JP4813248B2 - Colored curable composition, color filter and method for producing the same - Google Patents

Description

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

  Various methods have been proposed so far for producing the color filter as described above. In particular, a so-called color resist method in which a photosensitive resin composition containing a dye is exposed and developed to repeatedly perform a patterning process a required number of times has been widely put into practical use.

  The color resist method is a method for producing a color filter by a photolithographic method using a colored radiation-sensitive composition in which pigments are dispersed in various photosensitive compositions. This method uses pigments. It is stable to light, heat, and the like, and has a sufficient positional accuracy because it is patterned by a photolithography method, and is a suitable method for manufacturing a color filter for a large screen and a high-definition color display.

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

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

Conventionally, the use of dyes has been proposed for such problems (see, for example, Patent Documents 9 to 11).
On the other hand, it is known that a mixture of a violet dye and a cyan dye is used for a blue filter array of a color filter (see, for example, Patent Document 12).
Japanese Patent Laid-Open No. 1-102469 Japanese Patent Laid-Open No. 1-152499 JP-A-2-181704 JP-A-2-199403 Japanese Patent Laid-Open No. 4-76062 Japanese Patent Laid-Open No. 5-273411 JP-A-6-184482 JP-A-7-140654 JP-A-6-75375 JP 2002-14221 A Japanese Patent Publication No.7-111485 Japanese Patent Laid-Open No. 2002-14222

However, the dye-containing curable composition has the following problems, and further improvement has been demanded. That is,
(1) Dyes are generally inferior in heat resistance, light resistance and the like as compared with pigments, and have insufficient fastness.
(2) When the molar absorption light coefficient of the dye is low, a large amount of dye must be added. In this case, other compounds such as a polymerizable compound, a binder and a photopolymerization initiator in the curable composition The components must be relatively reduced, and the curability at the time of curing the composition, the heat resistance of the cured portion that has been cured, the developability of the non-cured portion, and the like are reduced.
(3) The dye often exhibits an interaction with other components in the curable composition, and it is difficult to adjust the developability (solubility) of the cured part and the non-cured part.
As described above, the dyes conventionally used in the photosensitive composition are not particularly satisfactory in fastness, and further have low solubility in the photosensitive composition and contain the dye at a high concentration. It was also difficult.

  In addition, as described above, the dye forming the mixture used in the blue filter array is insufficient in heat resistance and light resistance, and further improvement is desired.

  The present invention has been made in view of the above, and has excellent hue (molar extinction coefficient and color value) and vividness, and is excellent in light resistance, heat resistance, and pattern formation (developability). Composition, sharp color pattern (especially rectangular with good cross-sectional shape), high resolution, good hue, light resistance and heat resistance, and development residue in uncured areas can be prevented An object of the present invention is to provide a color filter manufacturing method capable of producing the color filter with high productivity (high cost performance), and to achieve the object.

  In the present invention, various dye compound derivatives having a good hue and high fastness to light and heat have been examined in detail. The dye having a specific structure particularly has fastness such as heat resistance and light resistance. Based on this knowledge, a colored curable composition, a color filter, and a method for producing the same were provided, and the above object was achieved.

<1> At least one azomethine dye represented by the following general formula (I), at least one tetraazaporphyrin dye represented by the following general formula (A), a polymerizable compound, and photopolymerization It is a colored curable composition characterized by containing an initiator .

In the general formula (I), R ¹¹ represents a hydrogen atom or a substituent, and R ¹² , R ¹³ , R ¹⁴ , and R ¹⁵ each independently represent a hydrogen atom or a substituent, R ¹⁶ and R ¹⁷ 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 ¹⁸ ) ═, and R ¹⁸ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group. R ¹² and R ¹³ , R ¹³ and R ¹⁶ , R ¹⁴ and R ¹⁵ , R ¹⁵ and R ¹⁷ , and R ¹⁶ and R ¹⁷ are bonded to each other to form a 5-membered, 6-membered, or 7-membered ring. May be.

In the general formula (A), ring A ¹ , ring A ² , ring A ³ , and ring A ⁴ are each independently

And at least one of ring A ¹ , ring A ² , ring A ³ , and ring A ⁴ is

Represents. R ¹ and R ² each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group, m represents an integer of 1 to 8, and n represents an integer of 1 to 4. However, R ¹ and R ² do not represent a hydrogen atom at the same time.

<2> At least one azomethine dye represented by the general formula (I), at least one tetraazaporphyrin dye represented by the general formula (A), a binder, and a photoacid generator Or the coloring curable composition characterized by containing a naphthoquinone diazide compound.
<3> The colored curable composition according to <1> or <2> , wherein the azomethine dye is an azomethine dye represented by the following general formula (II).

In the general formula (II), R ⁵¹ represents a hydrogen atom or a substituent, R ⁵² , R ⁵³ , and R ⁵⁴ each independently represent a hydrogen atom or a substituent, and R ⁵⁶ represents an alkyl group, an alkenyl. Represents a group, an aryl group, or a heterocyclic group. R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ and R ²⁴ each independently represents a hydrogen atom or a substituent. Zc and Zd each independently represent —N═ or —C (R ¹⁸ ) ═, and R ¹⁸ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group.

<4> In the general formula (A), R ¹ and R ² are each independently a hydrogen atom (provided that R ¹ and R ² do not represent a hydrogen atom at the same time), an unsubstituted alkyl group, Alternatively, the colored curable composition according to any one of <1> to <3>, which represents a “substituted alkyl group containing an oxygen atom in at least one form of an ether bond, a carbonyl bond, and an ester bond”.

<5> In the above general formula (A), R ¹ and R ² are each independently a hydrogen atom (however, R ¹ and R ² do not represent a hydrogen atom at the same time), having 1 to 12 carbon atoms. An unsubstituted alkyl group, or "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", and m is an integer of 1 to 4 The colored curable composition according to any one of the above items <1> to <4> .

<6> In the general formula (A), at least one of R ¹ and R ² has 2 to 12 carbon atoms containing 1 to 4 oxygen atoms in at least one form of an ether bond, a carbonyl bond, and an ester bond. The colored curable composition according to any one of <1> to <5> , which represents a substituted alkyl group.

<7> In the general formula (A), the colored curable composition according to <6> , wherein at least one of R ¹ and R ² represents a substituted alkyl group represented by the following formula (B).

In the formula (B), R ³ and R ⁴ 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”. , An alkylcarbonyl group, or an alkoxycarbonyl group, wherein at least one of R ³ and R ⁴ is 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 represents an alkoxycarbonyl group.

<8> In the formula (B), R ³ and R ⁴ are each independently a hydrogen atom, an unsubstituted alkyl group having 1 to 8 carbon atoms, “an oxygen atom is an ether bond, a carbonyl bond, or an ester bond. at least one 1-4 including substituted alkyl group having 2 to 10 carbon atoms in the form "alkoxycarbonyl group of the alkyl carbonyl group or 2 to 10 carbon atoms, from 2 to 10 carbon atoms, R ³ and R ⁴ At least one of the above <represented by a <2-10 substituted alkyl group containing 1 to 4 oxygen atoms in the form of at least one of an ether bond, a carbonyl bond, and an ester bond>, an alkylcarbonyl group, or an alkoxycarbonyl group 7> . The colored curable composition according to 7> .

<9> The colored curable composition according to any one of <1> and <3> to <8>, further comprising a binder.
<10> The colored curable composition according to any one of <1> and <3> to <9>, wherein the polymerizable compound is a radical polymerizable monomer.
<11> The colored curable composition according to any one of <1> and <3> to <10>, wherein the photopolymerization initiator is an oxime compound.
<12> The colored curable composition according to any one of <1> to <11>, further comprising a solvent.
<13> The colored curable composition according to <12>, wherein the solvent is an organic solvent.
<14> The colored curable composition according to any one of <2> to <13>, wherein the binder is an alkali-soluble binder.
<15> A color comprising at least one azomethine dye represented by the general formula (I) and at least one tetraazaporphyrin dye represented by the general formula (A) It is a filter.

<16> A step of coating the colored curable composition according to any one of <1> to <14> on a support, exposing through a mask, and developing to form a pattern. This is a method for manufacturing a color filter.
This manufacturing method may include a step of curing the pattern by heating and / or exposure as necessary, and may be configured to repeat these steps a plurality of times. May be configured to form a multi-color filter.

  According to the present invention, a colored curable composition having a good hue (molar extinction coefficient and color value) and vividness, and excellent in light resistance, heat resistance, and pattern formability (developability), and a pattern Is a sharp (especially rectangular with a good cross-sectional shape) and high resolution, has a good hue, excellent light resistance and heat resistance, and can prevent development residue in the uncured area, producing high color filters It is possible to provide a method for manufacturing a color filter that can be manufactured with high performance (high cost performance).

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

<Colored curable composition>
The colored curable composition of the present invention (hereinafter sometimes referred to as “the composition of the present invention”) has, as a colorant, an azomethine dye represented by the following general formula (I) and the following general formula ( A) a tetraazaporphyrin-based dye (hereinafter, sometimes collectively referred to as “the dye compound according to the present invention”), preferably including a binder, a polymerizable compound, and a radiation-sensitive compound. It becomes. Moreover, generally it can comprise using a solvent and can comprise using other components, such as a crosslinking agent, as needed.

-Colorant-
<Azomethine dye represented by formula (I)>
The colored curable composition of the present invention contains at least one azomethine dye represented by the following general formula (I). 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 (I), R ¹¹ represents a hydrogen atom or a substituent, and R ¹² , R ¹³ , R ¹⁴ , and R ¹⁵ each independently represent a hydrogen atom or a substituent, R ¹⁶ and R ¹⁷ 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 ¹⁸ ) ═, and R ¹⁸ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group. R ¹² and R ¹³ , R ¹³ and R ¹⁶ , R ¹⁴ and R ¹⁵ , R ¹⁵ and R ¹⁷ , and R ¹⁶ and R ¹⁷ are bonded to each other to form a 5-membered, 6-membered or 7-membered ring. May be.
Hereinafter, R ^{11 to} R ¹⁷ , Za and Zb in the general formula (I) will be described in detail.

In the general formula (I), R ¹¹ represents a hydrogen atom or a substituent. The substituent represented by R ¹¹ 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). For example, phenyl, naphthyl, etc.), 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 A group (preferably an alkoxy group having 1 to 48 carbon atoms, more preferably 1 to 12 carbon atoms such as Shi, 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 ¹¹ is a further substitutable group, it may be further substituted with the above R ¹¹ , and when it has two or more substituents, those substituents are They may be the same or different.

R < ¹² > -R < ¹⁵ > in general formula (I) represents a hydrogen atom or a substituent each independently, and the substituent represented by R < ¹² > -R < ¹⁵ > is synonymous with the substituent represented by said R < ¹¹ >. The preferred embodiment is also the same. When the substituent represented by R ^{12 to} R ¹⁵ is a further substitutable group, it may be substituted with the substituent represented by R ¹¹ , or may be substituted with two or more substituents These substituents may be the same or different.

In the general formula (I), R ¹⁶ and R ¹⁷ 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 ¹⁶ or R ¹⁷ , 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 ¹¹ , and preferred ranges thereof are also the same.

When R ¹⁶ and R ¹⁷ are further substitutable groups, they may be further substituted with the substituent represented by R ¹ , and when they are substituted with two or more substituents, The substituents may be the same or different.

In the general formula (I), Za and Zb each independently represent —N═ or —C (R ¹⁸ ) ═, and R ¹⁸ 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 ¹⁸ has the same meaning as the alkyl group, alkenyl group, aryl group, or heterocyclic group described for the substituent represented by R ^11. The same applies to each preferred range. In addition, when the substituent represented by R ¹⁸ is a further substitutable group, it may be further substituted with the substituent represented by R ¹¹ 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 ¹⁸ ). R ¹⁸ is preferably an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group. More preferred is an embodiment represented by the following general formula (II) or general formula (III).

In the general formula (I), R ¹² and R ¹³ , R ¹³ and R ¹⁶ , R ¹⁴ and R ¹⁵ , R ¹⁵ and R ¹⁷ , and R ¹⁶ and R ¹⁷ are bonded to each other to form 5 or 6 members. 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 ¹¹ , 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 (I), azomethine dyes represented by the following general formula (II) are preferable. Hereinafter, R ^{19 to} R ²⁴ , R ^{51 to} R ⁵⁴ , R ⁵⁶ , Zc, and Zd in the general formula (II) will be described in detail.

In the general formula (II), R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , and R ²⁴ each independently represent a hydrogen atom or a substituent. The substituents represented by R ^{19 to} R ²⁴ have the same meaning as the substituent represented by R ¹¹ , and preferred ranges thereof are the same.

When the substituent represented by R ^{19 to} R ²⁴ is a further substitutable group, it may be further substituted with the substituent represented by R ¹¹ and may be substituted with two or more substituents. The substituents may be the same or different.

In the general formula (II), R ⁵¹ represents a hydrogen atom or a substituent, and the substituent represented by R ⁵¹ has the same meaning as the substituent represented by R ¹¹ in the general formula (I), The preferred range is the same. When the substituent represented by R ⁵¹ is a further substitutable group, it may be further substituted with the substituent represented by R ¹¹ , or may be substituted with two or more substituents. These substituents may be the same or different.

In the general formula (II), R ⁵² , R ⁵³ , and R ⁵⁴ each independently represent a hydrogen atom or a substituent. R ⁵² is synonymous with R ¹² in the general formula (I), and the preferred embodiments thereof are the same, and R ⁵³ is synonymous with R ¹³ in the general formula (I), and the preferred embodiments thereof are also the same. R ⁵⁴ has the same meaning as R ¹⁴ in the general formula (I), and preferred embodiments thereof are the same, and R ⁵⁶ has the same meaning as R ¹⁶ in the general formula (I), and preferred embodiments thereof. Is the same.

When R ^{52 to} R ⁵⁴ are further substitutable groups, they may be substituted with the substituent represented by R ¹¹ , and when they are substituted with two or more substituents, The substituents may be the same or different.
In the general formula (II), R ⁵² and R ⁵³ , R ⁵³ and R ⁵⁶ , R ⁵⁶ and R ¹⁹ , R ⁵⁴ and R ²⁴ are bonded to each other to form a 5-membered, 6-membered or 7-membered ring. May be formed.

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

  Among the azomethine dyes represented by the general formula (II), azomethine dyes represented by the following general formula (III) are more preferable.

In the general formula ^{(III), R 19 ~R 24} , R 51 ~R 54 is an ^{R 19 ~R 24, R 51 ~R} 54 in the general formula (II) have the same meanings, R ⁵⁸ represents hydrogen An atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group is represented.

In the general formula (III), the alkyl group, alkenyl group, aryl group, and heterocyclic group represented by R ⁵⁸ are the alkyl group, alkenyl group, aryl group described for the substituent represented by R ¹¹ , And the same as the heterocyclic group, and the preferred embodiments thereof are also the same.
R ⁵⁸ may be further substituted with the substituent described in the above R ¹¹ , 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 (I) is preferably an azomethine dye represented by the general formula (II), and more preferably represented by the general formula (III). An azomethine dye.
Next, a preferable range of the dye represented by the general formula (III) will be described.

In the general formula (III), R ⁵¹ is an alkyl group, alkenyl group, aryl group, heterocyclic group, hydroxyl group, cyano group, alkoxy group, aryloxy group, heterocyclic oxy group, carbamoyloxy group, acyl group, 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 ⁵² , R ⁵³ and R ⁵⁴ are each independently a hydrogen atom, halogen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, alkoxy group, aryl Oxy group, alkoxycarbonyl group, Vamoyl group, amino group, anilino group, carbonamido group, ureido group, alkoxycarbonylamino group, sulfonamido group, sulfamoylamino group, azo group, alkylthio group, arylthio group, heterocyclic thio group, alkylsulfinyl group, aryl A sulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, a sulfo group, a phosphonyl group, or a phosphinoylamino group, wherein R ⁵⁶ is an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group, An azomethine dye in which R ⁵⁸ is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group, and R ^{19 to} R ²⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group Is preferred.

More preferably, in the general formula (III), R ⁵¹ 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 ⁵² , R ⁵³ , and R ⁵⁴ 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 ⁵⁶ is an alkyl group, alkenyl group, aryl group, or heterocyclic group, and R ⁵⁸ is a hydrogen atom, An alkyl group, an alkenyl group, an aryl group, or a heterocyclic group; I, independently R ¹⁹ to R ²⁴ are each a azomethine dye is a hydrogen atom or an alkyl group.

More preferably, in the general formula (III), R ⁵¹ is an alkyl group, aryl group, heterocyclic group, alkoxycarbonyl group, carbamoyl group, alkylthio group, arylthio group, alkylsulfonyl group, or arylsulfonyl group, R ⁵² , R ⁵³ , and R ⁵⁴ are each independently a hydrogen atom, halogen atom, alkyl group, alkoxy group, aryloxy group, alkoxycarbonyl group, carbamoyl group, carbonamido group, ureido group, alkoxycarbonylamino group, sulfone an amido group, an alkylthio group or an arylthio group, an R ⁵⁶ is an alkyl group or an aryl group, R ⁵⁸ is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group, R to ¹⁹ to R ²⁴ are each independently hydrogen atom or an alkyl group, a It is a methine-based dye.

More preferably, in the general formula (III), R ⁵¹ is an alkyl group, and R ⁵² , R ⁵³ , and R ⁵⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group. An azomethine group in which R ⁵⁶ is an alkyl group, R ⁵⁸ is an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group, and R ^{19 to} R ²⁴ are each independently a hydrogen atom or an alkyl group. It is a pigment.

Most preferably, in the general formula (III), R ⁵¹ is a tertiary alkyl group, and R ⁵² , R ⁵³ , and R ⁵⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group. R ⁵⁶ is an alkyl group, R ⁵⁸ is an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group, R ¹⁹ and R ²⁰ are alkyl groups, and R ^{21 to} R ²³ are An azomethine dye having a hydrogen atom and R ²⁴ is an alkyl group.

  Specific examples of the azomethine dyes represented by the general formula (I) (Exemplary dyes M-1 to M-84) are shown below. However, the present invention is not limited to these.

Next, a synthesis example of the azomethine dye represented by the general formula (I) will be described with reference to the following reaction scheme A as an example of the synthesis of the exemplified dye M-1. However, the present invention is not limited to this, and the exemplified dyes other than the exemplified dye M-1 can be obtained by a similar method.

<< Synthesis Example >>: Synthesis of Illustrative Dye M-1

(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 M-1 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 amorphous exemplified dye M-1.
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.

<Tetraazaporphyrin dye represented by formula (A)>
The colored curable composition of the present invention contains at least one tetraazaporphyrin-based dye represented by the following general formula (A). This dye 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 composition of this invention, you may make it use 2 or more types together besides containing the compound represented by general formula (A) individually by 1 type. The compound represented by the general formula (A) (the dye compound according to the present invention) includes tautomers (the same applies hereinafter).

In the general formula (A), ring A ¹ , ring A ² , ring A ³ , and ring A ⁴ each independently represent the following aromatic ring, and the direction of the condensed ring and substitution of a substituent bonded thereto: There are many isomers depending on the position.

Furthermore, at least one of the ring A ¹ , the ring A ² , the ring A ³ , and the ring A ⁴ represents the following aromatic ring.

  Specifically, as the basic skeleton of the general formula (A), there are five types of structures represented by the following formulas (3) to (7). Further, 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 (A), R ¹ and R ² each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group. However, R ¹ and R ² 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 ¹ or R ² is preferably an alkyl group having 1 to 12 carbon atoms, for example, 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 ¹ or R ² 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.

R ¹ and R ² are each independently a hydrogen atom (provided that R ¹ and R ² do not represent a hydrogen atom at the same time), an unsubstituted alkyl group, or “an oxygen atom connected to an ether bond, a carbonyl A preferred embodiment is a substituted alkyl group containing at least one form of a bond and an ester bond.

Of the above, R ¹ and R ² are each independently a hydrogen atom (wherein R ¹ and R ² do not represent a hydrogen atom at the same time), 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 form of an ether bond, a carbonyl bond, and an ester bond” is particularly preferable, and among them, R ¹ and R ² 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 solubility in a polar organic solvent It is preferable at a high point.

Further, an embodiment in which at least one of R ¹ and R ² 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 ¹ and R ² is a substituted alkyl group represented by the following formula (B) is preferable.

In the formula (B), R ³ and R ⁴ 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 ³ and R ⁴ 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 ³ or R ⁴ 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 ³ or R ⁴ 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 ³ or R ⁴ , 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 (A), 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 (A) includes a part or all of these many isomers.

  Hereinafter, exemplary compounds [specific examples 1 to 157] of the tetraazaporphyrin compound represented by the general formula (A) are shown. The present invention is not limited to these specific examples.

~ Method for producing tetraazaporphyrin compound represented by formula (A) ~
Hereinafter, the manufacturing method of the tetraazaporphyrin compound represented by the said general formula (A) is demonstrated. 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 ¹ R ² ( In the formula, R ¹ and R ² are synonymous with R ¹ and R ² in the general formula (A).) An organic amine compound (2 to 8 times molar ratio of the bromo-substituted tetraazaporphyrin compound) It is dropped while keeping the temperature at 15 ° C. or lower. After dripping, the tetraazaporphyrin compound represented by the said general formula (A) is obtained by stirring at 20-30 degreeC for 15-24 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.

  The compound represented by the general formula (A) (colorant) may be used in combination of other kinds, other colorants, salts of other colorants with metals and nitrogen-containing compounds, complexes, other You may use it simultaneously with the derivative | guide_body of a coloring agent, etc.

  In the colored curable composition of the present invention, as the colorant, the azomethine dyes represented by the general formulas (I) to (III) can be contained alone or in combination of two or more. The tetraazaporphyrin-based dyes represented by the general formula (A) can be used alone or in combination of two or more. Furthermore, known dyes can be used in combination, and examples of the known dyes include xanthene dyes and triarylmethane dyes.

  In the present invention, the azomethine dyes represented by the general formulas (I) to (III) and the tetraazaporphyrin dye represented by the general formula (A) are used in combination. A combination of an azomethine dye represented by (III) and a tetraazaporphyrin dye represented by formula (A) is preferred.

  The concentration of the coloring compound according to the present invention in the colored curable composition varies depending on the molecular weight and the molar extinction coefficient ε, but is preferably 0.5 to 80% by mass relative to the total solid components of the composition. 5-60 mass% is more preferable, and 0.5-50 mass% is especially preferable.

  Further, an azomethine dye represented by the general formula (I) (including those represented by the general formulas (II) to (III)), a tetraazaporphyrin dye represented by the general formula (A), and The content ratio [general formula (I) / general formula (A)] varies depending on the molecular weight and molar extinction coefficient ε, but is preferably 1/9 to 9/1, more preferably 1/4. ~ 4/1, particularly preferably 1/4 to 2/1.

<Binder>
The colored curable composition of this invention can be comprised suitably using at least 1 type of a binder. The binder that can be used in the present invention is not particularly limited as long as it is alkali-soluble, but is preferably selected from the viewpoints of heat resistance, developability, availability, and the like.

  The alkali-soluble binder (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, There are maleic acid copolymers, partially esterified maleic acid copolymers, and the like, and acidic cellulose derivatives having a carboxylic acid in the side chain are also useful. In addition, a polymer having a hydroxyl group with an acid anhydride added, a polyhydroxystyrene resin, a polysiloxane resin, poly (2-hydroxyethyl (meth) acrylate), polyvinylpyrrolidone, polyethylene oxide, polyvinyl Alcohol and the like are also useful.

  The alkali-soluble binder may be obtained by copolymerizing a hydrophilic monomer. Examples of the alkali-soluble binder include alkoxyalkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, glycerol (meth) acrylate, and (meth). Acrylamide, N-methylolacrylamide, 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 Doors and the like.

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

In order to improve the crosslinking efficiency, a polymer having a polymerizable group in the side chain, and a polymer having an allyl group, a (meth) acryl group, an allyloxyalkyl group, etc. as the polymerizable group in the side chain are also useful. It is.
Examples of the polymer having these polymerizable groups include KS resist-106 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), cyclomer P series (manufactured by Daicel Chemical Industries, Ltd.) and the like.

  From the viewpoint of increasing the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are also useful.

  Among these various binders, the alkali-soluble binder that can be used in the present invention includes, from the viewpoint of heat resistance, a polyhydroxystyrene resin, a polysiloxane resin, an acrylic resin, an acrylamide resin, and an acrylic / acrylamide copolymer resin. Acrylic resins, polyhydroxystyrene resins, and polysiloxane resins are more preferable. From the viewpoint of control of developability, an acrylic resin, an acrylamide resin, and an acrylic / acrylamide copolymer resin are preferable.

  Examples of the acrylic resin include a copolymer composed of a monomer selected from benzyl (meth) acrylate, (meth) acrylic acid, hydroxyethyl (meth) acrylate, (meth) acrylamide, and the like, and a polymerizable side chain. (Meth) acrylic resins such as KS resist 106 (both manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series and the like are preferable.

  An alkali-soluble phenol resin can also be used. This alkali-soluble phenol resin is suitable when the composition of the present invention is a positive composition. Examples of the alkali-soluble phenol resin include novolak resins and vinyl polymers.

  Examples of the novolak resin include those obtained by condensing phenols and aldehydes in the presence of an acid catalyst. Examples of the phenols include phenol, cresol, ethylphenol, butylphenol, xylenol, phenylphenol, catechol, resorcinol, pyrogallol, naphthol, and bisphenol A. Examples of the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, and the like. The phenols and aldehydes can be used alone or in combination of two or more.

  Specific examples of the novolak resin include a condensation product of metacresol, paracresol, or a mixture thereof and formalin. The novolak resin may be adjusted in molecular weight distribution using means such as fractionation. Moreover, you may mix the low molecular weight component which has phenolic hydroxyl groups, such as bisphenol C and bisphenol A, with a novolak resin.

The binder in the present invention is preferably a polymer having a weight average molecular weight (polystyrene conversion value measured by GPC method) of 1000 to 2 × 10 ⁵ , and more preferably 2000 to 1 × 10 ^5. A polymer of 5000 to 5 × 10 ⁴ is particularly preferable.

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

<Crosslinking agent>
The present invention contains an azomethine dye represented by the above-mentioned general formula (I) and a tetraazaporphyrin-based dye represented by the general formula (A) as a colorant, and is more resistant to light and heat than conventional ones. In addition to improving the properties and patterning properties, the cured reaction of the film can be advanced to obtain a cured film that is well cured. It is also possible to configure so as to obtain a deposited film.

  The crosslinking agent is not particularly limited as long as the film can be cured by a crosslinking reaction. For example, at least one selected from (a) an epoxy resin, (b) a methylol group, an alkoxymethyl group, and an acyloxymethyl group. A melamine compound substituted with one group, a guanamine compound, a glycoluril compound, or a urea compound, (c) a phenol compound substituted with at least one group selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group, naphthol A compound, or a hydroxyanthracene compound. Of these, polyfunctional epoxy resins are particularly preferred.

  The (a) epoxy resin may be any epoxy resin as long as it has an epoxy group and crosslinkability. For example, bisphenol A glycidyl ether, ethylene glycol diglycidyl ether, butanediol diglycidyl ether, hexanediol Diglycidyl ether, dihydroxybiphenyl diglycidyl ether, diglycidyl phthalate ester, N, N-diglycidyl aniline and other divalent glycidyl group-containing low molecular weight compounds, as well as trimethylolpropane triglycidyl ether, trimethylolphenol triglycidyl Trivalent glycidyl group-containing low molecular weight compounds typified by ether, TrisP-PA triglycidyl ether, pentaerythritol tetraglycidyl ether, tetramethylol bisphenol Tetravalent glycidyl group-containing low molecular weight compounds typified by tetra-A-glycidyl 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 in the case of melamine compounds, in the case of glycoluril compounds, guanamine compounds, and urea compounds. Although it is 2-4, Preferably it is 5-6 in the case of a melamine compound, and 3-4 in the case of a glycoluril compound, a guanamine compound, and a urea compound.

  Hereinafter, the melamine compound, guanamine compound, glycoluril compound and urea compound of (b) are collectively referred to as a compound (methylol group-containing compound, alkoxymethyl group-containing compound, or acyloxymethyl group-containing compound) according to (b). There is.

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

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

  Examples of the guanamine compound include, 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.
The compounds according to (b) may be used alone or in combination.

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

  The number of methylol groups, acyloxymethyl groups, and alkoxymethyl groups contained in the cross-linking agent (c) is at least two per molecule, and from the viewpoint of thermal crosslinkability and storage stability, phenol as a skeleton Compounds in which the 2nd and 4th positions of the compound are all substituted are preferred. In addition, the naphthol compound and hydroxyanthracene compound as the skeleton are preferably compounds in which all of the ortho-position and para-position of the OH group are substituted. The 3rd or 5th position of the phenolic compound serving as the skeleton may be unsubstituted or may have a substituent. In addition, the naphthol compound as a skeleton may be unsubstituted or may have a substituent other than 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 a phenol compound, a naphthol compound, a hydroxyanthracene compound, etc., in which the ortho-position or para-position of the phenolic OH group is unsubstituted. For example, phenol, cresol isomers, 2,3-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, bisphenols such as bisphenol A, 4,4′-bishydroxybiphenyl, TrisP-PA (Honshu Chemical) Kogyo Co., Ltd.), naphthol, dihydroxynaphthalene, 2,7-dihydroxyanthracene, and the like are used.

  Specific examples of the crosslinking agent (c) include trimethylolphenol, tri (methoxymethyl) phenol, a compound obtained by methoxymethylating one or two methylol groups of trimethylolphenol, trimethylol-3-cresol, tri ( Methoxymethyl) -3-cresol, a compound obtained by methoxymethylating one or two methylol groups of trimethylol-3-cresol, dimethylolcresol such as 2,6-dimethylol-4-cresol, tetramethylolbisphenol A, tetra Methoxymethyl bisphenol A, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylol bisphenol A, tetramethylol-4,4′-bishydroxybiphenyl, tetramethoxymethyl-4,4′-bishydroxybiphenyl, Tr Hexamethylol of sP-PA, hexamethoxymethyl of Tris P-PA, compounds in which 1 to 5 methylol groups have been methoxymethylated hexamethylol of Tris P-PA, Bis-hydroxymethyl naphthalene diol.

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

Among these compounds, trimethylolphenol, bishydroxymethyl-p-cresol, tetramethylolbisphenol A, trisP-PA (manufactured by Honshu Chemical Industry Co., Ltd.) or a methylol group thereof is preferable. Examples thereof include an alkoxymethyl group and a phenol compound substituted with both a methylol group and an alkoxymethyl group.
These compounds according to (c) may be used alone or in combination.

  When the crosslinking agent is contained, the content of the crosslinking agent (a) to (c) in the colored curable composition varies depending on the material, but it is 1 to the total solid content (mass) of the composition. 70 mass% is preferable, 5-50 mass% is more preferable, and 7-30 mass% is especially preferable. When the content is within the above range, a sufficient degree of curing and elution of the unexposed area can be maintained, and the degree of cure of the exposed area is not insufficient and the elution of the unexposed area is not significantly reduced. .

<Polymerizable compound>
The colored curable composition of the present invention can be suitably configured using at least one polymerizable compound (hereinafter sometimes referred to as “polymerizable monomer”). The polymerizable monomer is mainly contained when the colored curable composition is configured as a negative type.
Moreover, you may contain in the positive type | system | group containing the below-mentioned naphthoquinone diazide compound, In this case, the hardening degree of the pattern formed can be promoted more. Hereinafter, the polymerizable monomer will be described.

As the polymerizable monomer, a compound having a boiling point of 100 ° C. or higher under normal pressure and having at least one addition-polymerizable ethylenically unsaturated group is preferable. As the ethylenically unsaturated group, a (meth) acryloyl group is particularly preferable.
In addition, (meth) acryloyl represents acryloyl or methacryloyl, and the following (meth) acrylate similarly represents acrylate or methacrylate.

  Examples of polymerizable monomers 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, trimethylol Ethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, Hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxye) (I) Polyfunctional alcohols such as isocyanurate, glycerin and trimethylolethane, which are added with ethylene oxide or propylene oxide and then converted to (meth) acrylate, JP-B-48-41708, JP-B-50-6034, JP Urethane acrylates described in JP-A-51-37193, polyester acrylates described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, epoxy resins and ( Mention may be made of polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products with (meth) acrylic acid; and mixtures thereof. Furthermore, Journal of Japan Adhesion Association Vol. 20, no. 7, pages 300 to 308 are introduced as photocurable monomers and oligomers.

As content in the colored curable composition of a polymerizable monomer, 0.1-90 mass% is preferable with respect to the total solid, 1.0-80 mass% is still more preferable, 2.0-70 mass % Is particularly preferred.

<Radiation sensitive compounds>
The colored curable composition of this invention can be comprised suitably by containing at least 1 sort (s) of a radiation sensitive compound. The radiation sensitive compound according to the present invention is a compound capable of causing a chemical reaction such as generation of radical, generation of acid, generation of base, etc., against radiation such as UV, Deep UV, visible light, infrared light, electron beam, By inactivating the above binders by reactions such as crosslinking, polymerization, decomposition of acidic groups, polymerization of polymerizable monomers and oligomers coexisting in the coating film, crosslinking of the crosslinking agent, etc. It is used for the purpose of insolubilizing with a developer.

  In particular, when the colored curable composition is composed of a negative type, it preferably contains a photopolymerization initiator, and when it constitutes a positive type, it preferably contains a naphthoquinonediazide compound. .

~ Photoinitiator ~
The photopolymerization initiator is not particularly limited as long as it can polymerize the polymerizable monomer, and is preferably selected from the viewpoints of characteristics, initiation efficiency, absorption wavelength, availability, cost, and the like. In addition, you may further contain in the positive type | system | group using the following naphthoquinone diazide compound, In this case, the hardening degree of the pattern formed can be promoted more.

  As the photopolymerization initiator, at least one active halogen compound selected from a halomethyloxadiazole compound, a halomethyl-s-triazine compound, a benzyldimethyl ketal compound, an α-hydroxyketone compound, an α-aminoketone compound, a phosphor Finoxide compounds, metallocene compounds, 3-aryl substituted coumarin compounds, lophine dimers, triallylimidazole dimers, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, Examples include oxime compounds.

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

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

  Other 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-y ) -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-trichloro Methyl-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-naphth-2) -Yl) -4,6-bis-trichloromethyl-s-triazine, 2- (5-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4,7 -Dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-ethoxy-naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4,5-dimension Xyl-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 4- [p-N, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -S-triazine, 4- [o-methyl-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [p-N, N -Di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-methyl-pN, N-di (chloroethyl) aminophenyl] -2,6-di ( Trichloromethyl) -s-triazine, 4- (pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (pN-ethoxycarbonylmethylamino) Phenyl) -2,6-di (trichloromethyl) -s-triazine, 4- [pN, N-di (phenyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (PN-chloroethylcarbonylaminophenyl) -2,6-di (trichloromethyl) -s-triazine,

4- [pN- (p-methoxyphenyl) carbonylaminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [mN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-bromo-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s- Triazine, 4- [m-chloro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-fluoro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-bromo-pN, N-di (ethoxycarbonylmethyl) Minophenyl] -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 -p-N, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine,

4- [m-chloro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-fluoro-pN, N-di ( Chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (m-bromo-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s- Triazine, 4- (m-chloro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-fluoro-pN-ethoxycarbonylmethylaminophenyl) ) -2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloro) Til) -s-triazine, 4- (o-chloro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -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-tri 4- (o-chloro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-fluoro-pN-chloroethylaminophenyl)- 2,6-di (trichloromethyl) -s-triazine and the like can be mentioned.

  In addition, TAZ series (for example, TAZ-107, TAZ-110, TAZ-104, TAZ-109, TAZ-140, TAZ-204, TAZ-113, TAZ-123) manufactured by Midori Chemical, T manufactured by PANCHIM Series (eg, T-OMS, T-BMP, TR, TB), Irgacure series (eg, Irgacure 369, Irgacure 784, Irgacure 651, Irgacure 184, Irgacure 500, manufactured by Ciba Specialty Chemicals, Inc. IRGACURE 1000, IRGACURE 149, IRGACURE 819, IRGACURE 261), DAROCURE series (eg DAROCURE 1173),

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

  Examples of the α-aminoketone compounds include Irgacure series (Irgacure 907, Irgacure 369) manufactured by Ciba Specialty Chemicals, 2-methyl-1-phenyl-2-morpholinopropan-1-one, 2-methyl- Examples include 1- [4- (hexyl) phenyl] -2-morpholinopropan-1-one, 2-ethyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1.

  The oxime compound is not particularly limited, but 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 1- (O-acetyloxime) -1- [9-Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (4-methylsulfanyl-phenyl) -butane-1,2-butane-2-oxime-O-acetate 1- (4-methylsulfanyl-phenyl) -butan-1-oneoxime-O-acetate, hydroxyimino- (4-methylsulfanyl-phenyl) -acetic acid ethyl ester-O-acetate, hydroxyimino- (4-methylsulfanyl) -Phenyl) -acetic acid ethyl ester-O-benzoate and the like.

  As for the other initiators mentioned above, from the viewpoints of availability and stability, the benzyldimethyl ketal compound is Irgacure 651, and the α-hydroxyketone compound is Irgacure 184, 1173, 500, and the like. 1000, 2959, etc., the α-aminoketone compound is Irgacure 907, 369, etc., and the phosphine oxide compound (blend) is Irgacure 1700, 149, 1850, 819, 184, etc. As the metallocene compound, Irgacure 784, 261 and the like (both manufactured by Ciba Specialty Chemicals) are preferable, and analogs / peripheral compounds thereof are also preferable.

  As described above, since the photopolymerization initiator is preferably a compound that does not decompose and generate acid in terms of light resistance and heat resistance of the colorant (particularly dye), among the above, as a compound that does not generate acid by decomposition, Benzyldimethyl ketal compound, α-hydroxyketone compound, α-aminoketone compound, phosphine oxide compound, metallocene compound, oxime compound, triallylimidazole dimer, benzothiazole compound, benzophenone compound, acetophenone compound and derivatives thereof, and At least one selected from a cyclopentadiene-benzene-iron complex and a salt thereof is preferable. Furthermore, at least one selected from the group consisting of α-aminoketone compounds, phosphine oxide compounds, metallocene compounds, oxime compounds and triallylimidazole dimers is preferred.

  In addition to the above photopolymerization initiator, other known photopolymerization initiators can be used in the composition of the present invention. Specifically, the vicinal polykettle aldonyl compound described in US Pat. No. 2,367,660, the α described in US Pat. Nos. 2,367,661 and 2,367,670 A carbonyl compound, an acyloin ether described in US Pat. No. 2,448,828, an aromatic acyloin compound substituted with an α-hydrocarbon described in US Pat. No. 2,722,512, Polynuclear quinone compounds described in US Pat. Nos. 3,046,127 and 2,951,758, triallylimidazole dimer / p-aminophenyl ketone described in US Pat. No. 3,549,367 Benzothiazole compounds / trihalomethyl-s-triazine compounds described in Japanese Patent Publication No. 51-48516. The

  The content of the photopolymerization initiator in the colored curable composition is preferably 0.01 to 50% by mass, more preferably 1 to 30% by mass, and 1 to 20% by mass with respect to the solid content of the composition. Is particularly preferred. When the content of the photopolymerization initiator is in the range of 0.01 to 50% by mass, it is possible to prevent the molecular weight from becoming too low and the film strength from becoming weak.

  A sensitizer and a light stabilizer can be used in combination with the photopolymerization initiator. Specific examples thereof include, for example, 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, 2-ethoxyxanthone, thioxanthone, 2,4-diethylthioxanthone, acridone, 10-butyl-2-chloroacridone, benzyl, dibenzalacetone, p- (dimethylamino) phenylstyryl ketone, p -(Dimethylamino) phenyl-p-methylstyrene Luketones, benzophenones, p- (dimethylamino) benzophenones (or Michler ketones), p- (diethylamino) benzophenones, benzoanthrones, benzothiazole compounds described in Japanese Patent Publication No. 51-48516, etc., Tinuvin 1130, 400, etc. Is mentioned.

~ Naphthoquinonediazide compound ~
The naphthoquinonediazide compound is a compound having at least one o-quinonediazide group, such as o-naphthoquinonediazide-5-sulfonic acid ester, o-naphthoquinonediazide-5-sulfonic acid amide, o-naphthoquinonediazide-4-sulfone. Acid ester, o-naphthoquinonediazide-4-sulfonic acid amide, and the like. These ester compounds and amide compounds are produced by a known method using, for example, a phenol compound described in general formula (I) in JP-A-2-84650 and JP-A-3-49437. be able to.

  When the colored curable composition is constituted as a positive type, the above-mentioned binder (particularly alkali-soluble phenol resin) and crosslinking agent are usually about 2 to 50% by mass and about 2 to 30% by mass, respectively, in the solvent. It is preferable to dissolve at a ratio. Moreover, it is preferable that content of a naphthoquinone diazide compound and a coloring agent is normally added in the ratio of 2-30 mass% and 2-50 mass% with respect to the solution which melt | dissolved the binder and the crosslinking agent, respectively.

<Solvent>
In preparing the colored curable composition of the present invention, a solvent can generally be contained. The solvent is basically not particularly limited as long as it satisfies the solubility of each component and the applicability of the curable composition, but is particularly selected in consideration of the solubility, applicability, and safety of the binder. Is preferred.

  Specific examples of the solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, Methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc .;

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

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

  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, ethyl carbitol acetate, butyl Carbitol acetate, propylene glycol methyl ether, propylene glycol methyl ether acetate and the like are more preferable. Of these, ethyl lactate, cyclohexanone, and propylene glycol methyl ether acetate are most preferable.

<Other ingredients>
The composition of this invention can be comprised using the other component shown below in addition to the above-mentioned component.
-Thermal polymerization inhibitor-
It is preferable to add a thermal polymerization inhibitor to the composition of the present invention. Examples of the thermal polymerization inhibitor include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-t- Butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2-mercaptobenzimidazole, and the like are useful.

-Various additives-
In the composition of the present invention, various additives such as fillers, polymer compounds other than the above, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation agents and the like are blended as necessary. be able to.

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

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

  The colored curable composition of the present invention is used for forming colored pixels such as color filters used in liquid crystal display elements (LCDs) and solid-state imaging elements (for example, CCD, CMOS, etc.), and for printing inks and inkjets. It can be suitably used as a production application for inks and paints.

<< Color filter and manufacturing method thereof >>
Next, the color filter of the present invention will be described in detail through its manufacturing method.
In the method for producing a color filter of the present invention, the above-described colored curable composition of the present invention is used. The color filter of the present invention comprises the azomethine dye represented by the general formula (I) and the tetraazaporphyrin dye represented by the general formula (A) (including tautomers). It can be most suitably produced using the colored curable composition of the present invention described above.

Specifically, the colored curable composition is coated on a support by a coating method such as spin coating, cast coating, roll coating, etc. to form a radiation sensitive composition layer, and the layer is formed into a predetermined mask pattern. It can be produced by forming a negative or positive colored pattern by developing with a developer and developing with a developer (image forming step). At this time, if necessary, a curing step of curing the formed colored pattern by heating and / or exposure can be provided. As light or radiation used at this time, ultraviolet rays such as g-line, h-line and i-line are particularly preferably used.
In addition, when the colored curable composition is configured as a positive type, a step of post-baking the colored pattern after image formation can be provided.

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

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

  As the developer used in the method for producing a color filter of the present invention, any developer may be used as long as it has a composition that dissolves the uncured portion of the composition of the present invention but does not dissolve the cured portion forming the filter. it can. Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used. Examples of the organic solvent include the above-described solvents used for preparing the composition of the present invention.

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

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

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

[Examples 1 to 17, Comparative Example 1]
1) Preparation of dye-containing curable composition The compounds having the following compositions are mixed and dissolved, and the dye-containing curable compositions (1) to (17) of the present invention and a comparative dye-containing curable composition (20 ) Was prepared.

~ Synthesis of comparative compounds ~
12 g of copper phthalocyanine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to 120 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 130 to 135 ° C. over 2 hours, reacted at the same temperature for 4 hours, and then cooled to 80 ° C. Further, 20 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 neutrality to obtain a hydrated phthalocyanine sulfonyl chloride.

  Immediately thereafter, this was poured into 400 g of ice water, and after 30 minutes of dispersion and stirring at 10 ° C. or less, 20 g of 3-butoxypropylamine was added dropwise. Next, the temperature was raised to 20 to 30 ° C., and stirred for 18 hours at the same temperature. Then, the product was separated by filtration, dispersed in 200 g of water, filtered twice, and dried at 60 ° C. for 15 hours. As a result, 15 g of blue powder was obtained. This was further recrystallized with ethyl acetate to obtain 6.4 g of blue crystals (comparative compound). According to the X-ray fluorescence analysis, this blue crystal had 3.8 average sulfonamide groups per molecule depending on the intensity ratio between copper, which is the central metal of the phthalocyanine skeleton, and the sulfur atom of the sulfonamide group.

The details of the composition in Table 1 are as follows.
* Resin A: benzyl methacrylate / methacrylic acid copolymer (= 70/30 [molar ratio])
* Monomer A: DPHA manufactured by Nippon Kayaku Co., Ltd. (trade name; main component: dipentaerythritol hexaacrylate)
* TAZ-107: manufactured by Midori Chemical Co., Ltd. * TAZ-104: manufactured by Midori Chemical Co., Ltd. * Oxime A: 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2- Octanedione; Ciba Specialty Chemicals Co., Ltd. * Oxime B: 1- (O-acetyloxime) -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone ; Ciba Specialty Chemicals Co., Ltd. * F475: Surfactant made by Dainippon Ink & Chemicals, Inc.

[Example 18]: Positive type dye-containing curable composition The following composition was mixed to obtain a positive type dye-containing curable composition (18).
-Dye Compound According to the Present Invention Illustrative Dye M-9 (Dye Represented by General Formula (I)) ... 4.5 g
Specific Example 28 described above (dye represented by formula (A)) 1.5 g
・ Ethyl lactate: 80.0g
・ The following binder P-1 ... 18.0g
-Photo acid generator PAG-1 below: 2.0 g
・ Fluorosurfactant: 0.01g
[Product name: F-475, manufactured by Dainippon Ink & Chemicals, Inc.]

[Example 19]: Positive type dye-containing curable composition The following composition was mixed to obtain a positive type dye-containing curable composition (19).
-Dye Compound According to the Present Invention Illustrative Dye M-8 (Dye Represented by General Formula (I)) ... 4.5 g
Specific Example 28 described above (dye represented by formula (A)) 1.5 g
・ Ethyl lactate: 80.0g
・ Novolak resin condensed with p-cresol and formaldehyde (polystyrene equivalent molecular weight 5,500) 6.0 g
・ Hexamethoxymethylolmelamine ... 2.0g
-Esterified product of 2,3,4-trihydroxybenzophenone and o-naphthoquinonediazide-5-sulfonyl chloride 6.0 g
(Esterification rate: 80 mol%; quinonediazide compound)
-Esterified product of [4- (7,8-dihydroxy-2,4,4-trimethyl-2-chromanyl) pyrogallol] and o-naphthoquinonediazide-5-sulfonic acid
... 6.0g

2) Preparation of glass substrate with undercoat layer A resist CT-2000L solution (manufactured by Fuji Film Electronics Materials Co., Ltd.) was applied on a glass substrate using a spin coater so as to have a film thickness of 2 μm. A cured film (undercoat layer) was formed by heating and drying for a period of time.

3) Exposure and development of dye-containing curable composition (image formation)
Each of the dye-containing curable compositions obtained in 1) above was applied in turn using a spin coater so that the film thickness was 1 μm on the undercoat layer of the glass substrate with an undercoat obtained in 2). And prebaking at 100 ° C. for 120 seconds.
Next, the coating film was irradiated through a 2 cm square mask using a UV exposure apparatus. After irradiation, 100% CD-2000 (Fuji Film Electronics Materials Co., Ltd.) developer (Examples 1 to 17 and Comparative Example 1) or FHD-5 (Fuji Film Electronics Materials Co., Ltd.) developer (Examples 18 to 19) were used for development at 23 ° C. for 60 seconds. Subsequently, after rinsing with running water for 20 seconds, spray drying was performed to obtain a pattern image (color filter).

4) Evaluation The following evaluation was performed about dye containing curable composition (1)-(20) obtained by each Example and the comparative example. The evaluation results are shown in Table 2 below.
-1. Pattern formability
The pattern image formed as described above was confirmed by an ordinary method using an optical microscope, and evaluated according to the following evaluation criteria.
〔Evaluation criteria〕
◯: There was no development residue in the unexposed area, and a clean pattern was obtained.
X: The development residue of an unexposed part was remarkable.

-2. Heat resistance and light resistance
After coating and pre-baking as in 3) above, the film was hardened by heating at 200 ° C. for 5 minutes, and this cured film was spectroscopically measured with MCPD-1000 (manufactured by Otsuka Electronics Co., Ltd.). did.
<Heat resistance> After placing the glass substrate on which the cured film was formed on a hot plate at 200 ° C. for 1 hour, spectroscopic measurement was performed again, and this was set as the spectral value after heating with respect to the reference value. ΔE ^* ab was obtained with a chromaticity calculation program.
<Light resistance> After the glass substrate on which the cured film was formed was exposed to 200,000 lux × 20 hours with a light resistance tester (manufactured by Suga Test Instruments Co., Ltd.), spectroscopic measurement was performed again, and this was exposed to the reference value. For later spectroscopy, ΔE ^* ab was obtained from both values using a chromaticity calculation program.

  As shown in Table 2, in Examples, the light resistance and heat resistance were good, and the development residue was suppressed, and the pattern formation was excellent. On the other hand, in Comparative Example 1, the development residue in the unexposed area was remarkable and the pattern forming property was inferior, and the light resistance and heat resistance after curing were insufficient.

  In addition to the dye compound according to the present invention used in the above examples, the specific examples of the dye compound according to the present invention described above are structurally similar to the specific examples used above (the dye compound according to the present invention). As described above, it is possible to obtain excellent pattern forming properties as well as excellent light resistance and heat resistance.

Claims (11)

At least one azomethine dye represented by the following general formula (I), at least one tetraazaporphyrin dye represented by the following general formula (A), a polymerizable compound, a photopolymerization initiator, , the colored curable composition characterized by containing.


[In General Formula (I), R ¹¹ represents a hydrogen atom or a substituent, R ¹² , R ¹³ , R ¹⁴ , and R ¹⁵ each independently represent a hydrogen atom or a substituent, and R ¹⁶ and R ¹⁷ 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 ¹⁸ ) ═, and R ¹⁸ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group. R ¹² and R ¹³ , R ¹³ and R ¹⁶ , R ¹⁴ and R ¹⁵ , R ¹⁵ and R ¹⁷ , and R ¹⁶ and R ¹⁷ are bonded to each other to form a 5-membered, 6-membered, or 7-membered ring. May be. ]


[In General Formula (A), Ring A ¹ , Ring A ² , Ring A ³ , and Ring A ⁴ are each independently


And at least one of ring A ¹ , ring A ² , ring A ³ , and ring A ⁴ is


Represents. R ¹ and R ² each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group, m represents an integer of 1 to 8, and n represents an integer of 1 to 4. However, R ¹ and R ² do not represent a hydrogen atom at the same time. ] At least one azomethine dye represented by the following general formula (I), at least one tetraazaporphyrin dye represented by the following general formula (A), a binder, a photoacid generator or a naphthoquinone diazide A colored curable composition comprising a compound.


[In general formula (I), R ¹¹ Represents a hydrogen atom or a substituent, and R ¹² , R ¹³ , R ¹⁴ And R ¹⁵ Each independently represents a hydrogen atom or a substituent; ¹⁶ And R ¹⁷ Each independently represents an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group. Za and Zb are each independently -N = or -C (R ¹⁸ ) = And R ¹⁸ Represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group. R ¹² And R ¹³ , R ¹³ And R ¹⁶ , R ¹⁴ And R ¹⁵ , R ¹⁵ And R ¹⁷ And R ¹⁶ And R ¹⁷ May be bonded to each other to form a 5-, 6-, or 7-membered ring. ]


  [In General Formula (A), Ring A ¹ , Ring A ² , Ring A ^Three And ring A ^Four Each independently


Represents ring A ¹ , Ring A ² , Ring A ^Three And ring A ^Four At least one of


Represents. R ¹ And R ² Each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group, m represents an integer of 1 to 8, and n represents an integer of 1 to 4. However, R ¹ And R ² And do not represent hydrogen atoms at the same time. ] The colored curable composition according to claim 1 , wherein the azomethine dye is an azomethine dye represented by the following general formula (II).


[In the general formula (II), R ⁵¹ represents a hydrogen atom or a substituent, R ⁵² , R ⁵³ and R ⁵⁴ each independently represent a hydrogen atom or a substituent, and R ⁵⁶ represents an alkyl group, an alkenyl. Represents a group, an aryl group, or a heterocyclic group. R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ and R ²⁴ each independently represents a hydrogen atom or a substituent. Zc and Zd each independently represent —N═ or —C (R ¹⁸ ) ═, and R ¹⁸ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group. ] Furthermore, the coloring curable composition of Claim 1 or Claim 3 containing a binder. The colored curable composition according to claim 1, 3 or 4, wherein the polymerizable compound is a radical polymerizable monomer. The colored curable composition according to claim 1, wherein the photopolymerization initiator is an oxime compound. The colored curable composition according to any one of claims 1 to 6, further comprising a solvent. The colored curable composition according to claim 7, wherein the solvent is an organic solvent. The colored curable composition according to any one of claims 2 to 8, wherein the binder is an alkali-soluble binder. A color filter comprising at least one azomethine dye represented by the following general formula (I) and at least one tetraazaporphyrin dye represented by the following general formula (A).


[In General Formula (I), R ¹¹ represents a hydrogen atom or a substituent, R ¹² , R ¹³ , R ¹⁴ , and R ¹⁵ each independently represent a hydrogen atom or a substituent, and R ¹⁶ and R ¹⁷ 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 ¹⁸ ) ═, and R ¹⁸ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group. R ¹² and R ¹³ , R ¹³ and R ¹⁶ , R ¹⁴ and R ¹⁵ , R ¹⁵ and R ¹⁷ , and R ¹⁶ and R ¹⁷ are bonded to each other to form a 5-membered, 6-membered, or 7-membered ring. May be. ]


[In General Formula (A), Ring A ¹ , Ring A ² , Ring A ³ , and Ring A ⁴ are each independently


And at least one of ring A ¹ , ring A ² , ring A ³ , and ring A ⁴ is

Represents. R ¹ and R ² each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group, m represents an integer of 1 to 8, and n represents an integer of 1 to 4. However, R ¹ and R ² do not represent a hydrogen atom at the same time. ] A color filter comprising a step of applying a colored curable composition according to any one of claims 1 to 9 on a support, exposing through a mask, and developing to form a pattern. Manufacturing method.