol, phenothiazine, azomethine other than the above, xanthene, phthalocyanine other than the above, benzopyran, indigo And pigments such as anthrapyridone.

  When the resist system is subjected to water or alkali development, at least one of acid dyes and derivatives thereof may be suitably used in that the dye is completely removed by development. In addition, it is also useful to select and use at least one of direct dyes, basic dyes, mordant dyes, acid mordant dyes, azoic dyes, disperse dyes, oil-soluble dyes, food dyes, and derivatives thereof as appropriate. is there.

  Hereinafter, the acid dye and its derivative will be described. The acidic dye is not particularly limited as long as it is a pigment having an acidic group such as a sulfonic acid, a carboxylic acid, or a phenolic hydroxyl group, but is soluble in an organic solvent or a developer used for the preparation of a composition or a development process, It is selected in consideration of all required performances such as salt formation with a basic compound, absorbance, interaction with other components in the curable composition, light resistance, heat resistance and the like.

  Specific examples and preferred examples of the acid dye include dyes described in JP-A-2005-227722, but the invention is not limited thereto.

When the acid dye is contained as a constituent component of the composition, it may be better to use it as a derivative of the acid dye because it may have insufficient solubility in the organic solvent used for preparation.
As the derivative of the acidic dye, an inorganic salt of an acidic dye having an acidic group such as sulfonic acid or carboxylic acid, a salt of an acidic dye and a nitrogen-containing compound, a sulfonamide of an acidic dye, or the like can be used. Although it will not specifically limit if it can melt | dissolve in the solution of the prepared composition, The solubility with respect to the organic solvent and the developing solution used at the time of a development process, a light absorbency, interaction with the other component in a composition, light resistance In addition, it is selected in consideration of all necessary performance such as heat resistance.

The salt of said acidic dye and a nitrogen-containing compound is demonstrated. The method of forming a salt with an acid dye and a nitrogen-containing compound may be effective for improving the solubility of the acid dye (providing solubility in an organic solvent) and improving heat resistance and light resistance.
The nitrogen-containing compound that forms a salt with an acid dye, and the nitrogen-containing compound that forms an amide bond with an acid dye to obtain a sulfonamide of an acid dye are organic solvents or salts used during preparation or development processing of the salt or amide compound. Taking into account all of the solubility in the developer, salt formation, absorbance / color value of the dye, interaction with other components in the dye-containing negative curable composition, heat resistance as a colorant, and light resistance Selected. When selecting only in terms of absorbance and color value, the nitrogen-containing compound is preferably as low as possible in molecular weight, particularly preferably having a molecular weight of 300 or less, more preferably having a molecular weight of 280 or less, and a molecular weight of 250 or less. Those are particularly preferred.

The molar ratio of the nitrogen-containing compound / acid dye in the salt of the acid dye and the nitrogen-containing compound (hereinafter referred to as “n”) will be described. The molar ratio n is a value that determines the molar ratio between the acidic dye molecule and the amine compound that is a counter ion, and can be freely selected according to the salt forming conditions of the acidic dye-amine compound. Specifically, n is a numerical value satisfying 0 <n ≦ 10 among the number of functional groups of an acid in an acid dye for practical use, solubility in an organic solvent or a developer, salt formation, absorbance, dye content It can be selected in consideration of all necessary performances such as interaction with other components in the negative curable composition, light resistance, heat resistance and the like. When selecting only from the viewpoint of absorbance, n is preferably a numerical value satisfying 0 <n ≦ 4.5, more preferably a numerical value satisfying 0 <n ≦ 4, and particularly preferably a numerical value satisfying 0 <n ≦ 3.5. .
Since the acidic dye shown above has become an acidic dye by introducing an acidic group in its structure, it can be made a non-acidic dye by changing its substituent. In some cases, the acid dye works favorably during alkali development, but on the other hand, it may become over-developed, and a non-acid dye may be preferably used.

  The organic solvent-soluble dye or / and other organic solvent-soluble dye essential to the present invention may have at least one addition-polymerizable ethylenically unsaturated double bond in the structure thereof. The organic solvent-soluble dye may be bonded to the resin.

The maximum value of the molar extinction coefficient ε in the visible light region of the organic solvent-soluble dye or / and other organic solvent-soluble dye essential to the present invention is usually 10,000 to 100,000, preferably 15,000 to 80,000, particularly 20,000 to 50,000. preferable. When the maximum value of ε is lower than 10,000, it is necessary to increase the addition amount of the dye and the sensitivity is lowered. If the maximum value of ε exceeds 100,000, it becomes difficult to adjust the hue.
(Maximum molar extinction coefficient ε in the visible light region of the transition metal complex according to the present invention) / (Molar extinction coefficient in the visible light region of the organic solvent-soluble dye or / and other organic solvent-soluble dyes essential for the present invention) The ratio of the maximum value of ε is usually from 0.01 to 0.7, preferably from 0.05 to 0.5, particularly preferably from 0.1 to 0.3. When this ratio is less than 0.01, light resistance decreases, and when it exceeds 0.7, the hue is not stable.

  The concentration of the organic solvent soluble dye in the total solid component in the dye-containing negative curable composition varies depending on the type of the dye, but is usually 0.5 to 97% by mass, preferably 40 to 95% by mass, 45-90 mass% is especially preferable.

(B) Oxime-based photopolymerization initiator The dye-containing negative curable composition of the present invention contains at least one oxime-based photopolymerization initiator (initiator according to the present invention). This oxime-based photopolymerization initiator can be polymerized and cured together with a radically polymerizable monomer described later when the dye-containing negative curable composition is constituted as a negative type.

  Examples of the oxime photopolymerization initiator include, for example, JP 2000-80068, JP 2001-233842, WO 2005-080337, JP 2001-235858, JP 2002-519732, Examples thereof include compounds described in Table 2004-534797, WO 2004-050653, and the like. However, it is not limited to these.

  Specific examples of the oxime photopolymerization initiator include 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 1- (4-methylsulfanyl-phenyl)- Butane-1,2-butane-2-oxime-O-acetate, 1- (4-methylsulfanyl-phenyl) -butan-1-one oxime-O-acetate, hydroxyimino- (4-methylsulfanyl-phenyl) -acetic acid Ethyl ester-O-acetate, hydroxyimino- (4-methylsulfanyl-phenyl) -acetic acid ethyl ester-O-benzoate, 1- (O-acetyloxime) -1- [9-ethyl-6- (2-methyl) A preferred example is benzoyl) -9H-carbazol-3-yl] ethanone.

  Among the above, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 1- (O-acetyloxime) -1- [9-ethyl-6- ( 2-methylbenzoyl) -9H-carbazol-3-yl] ethanone is particularly preferred.

  The oxime photopolymerization initiator has the following isomers (A) and (B) in terms of the compound structure, but may be used as a mixture of isomers or only one isomer.

In (A) and (B), R ¹ and R ² represent the above-mentioned “substituent”, and R ³ represents the organic group. However, R ¹ and R ² do not represent hydrogen atoms at the same time.

In the present invention, two or more oxime photopolymerization initiators may be mixed and used at an arbitrary mass ratio.
It is preferable that the composition of this invention also contains other photoinitiators other than an oxime system photoinitiator.

Next, other photopolymerization initiators that can be used in combination with the oxime photopolymerization initiator will be described.
The other photopolymerization initiator is not particularly limited as long as it can cause a monomer having a polymerizable group to undergo a polymerization reaction, but is preferably selected from the viewpoint of characteristics, initiation efficiency, absorption wavelength, availability, cost, and the like. .

  As other photopolymerization initiators, (tri) halomethyltriazine compounds, α-aminoketone compounds, and acylphosphine (oxide) compounds are suitable.

  Examples of the (tri) halomethyltriazine compounds include, for example, vinyl-halomethyl-s-triazine compounds described in JP-B-59-1281, and JP-A-53-133428 as halomethyl-s-triazine compounds. 2- (naphth-1-yl) -4,6-bis-halomethyl-s-triazine compound and 4- (p-aminophenyl) -2,6-di-halomethyl-s-triazine compound described in the above, Can be mentioned.

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- [pN- (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) aminopheny ] -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 (chloroethyl) 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-p-N, 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 to the above, 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 Co., Ltd. may be mentioned. .

  Examples of the α-aminoketone compound include Irgacure series (for example, Irgacure 907 and Irgacure 369) manufactured by Ciba Specialty Chemicals, 2-methyl-1-phenyl-2-morpholinopropan-1-one, 2-methyl-1- [4- (hexyl) phenyl] -2-morpholinopropan-1-one, 2-ethyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, etc. It is done.

  Although it does not specifically limit as said acylphosphine (oxide) type compound, Irgacure 819, Darocur 4265, Darocur TPO, etc. by Ciba Specialty Chemicals are mentioned.

  In addition to the above photopolymerization initiator, other known photopolymerization initiators can be used in the dye-containing negative curable composition of the present invention. For example, vicinal polykettle aldonyl compounds described in US Pat. No. 2,367,660, and α-carbonyl compounds described in US Pat. Nos. 2,367,661 and 2,367,670. An acyloin ether described in US Pat. No. 2,448,828, an α-hydrocarbon substituted aromatic acyloin compound described in US Pat. No. 2,722,512, US Pat. , 046,127 and 2,951,758, the triarylimidazole dimer / p-aminophenyl ketone combination described in US Pat. No. 3,549,367, Examples include benzothiazole compounds / trihalomethyl-s-triazine compounds described in JP-A-51-48516.

  Specifically, at least one active halogen compound selected from halomethyloxadiazole compounds and halomethyl-s-triazine compounds, 3-aryl-substituted coumarin compounds, lophine dimers, benzophenone compounds, acetophenone compounds and derivatives thereof, And cyclopentadiene-benzene-iron complex and salts thereof.

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

  Further, T series manufactured by PANCHIM is also effective, and examples thereof include T-OMS, T-BMP, TR, and TB. The Irgacure series manufactured by Ciba Specialty Chemicals is also effective, and examples thereof include Irgacure 651, Irgacure 184, Irgacure 500, Irgacure 1000, Irgacure 149, Irgacure 261, Darocur 1173, and the like.

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

  A sensitizer and a light stabilizer can be used in combination with these photopolymerization initiators. Specific examples include benzoin, benzoin methyl ether, 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, thioxanthone, 2,4-diethylthioxanthone, acridone, 10-butyl-2-chloroacridone, benzyl, dibenzalacetone, p- (dimethylamino) phenylstyryl ketone, p- (dimethylamino) phenyl-p -Methylstyryl ketone, benzophenone, p- (di Chiruamino) benzophenone (or Michler's ketone), p- (diethylamino) benzophenone, and benzanthrone, etc., benzothiazole compounds described in JP-B-51-48516, etc., Tinuvin 1130, the 400, and the like

  The oxime photopolymerization initiator or / and other photopolymerization initiator essential for the present invention includes at least one addition-polymerizable ethylenically unsaturated double bond, a perfluoroalkyl structure, or siloxane in the structure. It may have a group having at least one surface active function such as a structure. These initiators may be bonded to the resin.

The total amount of the photopolymerization initiator in the dye-containing negative curable composition is usually 5% by mass or more based on the total solid content of the composition. Furthermore, 9 mass% or more is preferable with respect to the total solid content, and it is more preferable that it is 12 mass% or more. Moreover, the upper limit of this total amount is 40 mass% normally, Preferably it is 30 mass% or less, More preferably, it is 20 mass% or less.
Of the total amount, from the viewpoint of the effect of the present invention, the content ratio of the initiator (oxime photopolymerization initiator) in the present invention is preferably 100 to 30% by mass, and more preferably 100 to 40% by mass.

  In the dye-containing negative curable composition, the mass ratio (B / B) of the total amount of the photopolymerization initiator (B) including the oxime-based photopolymerization initiator and the total amount of the (C) radical polymerizable monomer described later is used. C) is usually 0.1 or more and 1 or less, preferably 0.25 or more and 0.75 or less, and more preferably 0.3 or more and 0.70 or less. When the mass ratio (B / C) is within the above range, the polymerization reaction can be performed satisfactorily and the polymerization rate increases, but the molecular weight does not decrease and the film strength does not decrease.

  In the present invention, among the above, two kinds of pyrazole azo compounds and pyridone azo compounds, or two kinds of sulfur-containing organic group-substituted phthalocyanines and pyrazole azo compounds, or sulfur-containing organic group-substituted phthalocyanines and pyrazolotriazole-containing azomethine series A combination of two kinds of compounds and an oxime photopolymerization initiator is preferred.

  It is preferable to further add a thermal polymerization inhibitor together with the above photopolymerization initiator. 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.

(C) Radical polymerizable monomer The dye-containing negative curable composition of the present invention contains at least one radical polymerizable monomer. As the radical polymerizable monomer, a compound having at least one addition-polymerizable ethylenically unsaturated double bond and having a boiling point of 100 ° C. or higher under normal pressure is preferable.

  Examples include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethanetri (Meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (Meth) acrylate,

Trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, polymethic alcohol such as glycerin and trimethylolethane, and then (meth) acrylated after adding ethylene oxide or propylene oxide, Urethane acrylates as described in JP-B-48-41708, JP-B-50-6034, JP-A-51-37193, JP-A-48-64183, JP-B-49-43191, Mention polyfunctional acrylates and methacrylates such as polyester acrylates, epoxy resins and epoxy acrylates which are reaction products of (meth) acrylic acid and mixtures thereof described in JP-B-52-30490 Can do. Furthermore, the Japan Adhesion Association Vol. 20, no. 7, pages 300 to 308 are introduced as photocurable monomers and oligomers.

  In addition to the above, radically polymerizable monomers containing carboxyl groups such as the following general formulas (V-1) and (V-2) can also be suitably used. In general formulas (V-1) and (V-2), when T or G is an oxyalkylene group, the terminal on the carbon atom side is bonded to R, X, and W.

In the said general formula (V-1), n is 0-14 and m is 1-8. In the said general formula (V-2), W is R or X synonymous with general formula (V-1), and 3 or more W is R among six W. p is 0-14 and q is 1-8. A plurality of R, X, T, and G present in one molecule may be the same or different.
Of the radical polymerizable monomers represented by the general formulas (V-1) and (V-2), the following specific examples (Exemplary Compounds M-1 to M-12) are specifically preferred. Exemplified compounds M-2, M-3, and M-5 are preferred.

  The content of the radically polymerizable monomer in the dye-containing negative curable composition is preferably 20% by mass or more and preferably 30% by mass or more in terms of solid content in the total solid content of the composition. More preferably, it is most preferable to contain 35% by mass or more.

(D) Organic solvent The dye-containing negative curable composition of the present invention uses at least one organic solvent (also simply referred to as “solvent” in the present specification). The solvent is not particularly limited as long as the solubility of each component and the coating property of the dye-containing negative curable composition are satisfied, but particularly considering the solubility, coating property, and safety of the dye and the alkali-soluble binder. Are preferably selected.

  Examples of the organic solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, and lactic acid. Ethyl, 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, and 3-heptanone are preferred; aromatic hydrocarbons such as toluene and xylene are preferred.

  Of these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, ethylcarbi Tall acetate, butyl carbitol acetate, propylene glycol methyl ether, propylene glycol methyl ether acetate and the like are more preferable.

  Among the above, in terms of applicability and sensitivity, an aspect configured by selecting at least one from cyclohexanone, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and ethyl 3-ethoxypropionate is preferable. Furthermore, the aspect comprised by selecting at least 1 sort (s) from propylene glycol monomethyl ether and ethyl 3-ethoxypropionate from the point of resolution is more preferable.

The content of the organic solvent in the dye-containing negative curable composition is preferably 5 to 99.5% by mass, more preferably 10 to 90% by mass in the total amount of the composition, It is most preferable to contain 15-80 mass% or more.
If the amount is less than 5% by mass, the viscosity may increase and may not be uniformly applied. If the amount exceeds 99.5% by mass, the viscosity may decrease and may not be applied to a thick film (˜3 μm). A range is preferred.

(E) Transition metal complex Further, the dye-containing negative curable composition of the present invention has a transition metal complex in which the maximum molar extinction coefficient ε in the visible light region is smaller than the molar extinction coefficient ε of the organic solvent-soluble dye. Is preferably used.
This transition metal complex is a negative curable composition containing a dye, in which a negative, neutral or positive monodentate or multidentate ligand is coordinated around a transition metal atom or transition metal ion. And it is effective in improving the light resistance of a color filter using the same.

  The transition metal complex in the present invention preferably has a molar extinction coefficient ε in the visible light region (380 to 780 nm) of 0 or more and 8000 or less in terms of color sharpness. Further, as the transition metal complex, more preferably, the maximum value of the molar extinction coefficient ε in the wavelength range is from 0 to 6000, and even more preferably from 0 to 3000.

Examples of transition metals constituting transition metal atoms and transition metal ions of transition metal complexes and preferred examples thereof include those described in JP-A No. 2004-295116.
Particularly preferred transition metal complexes are cobalt (II) acetylacetonate, cobalt (II) hexafluoroacetylacetonate hydrate, nickel (II) acetylacetonate, and di-n-butyldithiocarbamate nickel (II).
The most preferred transition metal complex is cobalt (II) acetylacetonate, cobalt (II) hexafluoroacetylacetonate hydrate.

The content of the transition metal complex in the dye-containing negative curable composition is preferably 40% by mass or less, more preferably 30% by mass or less, and still more preferably 20% by mass or less with respect to the organic solvent-soluble dye. Most preferably, it is 0.5 to 15% by mass.
If the content exceeds 40% by mass, the pattern shape and pattern strength may be lowered.

(F) Other components-Resin (binder)-
The dye-containing negative curable composition of the present invention preferably further uses a resin (binder). The resin can be appropriately selected from known resins regardless of whether it is alkali-soluble or alkali-insoluble.

  As the resin, an alkali-soluble resin (hereinafter referred to as an alkali-soluble binder) is preferable. Hereinafter, the alkali-soluble binder will be described.

The alkali-soluble binder 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-58-12777, and JP-B-54-25957. Methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, as described in JP-A-59-53836 and JP-A-59-71048. 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 also useful.

In addition to the above, those obtained by adding an acid anhydride to a polymer having a hydroxyl group, polyhydroxystyrene resins, polysiloxane resins, poly (2-hydroxyethyl (meth) acrylate), polyvinylpyrrolidone and polyethylene oxide, Polyvinyl alcohol and the like are also useful.
Moreover, you may copolymerize the monomer which has hydrophilic property, As an example, alkoxyalkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, glycerol (meth) acrylate, (meth) acrylamide, N-methylol acrylamide, Secondary or tertiary alkylacrylamide, dialkylaminoalkyl (meth) acrylate, morpholine (meth) acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, vinyltriazole, methyl (meth) acrylate, ethyl (meth) acrylate Branched or linear propyl (meth) acrylate, branched or linear butyl (meth) acrylate, phenoxyhydroxypropyl (meth) acrylate, and the like.

  In addition, the hydrophilic monomer includes 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 group and its salt, a morpholinoethyl group, and the like. A monomer or the like is also useful.

  In addition, from the viewpoint of improving the crosslinking efficiency, a polymer having a polymerizable group in the side chain and a polymer containing an allyl group, a (meth) acryl group, an allyloxyalkyl group or the like in the side chain is also useful. Hereinafter, examples of the polymer containing these polymerizable groups are shown, but the polymer is not limited thereto as long as it contains an alkali-soluble group such as a COOH group, an OH group, and an ammonium group and an unsaturated bond between carbon atoms.

  As a specific example, a copolymer of an OH group such as 2-hydroxyethyl acrylate, a COOH group such as methacrylic acid, and a monomer such as an acrylic or vinyl compound copolymerizable with these, an OH group A compound obtained by reacting an epoxy ring having reactivity with a compound having a carbon-carbon unsaturated bond group (for example, a compound such as glycidyl acrylate) can be used.

  As the compound having reactivity with the OH group, a compound having an acid anhydride, an isocyanate group, and an acryloyl group can be used in addition to the epoxy ring. Further, a compound obtained by reacting an unsaturated carboxylic acid such as acrylic acid with a compound having an epoxy ring described in JP-A-6-102669 and JP-A-6-1938 is saturated or unsaturated polybasic. A reaction product obtained by reacting an acid anhydride can also be used.

  Examples of the compound having both an alkali solubilizing group such as a COOH group and an intercarbon unsaturated group include, for example, Dynal NR series (manufactured by Mitsubishi Rayon Co., Ltd.); Photomer 6173 (COOH group-containing Polyurethane acrylic oligomer, Diamond Shamrock Co., Ltd.). Ltd.); Biscote R-264, KS resist 106 (both made by Osaka Organic Chemical Industry Co., Ltd.); Cyclomer P series, Plaxel CF200 series (both made by Daicel Chemical Industries, Ltd.); Ebecryl 3800 (Daicel Yu) CB Co., Ltd.).

  When the resin (binder) is contained, the content of the resin in the dye-containing negative curable composition is usually 0.5 to 90% by mass with respect to the total solid content of the composition.

~ Surfactant ~
It is preferable that a surfactant may be further used in the composition of the present invention. The surfactant can be selected from known surfactants according to the purpose and the like.
Preferred surfactants are polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, polyoxyethylene nonylphenol Polyoxyethylene alkyl allyl ethers such as ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate Sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, Ftop EF301, EF303, EF352 (manufactured by Shin-Akita Kasei Co., Ltd.), MegaFuck F171, F173 (manufactured by Dainippon Ink and Chemicals), Florard FC430, FC431 (manufactured by Sumitomo 3M), Asahi Guard AG710, Surflon S- 382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.), Troysol S-366 (manufactured by Troy Chemical Co., Ltd.), etc. Siloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co.) and acrylic or methacrylic acid-based (co) polymer Polyflow No. 75, no. 95 (manufactured by Kyoeisha Yushi Chemical Co., Ltd.).
The surfactant is any one of fluorine and / or silicon surfactants (fluorine surfactants and silicon surfactants, surfactants containing both fluorine atoms and silicon atoms), or It is preferable to contain 2 or more types.
As these surfactants, for example, JP-A-62-36663, JP-A-61-226746, JP-A-61-226745, JP-A-62-170950, JP-A-63- No. 34540, JP-A-7-230165, JP-A-8-62834, JP-A-9-54432, JP-A-9-5988, JP-A 2002-277862, US Pat. No. 5,405,720 , No. 5,360,692, No. 5,529,881, No. 5,296,330, No. 5,543,098, No. 5,576,143, No. 5,294,511, No. 5,824,451. The following commercially available surfactants can also be used as they are.

Examples of commercially available surfactants that can be used include F-top EF301 and EF303 (manufactured by Shin-Akita Kasei Co., Ltd.), Florard FC430 and 431 (manufactured by Sumitomo 3M Co., Ltd.), MegaFuck F171, F173, F176 and F189, R08 (Dainippon Ink Chemical Co., Ltd.), Surflon S-382, SC101, 102, 103, 104, 105, 106 (Asahi Glass Co., Ltd.), Troisol S-366 (Troy Chemical Co., Ltd.), etc. Fluorine-based surfactant or silicon-based surfactant. Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon surfactant.
In addition to the known surfactants described above, the surfactant is derived from a fluoroaliphatic compound produced by a telomerization method (also referred to as a telomer method) or an oligomerization method (also referred to as an oligomer method). A surfactant using a polymer having a fluoroaliphatic group can be used. The fluoroaliphatic compound can be synthesized by the method described in JP-A-2002-90991.

As the polymer having a fluoroaliphatic group, a copolymer of a monomer having a fluoroaliphatic group and (poly (oxyalkylene)) acrylate and / or (poly (oxyalkylene)) methacrylate is preferable and distributed irregularly. Or may be block copolymerized. Examples of the poly (oxyalkylene) group include a poly (oxyethylene) group, a poly (oxypropylene) group, a poly (oxybutylene) group, and the like, and a poly (oxyethylene, oxypropylene, and oxyethylene group). A unit having different chain lengths in the same chain length, such as a block linked body) or a poly (block linked body of oxyethylene and oxypropylene) group, may be used. Furthermore, a copolymer of a monomer having a fluoroaliphatic group and (poly (oxyalkylene)) acrylate (or methacrylate) is not only a binary copolymer but also a monomer having two or more different fluoroaliphatic groups, Further, it may be a ternary or higher copolymer obtained by simultaneously copolymerizing two or more different (poly (oxyalkylene)) acrylates (or methacrylates).
Examples of commercially available surfactants include Megafac F178, F-470, F-473, F-475, F-476, and F-472 (Dainippon Ink Chemical Co., Ltd.). Further, a copolymer of an acrylate (or methacrylate) having a C ₆ F ₁₃ group and (poly (oxyalkylene)) acrylate (or methacrylate), an acrylate (or methacrylate) having a C ₆ F ₁₃ group and (poly (oxy Copolymer) of (ethylene)) acrylate (or methacrylate) and (poly (oxypropylene)) acrylate (or methacrylate), acrylate (or methacrylate) and (poly (oxyalkylene)) acrylate having C ₈ F ₁₇ groups (or Copolymer of acrylate (or methacrylate), (poly (oxyethylene)) acrylate (or methacrylate), and (poly (oxypropylene)) acrylate (or methacrylate) having a C ₈ F ₁₇ group. Coalescence And the like.
These surfactants may be added alone or in some combination.

  When the surfactant is contained, the content of the surfactant in the dye-containing negative curable composition is preferably 0.0001 to 5% by mass relative to the total mass of the composition, 0.001 to 1 The mass% is more preferable.

~ Crosslinking agent ~
In the present invention, it is also possible to obtain a film that has been further cured by using a crosslinking agent. Hereinafter, the crosslinking agent will be described.
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 acyloxymethyl. At least one substituent selected from a melamine compound, a guanamine compound, a glycoluril compound or a urea compound, (c) a methylol group, an alkoxymethyl group, and an acyloxymethyl group, which is substituted with at least one substituent selected from the group A phenol compound, a naphthol compound or a hydroxyanthracene compound substituted with Of these, polyfunctional epoxy resins are preferred.

  The epoxy resin (a) may be any epoxy resin as long as it has an epoxy group and has crosslinkability, for example, bisphenol A diglycidyl ether, ethylene glycol diglycidyl ether, butanediol diglycidyl ether. Divalent glycidyl group-containing low molecular weight compounds such as hexanediol diglycidyl ether, dihydroxybiphenyl diglycidyl ether, diglycidyl phthalate, N, N-diglycidyl aniline, trimethylolpropane triglycidyl ether, Trivalent glycidyl group-containing low molecular weight compounds represented by methylolphenol triglycidyl ether, TrisP-PA triglycidyl ether, pentaerythritol tetraglycidyl ether, tetramethylol vinyl Tetravalent glycidyl group-containing low molecular weight compounds typified by phenol A tetraglycidyl ether, polyvalent glycidyl group-containing low molecular weight compounds such as dipentaerythritol pentaglycidyl ether and dipentaerythritol hexaglycidyl ether, polyglycidyl ( And glycidyl group-containing polymer compounds represented by 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol and the like. .

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

  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, for example, tetramethylolguanamine, tetramethoxymethylguanamine, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylolguanamine, or a mixture thereof, tetramethoxyethylguanamine, tetraacyloxymethylguanamine, tetramethylol. Examples thereof include compounds in which 1 to 3 methylol groups of guanamine are acyloxymethylated 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 obtained by acylating 1 to 3 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.
These compounds according to (b) may be used alone or in combination.

  The crosslinking agent (c), that is, the phenol compound, naphthol compound or 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, the thermal cross-linking suppresses intermixing with the overcoated photoresist and further increases the film strength. 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 or alkoxymethyl groups contained in the crosslinking agent (c) is at least 2 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 3-position or 5-position of the phenol compound may be unsubstituted or may have a substituent.
The naphthol compound may be unsubstituted or substituted except for the ortho position of the OH group.

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 phenolic compounds, naphthols, hydroxyanthracene compounds in which the ortho-position or para-position of the phenolic OH group is unsubstituted, and examples thereof include phenol and cresol isomers, 2 , 3-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, bisphenols such as bisphenol A, 4,4'-bishydroxybiphenyl, TrisP-PA (Honshu Chemical Industry) Naphthol, dihydroxynaphthalene, 2,7-dihydroxyanthracene, etc. are used.

  Specific examples of the crosslinking agent (c) include, as a phenol compound or a naphthol compound, for example, a compound obtained by methoxymethylating one or two methylol groups of trimethylolphenol, tri (methoxymethyl) phenol, trimethylolphenol, Trimethylol-3-cresol, tri (methoxymethyl) -3-cresol, compounds obtained by methoxymethylating 1 to 2 methylol groups of trimethylol-3-cresol, 2,6-dimethylol-4-cresol and the like Compounds obtained by methoxymethylating 1 to 3 methylol groups of methylol cresol, tetramethylol bisphenol A, tetramethoxymethyl bisphenol A, tetramethylol bisphenol A, tetramethylol-4,4′-bishydroxybiphenyl, tetramethyl A compound obtained by methoxymethylating 1 to 5 methylol groups of xymethyl-4,4′-bishydroxybiphenyl, hexamethylol of TrisP-PA, hexamethoxymethyl of TrisP-PA, hexamethylol of TrisP-PA, Bishydroxymethyl naphthalene diol, etc. are mentioned.

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.

  In the present invention, it is not always necessary to contain a crosslinking agent. When a crosslinking agent is contained, the total content of the crosslinking agents (a) to (c) in the dye-containing negative curable composition varies depending on the material, but is based on the total solid content (mass) of the composition. 1 to 70% by mass is preferable, and 5 to 50% by mass is more preferable.

~ Various additives ~
In the dye-containing negative curable composition of the present invention, various additives, for example, fillers, polymer compounds other than those described above, adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation agents, etc., if necessary 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; 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) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane Adhesion promoters such as 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl-6-tert-butylphenol), 2,6 -Antioxidants such as di-t-butylphenol; ultraviolet absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxybenzophenone; and sodium polyacrylate And the like.

Further, when the alkali solubility of the uncured part is promoted and the developability of the dye-containing negative curable composition of the present invention is further improved, the composition has an organic carboxylic acid, preferably a molecular weight of 1000 or less. Of low molecular weight organic carboxylic acids 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.
In addition, what has a carboxyl group can also be mentioned as a specific example among the said components (D).

<Water content of the composition>
The water content of the composition of the present invention is required to be less than 1.0% by mass when filled in a closed container such as glass, metal, or plastic as a dye-containing negative curable composition.
By setting the water content of the composition of the present invention to less than 1.0% by mass, the temporal stability of the composition is improved, and the rate of pattern variation due to exposure dose variation is reduced.
Among the above, the water content is preferably less than 0.7% by mass, and more preferably less than 0.5% by mass.
By making the water content of the composition of this invention into less than 0.7 mass%, it is preferable from a viewpoint of temporal stability.
The water content in the present invention is a ratio of moisture to the total amount of the composition, and is represented by mass%.
The water content in the composition of the present invention can be determined by a known method such as the Karl Fischer method, and the present invention adopts this.

  In order to obtain a composition having a moisture content of less than 1.0% by mass of the present invention, each component constituting the composition of the present invention and each component added as necessary are heated to such an extent that they do not decompose. , A method of drying under reduced pressure, each component constituting the composition, and a method of distilling water by heating the organic solvent solution of each component added as necessary under reduced pressure, each component constituting the composition And each component to be added as necessary, for example, a method of adjusting by dehydrating with a molecular sieve (manufactured by Union Showa Co., Ltd.) known as a molecular sieve, each component constituting the composition of the present invention, and if necessary Although there is a method of directly treating the organic solvent solution of each component to be added with a molecular sieve, the method is not limited to these as long as the water content in the composition can be reduced.

  The dye-containing negative curable composition of the present invention is used for forming colored pixels such as color filters used in liquid crystal display devices (LCDs), solid-state imaging devices (eg, CCDs, CMOSs, etc.), electroluminescent color filters, etc. Also, it can be suitably used as a production application for printing ink, inkjet ink, paint, 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, a color filter is produced using the above-described dye-containing negative curable composition of the present invention.
Furthermore, the method for producing a color filter of the present invention includes at least one step of coating the dye-containing negative curable composition on a support, exposing through a mask, and developing to form a pattern.
Specifically, the radiation-sensitive composition layer is formed by coating the dye-containing negative curable composition of the present invention on a support by a coating method such as spin coating, cast coating, roll coating, and the like. Is exposed through a predetermined mask pattern and developed with a developer to form a negative colored pattern (image forming step). Moreover, the hardening process which hardens | cures the formed coloring pattern by heating and / or exposure as needed may be included.
By repeating the image forming step (and the curing step if necessary) as many times as desired, a color filter having a desired hue can be produced.
As light or radiation used at this time, ultraviolet rays such as g-line, h-line and i-line are particularly preferable.

  The color filter of the present invention uses the above-described dye-containing negative curable composition of the present invention, and preferably has one or more colored regions (for example, red (R), green (G ) And blue (B) (colored regions of three colors) are provided in a desired pattern shape (for example, a stripe shape, a lattice shape, a delta array shape, etc.). The color filter of the present invention can be most suitably produced by the method for producing a color filter of the present invention.

When providing a colored region of one or more colors on the support, the dye-containing negative type in which at least one color of the colored region constituting the color filter includes at least one selected from the following (1) to (3) The aspect currently formed using the curable composition is preferable.
(1) Two kinds of pyrazole azo compounds and pyridone azo compounds (2) Two kinds of sulfur-containing organic group-substituted phthalocyanines and pyrazole azo compounds (3) Two of sulfur-containing organic group-substituted phthalocyanines and pyrazolotriazole-containing azomethine compounds Species Details of the compounds in the above (1) to (3) and preferred embodiments are as described above.

Examples of the support include soda glass, Pyrex (registered trademark) glass, and quartz glass used for liquid crystal display elements and the like, and those obtained by attaching a transparent conductive film thereto, and photoelectric conversion element substrates used for imaging elements and the like. Examples thereof include a silicon substrate and a complementary metal oxide semiconductor (CMOS). These substrates may have black stripes that separate pixels.
Further, if necessary, an undercoat layer may be provided on these substrates in order to improve adhesion with the upper layer, prevent diffusion of substances, or planarize the substrate surface.

  Any developer can be used as long as it has a composition that dissolves the uncured portion of the dye-containing negative curable composition of the present invention but does not dissolve the cured portion. Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used. As an organic solvent here, the above-mentioned organic solvent used when preparing the dye-containing negative curable composition of this invention is mentioned.

  Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide. , 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 liquid crystal display element (LCD) or a solid-state imaging element (for example, CCD, CMOS, etc.), and is particularly suitable for a high-resolution CCD element, CMOS, etc. exceeding 1 million pixels. is there. 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.

(Examples 1-10, Comparative Examples 1-6)
1) Preparation of resist solution A compound having the following composition was mixed and dissolved to prepare a resist solution.
Propylene glycol monomethyl ether acetate 19.20 parts (PGMEA)
-36.67 parts of ethyl lactate-30.51 parts of resin (binder) [benzyl methacrylate / methacrylic acid / 2-hydroxyethyl methacrylic acid copolymer (molar ratio = 60: 20: 20, weight average molecular weight = 30000) 41% PGMEA solution]
・ Dipentaerythritol hexaacrylate 12.20 parts (photopolymerizable compound)
・ Polymerization inhibitor (p-methoxyphenol) 0.0061 part ・ Fluorosurfactant 0.83 part (F-475, manufactured by Dainippon Ink & Chemicals, Inc.)
-Photopolymerization initiator 0.586 parts (TAZ-107 (trihalomethyltriazine photopolymerization initiator), manufactured by Midori Chemical Co., Ltd.)

2) Production of glass substrate with undercoat layer A 6-inch silicon wafer was heat-treated in an oven at 200 ° C. for 30 minutes or more. Next, the resist solution was applied onto the silicon wafer so as to have a dry film thickness of 2 μm, and further heated and dried in an oven at 220 ° C. for 1 hour to form an undercoat layer, thereby obtaining a silicon wafer substrate with an undercoat layer. .

3) Preparation of dye-containing negative curable composition The components shown in Table 1 below (the amounts were as shown in Table 1) were dissolved in the organic solvent shown in Table 1 below. Then, molecular sieves 4A (pellet shape) was added at a rate of 1 g with respect to 10 g of these solutions, and stirred for 12 hours. From this solution, molecular sieves were filtered off under a dry nitrogen atmosphere to obtain dye-containing negative curable compositions N-1 to N-16. However, only the compositions N-12 and N-13 were not treated with the molecular sieves 4A.
3-1) Measurement of water content of composition 50 μL of each of the dye-containing negative curable compositions N-1 to N-16 obtained in 3) above is taken out and placed in a Karl Fischer moisture meter MKC-120 (manufactured by KYOTOELECTRONICS). The water content was evaluated.

4) Exposure and development of dye-containing negative curable composition (image forming process)
The dye-containing negative curable compositions N-1 to N-16 obtained in 3) were filtered using a filter. After filtration, the dye-containing negative curable compositions N-1 to N-16 are each 0.8 μm in thickness on each undercoat layer of the separate undercoat layer-coated silicon wafer substrate obtained in 2) above. In this way, the coating was applied using a spin coater, and the coated film was heat-treated (prebaked) at 100 ° C. for 120 seconds.

  The coating film obtained above was irradiated using an i-line reduction projection exposure apparatus with a wavelength of 365 nm through a mask having a line width of 2 μm and changing the exposure amount by 100 mJ. After irradiation, the film was developed using a developer of 60% CD-2000 (manufactured by FUJIFILM Electronics Materials) at 23 ° C. for 60 seconds. Subsequently, after rinsing with running water for 20 seconds, spray drying was performed to obtain a colored filter film (color filter). The formation of the image was confirmed by an ordinary method using an optical microscope and SEM photograph observation.

5) Evaluation With respect to the dye-containing negative curable compositions N-1 to N-16 and color filters obtained in the above-described Examples and Comparative Examples, the line width variation rate due to change in exposure amount and time-dependent change according to the method described below. An increase in the number of coating defects was evaluated. The evaluation results are shown in Table 1 below.

-1. Evaluation of line width variation rate due to exposure change-
In the 2 μm width pattern obtained above, the exposure amount at which the dot-space width is 1: 1 is the appropriate exposure amount (sensitivity), and the line width when the exposure amount is increased or decreased by 100 mJ from this appropriate exposure amount The variation rate was calculated from the following equation. In addition, “||” in the following formula represents an absolute value.
Line width fluctuation rate (%) =
| (Line width ^* when deviated 100mJ from the proper exposure) - (the line width at proper exposure amount) | / (line width at proper exposure amount) × 100
* Here, out of the line widths when increased or decreased by 100 mJ from the appropriate exposure amount, the one that is more deviated from the line width at the appropriate exposure amount was used. The smaller the value of the line width variation rate, the better the performance.

-2. Evaluation of coating defect increase over time-
The dye-containing negative curable compositions N-1 to N-16 immediately after the preparation obtained in 3) above are completely applied on the respective undercoat layers of the silicon wafer substrate with an undercoat layer obtained in 2). It applied similarly. And this coating film was observed with the optical microscope, the number of hole-shaped and radial coating defects was counted, and the total of the said number of defects seen in one 6-inch wafer was made into the number of coating defects.
Separately, the dye-containing negative curable compositions N-1 to N-16 obtained in 3) above were stored at 25 ° C. for 2 weeks, and the total number of coating and coating defects was similarly determined. Subsequently, the number of coating defects increased over time was calculated from the following formula and used as an index for evaluating the temporal stability of the dye-containing negative curable composition. The stability over time indicates that the smaller this value, the better the performance.

Increased number of coating defects over time =
(Number of coating defects when aged for 2 weeks)-(Number of coated defects when not aged)

-3. Evaluation of line width variation rate over time-
For each of the undercoat layers of the silicon wafer substrate with an undercoat layer obtained in 2) above for the dye-containing negative curable compositions N-1 to N-16 obtained in 3) above, 4) and In exactly the same manner, a coating film was obtained by coating.
The coating film obtained above was irradiated with an exposure amount of 800 mJ through a mask having a wavelength of 365 nm and a line width of 2 μm using an i-line reduction projection exposure apparatus. After irradiation, development was carried out in the same manner as in 4) above, and the line width at 800 mJ exposure in a 2 μm width pattern was determined by SEM photograph observation.
Separately, the dye-containing negative curable compositions N-1 to N-16 obtained in 3) above were stored at 25 ° C. for 2 weeks, and then coated, exposed and developed in the same manner as described above. The line width at 800 mJ exposure was determined by SEM photograph observation, and the line width variation rate over time was calculated from the following formula and evaluated.
In addition, “||” in the following formula represents an absolute value. The line width variation rate indicates that the smaller the value, the better the performance.
Line width variation rate over time (%) =
| (Line width when not aging) − (Line width when aging for 2 weeks) | / (Line width when not aging) × 100

  As shown in Table 1, in Examples 1 to 10, the increase in coating defects with time was small, and the line width variation rate was small and good. On the other hand, in Comparative Examples 1-6, the increase in the coating defect with time was remarkable, the line width variation rate of the formed pattern was large, and was inferior to the Examples.

The details of each component in Table 1 are shown below.
(A) Dye The column of the name of an Example shows the number of the exemplary compound of the organic solvent soluble dye mentioned above. A synthesis example of a part of the dye to be used will be described later.
Dyes H-1 to H-4 of Comparative Examples
* Dye in Comparative Example H-1: Varifast Yellow 1101
-H-2: C.I. I. Acid Red 249
・ H-3: Variefast Blue 2620
H-4: C.I. I. Acid Red 80
-H-5: Variast Red 1360
(B) Photopolymerization initiator B-1: Irgacure OXE01 (manufactured by Ciba Specialty Chemicals; initiator according to the present invention)
B-2: CGI-242 (manufactured by Ciba Specialty Chemicals; initiator according to the present invention)
B-3: Irgacure 369 (manufactured by Ciba Specialty Chemicals; α-aminoketone photopolymerization initiator)
B-4: TAZ-107 (manufactured by Midori Chemical Co .; trihalomethyltriazine photopolymerization initiator)
B-5: Irgacure 819 (manufactured by Ciba Specialty Chemicals; amylphosphine photopolymerization initiator)
B-6: 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole (biimidazole photopolymerization initiator)
(C) Radical polymerizable monomer. C-1: A mixture of the exemplified compound (M-2) and dipentaerythritol hexaacrylate described above of radical polymerizable monomer, 3: 7. C-2: Dipentaerythritol hexaacrylate ( D) Organic solvent D-1: Cyclohexanone D-2: Ethyl lactate D-3: Propylene glycol monomethyl ether acetate (PGMEA)
D-4: Propylene glycol monomethyl ether D-5: Ethyl 3-ethoxypropionate (E) transition metal complex E-1: Cobalt (II) acetylacetonate E-2: Di-nbutyldithiocarbamate nickel (II)
(F) Other components * Surfactant F-1: Fluorosurfactant F-475 [manufactured by Dainippon Ink & Chemicals, Inc.]
* Resin (binder)
G-1: benzyl methacrylate / methacrylic acid / 2-hydroxyethyl methacrylic acid = 7/2/1 (molar ratio), copolymer Mw = 25,000, Mw / Mn is 2.5)
* Polymerization inhibitor I-1: p-methoxyphenol

-Synthesis example-
The synthesis of dye A4-1, which is the exemplified compound, will be described in detail with reference to the following scheme as an example.
(Synthesis of Dye A4-1)

<Synthesis of Intermediate Product B>
First, 25.0 g (0.162 mol) of Compound A was dissolved in a mixed solvent of 100 ml of methanol and 23 ml of triethylamine, and further cooled and stirred at 5 ° C., and further 9 ml of 30% hydrogen peroxide solution was kept at an internal temperature of 25 ° C. While dripping. The reaction solution after dropping was further stirred at 25 ° C. for 30 minutes, cooled again to 5 ° C., 15 ml of concentrated hydrochloric acid was added dropwise with stirring, 200 ml of water was further added, and the mixture was stirred at 25 ° C. for 1 hour. The precipitated crystals were filtered, washed thoroughly with water, and dried to obtain 24.7 g of intermediate product B as white crystals (yield 99.5%).

<Synthesis of Intermediate Products C, D, and E>
Subsequently, 100 ml of toluene and 0.25 ml of dimethylacetamide were added to 17.5 g (0.114 mol) of the intermediate product B obtained above, and further 25 ml of thionyl chloride was added dropwise over 10 minutes under reflux. This was further heated under reflux for 1 hour and then concentrated under reduced pressure to obtain a viscous liquid. On the other hand, while adding 10 ml of dimethylacetamide and 100 ml of acetonitrile to 38.0 g (0.235 mol) of diethoxyethylamine and stirring at 10 ° C., the viscous liquid was kept at 15 ° C. over 15 minutes. It was dripped. After further stirring for 30 minutes, this was poured into a mixed solution of 100 ml of water and 100 ml of ethyl acetate, and the ethyl acetate phase was separated and washed twice with 100 ml of water. The ethyl acetate phase was dried using magnesium sulfate, and ethyl acetate was distilled off under reduced pressure to obtain an intermediate product C which was a pale yellow viscous liquid.
Next, 50 ml of water, 200 ml of ethanol, and 12 g of zinc powder were added to the intermediate product C, and a solution obtained by diluting 10 ml of sulfuric acid in 40 ml of water was added dropwise over 20 minutes under reflux with heating. The mixture was further heated and stirred for 30 minutes and then cooled, and insoluble matters were separated by filtration. To the resulting solution were added 50 ml of saturated brine and 100 ml of ethyl acetate, and the mixture was separated, and the ethyl acetate phase was washed twice with 100 ml of water. The ethyl acetate phase was dried using magnesium sulfate, and the ethyl acetate was distilled off under reduced pressure to obtain an intermediate product D which was a pale yellow viscous liquid.
Next, 70 ml of dimethylacetamide and 15 g (0.108 mol) of potassium carbonate were added to this intermediate product D under stirring in a nitrogen atmosphere, and 19.7 g (0. 113 mol) was gradually added while maintaining the temperature below 25 ° C. This was further stirred for 30 minutes, and then poured into 300 ml of water with stirring. The obtained crystals were filtered, and the crystals were thoroughly washed with water. The obtained crystals were recrystallized with 70 ml of methanol, and the precipitated crystals were washed with 30 ml of cold methanol and dried to obtain 35.0 g of intermediate product E as white crystals (yield 72.6%).

<Synthesis of Dye A4-1>
Next, 150 ml of butanol, 6.7 g (0.070 mol) of ammonium carbonate, and 4.7 g (0.035 mol) of copper chloride are added to 34.4 g (0.081 mol) of the intermediate product E, and the mixture is heated and stirred. For 7 hours. Thereafter, butanol was distilled off under reduced pressure, and the resulting solid was purified by silica gel column chromatography to obtain 25 g of a dye A4-1 powder (yield 72.7%). When the maximum absorption wavelength (λ _max ) and molar extinction coefficient (ε) of the obtained dye were measured with a spectrophotometer UV-2400PC (manufactured by Shimadzu Corporation), the maximum absorption wavelength λ _max 706. It was 8 nm and ε55,600.

(Synthesis of Dye A4-12)
In the same manner as in A4-1, Compound A was changed to Compound A ′, diethoxyethylamine was changed to 1-methoxypropanol, and 3-nitrophthalonitrile was changed to 4-nitrophthalonitrile to obtain Dye A4-12. .

(Synthesis of Dye A5-28)
19.6 g of phthalic anhydride, 22.2 g of 4-bromophthalic anhydride, 16.7 g of pyridine-2,3-dicarboxylic acid, 144 g of urea, 9.9 g of cuprous chloride, and 1.6 g of ammonium molybdate -It suspended in 400 mL of chloronaphthalene, and it stirred at 190-220 degreeC for 5 hours. The reaction mixture was poured into 250 mL of methanol, filtered, washed with methanol, water, and acetone in that order, and then dried to obtain 31.3 g of a blue bromo-substituted tetraazaporphyrin compound.
13.1 g of the obtained bromo-substituted tetraazaporphyrin compound was added to 100 g of chlorosulfonic acid in small portions at 20 ° C. or less over 30 minutes. Next, the temperature was raised to 70 to 80 ° C., stirred at the same temperature for 1 hour, heated to 140 to 145 ° C. over 2 hours, reacted at the same temperature for 4 hours, and then cooled to 80 ° C. Further, 30 g of thionyl chloride was added dropwise over 1 hour while maintaining the temperature at 70 to 80 ° C., followed by stirring at 70 to 80 ° C. for 4 hours. It cooled to 15-20 degreeC and stirred at the same temperature for 12 hours. The reaction mixture was discharged into 1000 g of ice water in small portions, and then the precipitate was separated by filtration and washed with ice water until neutral, to obtain a sulfonyl chloride of a hydrated paste-like bromo-substituted tetraazaporphyrin compound. Immediately thereafter, this was poured into 400 g of ice water, and after 30 minutes of dispersion and stirring at 10 ° C. or lower, 30 g of 2-amino-1- (2-ethoxyethoxy) butane was added dropwise. Next, the temperature was raised to 20 to 30 ° C. and stirred at the same temperature for 18 hours. The product was separated by filtration, dispersed in 200 g of water and filtered twice, and then dried at 60 ° C. for 16 hours. 18 g of blue powder was obtained. This was further recrystallized with ethyl acetate to obtain 10 g of blue crystals.
As a result of X-ray fluorescence analysis, this blue crystal has an average sulfonamide group of 1.9 per molecule due to the strength ratio of copper and sulfonamide group sulfur atom and bromine as the central metal of the bromo-substituted tetraazaporphyrin skeleton It was confirmed that the number of bromine atoms was 1.2.
Further, 5 g of the obtained blue crystals were separated and purified by silica gel column chromatography with a mixed solution of ethyl acetate / methanol to obtain 1.5 g of purified blue powder. As a result of X-ray fluorescence analysis, the purified blue powder has two sulfonamide groups per molecule and one bromine based on the strength ratio of copper and sulfonamide group sulfur atom and bromine, which are the central metals of the bromo-substituted tetraazaporphyrin skeleton. As a result of FD-MS analysis, from m / z = 1100.2, it was confirmed that the compound was composed mainly of the dye A5-28 described above in which one pyridine ring was introduced. did.

(Synthesis of Dye A5-29)
14.8 g of phthalic anhydride, 45.4 g of 4-bromophthalic anhydride, 16.7 g of pyridine-2,3-dicarboxylic acid, 144 g of urea, 9.9 g of cuprous chloride, and 1.6 g of ammonium molybdate , 3-Dimethyl-2-imidazolidinone, suspended in 400 mL, and stirred at 190 to 220 ° C. for 5 hours. Subsequently, the same post-treatment as in A5-28 was performed to obtain 41.1 g of a bromo-substituted tetraazaporphyrin compound. Moreover, chlorosulfonation, amidation, and a post-process were performed similarly to said A5-28, and 15.5g of blue crystals were obtained.

  As a result of fluorescent X-ray analysis, this blue crystal has an average sulfonamide group of 2.1 per molecule depending on the strength ratio of the copper atom of the bromo-substituted tetraazaporphyrin skeleton and the sulfur atom and bromine of the sulfonamide group. It was confirmed that the number of bromine atoms was 2.2.

  Further, 5 g of the obtained blue crystals were separated and purified by silica gel column chromatography with an ethyl acetate / methanol mixed solution to obtain 1.0 g of purified blue powder. As a result of fluorescent X-ray analysis, the purified blue powder has two sulfonamide groups per molecule and bromine atoms depending on the strength ratio of copper and sulfonamide group sulfur atoms and bromine, which are the central metals of the bromo-substituted tetraazaporphyrin skeleton. Is a compound mainly composed of the above-mentioned dye A5-29 in which one pyridine ring is introduced from m / z = 1178.1 as a result of FD-MS analysis. It was confirmed.

(Synthesis of Dye A5-30)
4-bromophthalic anhydride 68.1 g, pyridine-2,3-dicarboxylic acid 16.7 g, urea 144 g, cuprous chloride 9.9 g, and ammonium molybdate 1.6 g were mixed with 1,3-dimethyl-2- The suspension was added to 400 mL of imidazolidinone and stirred at 190 to 220 ° C. for 5 hours. Subsequently, the same post-treatment as in A5-28 was performed to obtain 25 g of a bromo-substituted tetraazaporphyrin compound. Moreover, chlorosulfonation, amidation, and a post-process were performed similarly to said A5-28, and the blue crystal 9.9g was obtained.

Further, 5 g of the obtained blue crystals were separated and purified by silica gel column chromatography with an ethyl acetate / methanol mixed solution to obtain 3.0 g of purified blue powder. As a result of X-ray fluorescence analysis, the purified blue powder has two sulfonamide groups per molecule and bromine atoms depending on the strength ratio of copper and sulfonamide group sulfur atom and bromine, which are the central metals of the bromo-substituted tetraazaporphyrin skeleton. Is a compound mainly composed of the above-described dye A5-30 in which one pyridine ring is introduced from m / z = 1256.0 as a result of FD-MS analysis. It was confirmed.
In addition, it can synthesize | combine similarly to the above also about another above-mentioned exemplary compound by changing into a desired compound according to the target dye.

Claims (5)

  (A) at least two organic solvent-soluble dyes selected from heterocyclic azo compounds, phthalocyanine compounds, and azomethine compounds; (B) at least one oxime photopolymerization initiator; and (C) at least one kind. A dye-containing negative curable composition containing the radical polymerizable monomer of (D) and at least one organic solvent, wherein the water content of the composition is less than 1% by mass relative to the total amount of the composition A dye-containing negative curable composition characterized by that.   The at least two organic solvent-soluble dyes are selected from nitrogen-containing heterocyclic azo compounds, organic group-substituted phthalocyanine compounds, and nitrogen-containing heterocyclic azomethine compounds. A dye-containing negative curable composition. The dye-containing negative curable composition according to claim 1 or 2, wherein the at least two kinds of organic solvent-soluble dyes include at least one selected from the following (1) to (3). object.
(1) Two types of pyrazole azo compounds and pyridone azo compounds (2) Two types of sulfur-containing organic group-substituted phthalocyanines and pyrazole azo compounds (3) Two of sulfur-containing organic group-substituted phthalocyanines and pyrazolotriazole-containing azomethine compounds seed   A color filter comprising the dye-containing negative curable composition according to any one of claims 1 to 3.   A color comprising the steps of applying the dye-containing negative curable composition according to any one of claims 1 to 4 on a support, exposing through a mask, and developing to form a pattern. A method for manufacturing a filter.