JP2011039319A - Colored curable composition, color filter and method for producing the same, and solid-state imaging device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a colored curable composition in which decolorization liable to occur when a dye is used as a colorant is prevented from occurring. <P>SOLUTION: The colored curable composition comprises: at least (A-1) a complex in which a compound represented by general formula (I) coordinates with a metal atom or a metal compound; (A-2) a phthalocyanine pigment; (B) a dispersant; (C) a crosslinking agent which initiates crosslinking by the action of an acid; (D) a photoacid generator; and (E) an organic solvent, wherein R<SP>1</SP>to R<SP>6</SP>are a hydrogen atom or a substituent, and R<SP>7</SP>is a hydrogen atom, a halogen atom, alkyl, aryl or a heterocyclic group. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a colored curable composition, a color filter using the same, a method for producing the same, and a solid-state imaging device including the color filter.

  As a method for producing a color filter used for a liquid crystal display element (LCD or the like) or a solid-state image pickup element (CCD or CMOS), a pigment dispersion method is widely known.

The pigment dispersion method is a method for producing a color filter by a photolithography method using a colored photosensitive composition in which a pigment is dispersed in various photosensitive compositions. This is a method suitable for producing a color filter with high positional accuracy, a large screen, and high definition because patterning is performed by a photolithography method. When a color filter is produced by a pigment dispersion method, a photosensitive composition is applied on a glass substrate by a spin coater or a roll coater to form a coating film, and a colored pixel is formed by pattern exposure and development of the coating film. The color filter is obtained by repeating this operation for each color.
As a colored photosensitive composition using a pigment, for example, a blue colored composition for a color filter containing a phthalocyanine pigment is known (for example, see Patent Document 1).

  In the case of manufacturing a display element such as a liquid crystal display element or a solid-state imaging element by providing a color filter using a pigment, a pigment having a finer particle size is required from the viewpoint of improving the contrast. This is due to a factor that the polarization axis rotates due to light scattering, birefringence, and the like by the pigment. If the pigment is not sufficiently refined, light is scattered and absorbed by the pigment, the light transmittance is lowered, the contrast is lowered, and further, the curing sensitivity at the time of pattern exposure is lowered.

  In particular, in color filters for solid-state image sensors, in recent years, further higher definition has been desired. Therefore, it is difficult to further improve the resolution with a conventional pigment dispersion system. That is, there is a problem that color unevenness occurs due to the influence of coarse pigment particles. Therefore, the pigment dispersion system is not suitable for applications requiring a fine pattern with a pixel size of 1.5 to 3.0 μm square, such as a solid-state imaging device.

  In response to this situation, a technique that uses a dye instead of a pigment has been proposed. Since the dye is dissolved in a solvent and dispersed in molecular units, problems such as color unevenness due to the influence of coarse particles can be avoided as compared with the conventional pigment dispersion method.

  On the other hand, since the dye is soluble in the organic solvent, when the organic solvent is dropped on the fine pattern formed by exposure and development, the dye contained in the fine pattern may be dissolved in the organic solvent. In the manufacturing process of the color filter, after forming the fine pattern of the first color, the colored photosensitive composition of the next color is directly applied thereon, and at this time, the dye contained in the fine pattern of the first color is applied. In some cases, a phenomenon occurs in which the colored photosensitive composition of the next color is dissolved in a coating solvent (hereinafter, this phenomenon is referred to as “color loss”).

JP 2001-33616 A

  As described above, by using a coloring composition containing a dye, problems such as color unevenness due to coarse particles of the pigment can be avoided, but the coloring composition of the next color is superimposed on an existing pattern. When applied, it tends to cause color loss to the solvent.

  The present invention has been made in view of the above, and a colored curable composition in which occurrence of color loss that is likely to occur when a dye is used as a colorant is prevented. It is an object of the present invention to provide a solid-state imaging device capable of performing an image display excellent in color reproducibility, a manufacturing method thereof, and color reproducibility, and to achieve the object.

Specific means for achieving the above object are as follows. That is, the present invention
<1> (A-1) Complex in which compound represented by general formula (I) below is coordinated to metal atom or metal compound, (A-2) phthalocyanine pigment, (B) dispersant, (C) acid A colored curable composition comprising at least a crosslinking agent that crosslinks by the action of (D), a photoacid generator, and (E) an organic solvent.

In the general formula (I), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ each independently represents a hydrogen atom or a substituent. R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group.

  <2> The above-mentioned <1>, wherein the compound (A-1) in which the compound represented by the general formula (I) is coordinated to a metal atom or a metal compound is a compound represented by the following general formula (II-1) > The colored curable composition described in the above.

In the general formula (II-1), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ each independently represent a hydrogen atom or a substituent. R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. Ma represents a metal atom or a metal compound. X ² represents a group necessary for neutralizing the electric charge of Ma, and X ¹ represents a group capable of binding to Ma. X ¹ and X ² may be bonded to each other to form a 5-membered, 6-membered, or 7-membered ring.

  <3> The above-mentioned <1>, wherein a complex in which the compound represented by the general formula (I-1) is coordinated to a metal atom or a metal compound is a compound represented by the following general formula (II-2) > The colored curable composition described in the above.

In the general formula (II-2), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ , and R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , and R ¹³ are: Each independently represents a hydrogen atom or a substituent. R ⁷ and R ¹⁴ each independently represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. Ma represents a metal atom or a metal compound.

  <4> The compound (A-1) in which the compound represented by the general formula (I) is coordinated to a metal atom or a metal compound is the compound represented by the following general formula (III). It is the colored curable composition of description.

In the general formula (III), R ² , R ³ , R ⁴ , and R ⁵ each independently represent a hydrogen atom or a substituent. R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. Ma represents a metal atom or a metal compound, and X ³ represents NR (R represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group. ), A nitrogen atom, an oxygen atom, or a sulfur atom, and X ⁴ represents NRa (Ra represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group. Represents an oxygen atom or a sulfur atom. Y ¹ represents NRc (Rc represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group) or a group containing a carbon atom; ² represents a nitrogen atom or a group containing a carbon atom. R ⁸ and R ⁹ each independently represents an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylamino group, an arylamino group, or a heterocyclic amino group. R ⁸ and Y ¹ may be bonded to each other to form a 5-, 6-, or 7-membered ring, and R ⁹ and Y ² are bonded to each other to form a 5-, 6-, or 7-membered ring. The ring may be formed. X ⁵ represents a group capable of binding to Ma, and a represents 0, 1, or 2.

<5> The colored curable property according to any one of <1> to <4>, wherein the metal atom or the metal compound is any one of Fe, Zn, Co, V = O, and Cu. It is a composition.
<6> The colored curable composition according to any one of <1> to <5>, wherein R ³ and R ⁴ are each a phenyl group.
<7> according to at least one of said ^{R 2} and said ^{R 5} is any one of <1> to the <6> is 2,6-di -tert- butyl-4-methyl cyclohexyloxy carbonyl group The colored curable composition.
<8> A layer forming step of forming a colored curable composition layer by applying the colored curable composition according to any one of <1> to <7> above on a support, and a mask. And a pattern forming step of developing the colored curable composition layer and then developing to form a colored pattern.
The <9> said pattern formation process is a manufacturing method of the color filter as described in said <8> including the process of heating the said colored curable composition layer before image development after exposure.
<10> A color filter manufactured by the method for manufacturing a color filter according to <8> or <9>.
<11> A solid-state imaging device including the color filter according to <10>.

ADVANTAGE OF THE INVENTION According to this invention, the colored curable composition by which generation | occurrence | production of the color loss which is easy to occur when a dye was used as a coloring agent was prevented can be provided. Also,
ADVANTAGE OF THE INVENTION According to this invention, generation | occurrence | production of color loss can be suppressed and the color filter which has a desired hue, and its manufacturing method can be provided. further,
ADVANTAGE OF THE INVENTION According to this invention, the solid-state image sensor which can perform the image display excellent in color reproducibility can be provided.

≪Colored curable composition≫
First, the colored curable composition of the present invention will be described.
The colored curable composition of the present invention comprises (A-1) a complex in which the compound represented by formula (I) is coordinated to a metal atom or a metal compound, (A-2) a phthalocyanine pigment, and (B) dispersion. It includes at least an agent, (C) a crosslinking agent that crosslinks by the action of an acid, (D) a photoacid generator, and (E) an organic solvent, and may be configured using other components as necessary.

  Hereinafter, components (A-1), (A-2), (B), (C), (D), and (E) will be described.

[(A-1) Complex in which compound represented by formula (I) is coordinated to metal atom or metal compound]
The colored curable composition of the present invention includes, as one colorant, a complex in which a compound represented by the following general formula (I) is coordinated to a metal atom or a metal compound (hereinafter referred to as “specific complex” or “ This is referred to as “specific complex” in the invention.

-Dipyrromethene compounds-
First, the dipyrromethene compound represented by the general formula (I) constituting the specific complex will be described.

In said general formula (I), R < ¹ > -R < ⁶ > represents a hydrogen atom or a substituent each independently. R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group.

In the general formula (I), the substituents represented by R ^{1 to} R ⁶ are the following monovalent groups (hereinafter, the listed groups of monovalent groups may be collectively referred to as “substituent R”). .).
That is, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom), an alkyl group (preferably a linear, branched or cyclic alkyl group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms). For example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, dodecyl group, hexadecyl group, cyclopropyl group, A cyclopentyl group, a cyclohexyl group, a 1-norbornyl group, a 1-adamantyl group), an alkenyl group (preferably an alkenyl group having 2 to 48 carbon atoms, more preferably 2 to 18 carbon atoms, such as a vinyl group, an allyl group, 3 -Buten-1-yl group), an aryl group (preferably an aryl group having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms, For example, a phenyl group, a naphthyl group), a heterocyclic group (preferably a C1-C32, more preferably a C1-C18 heterocyclic group such as a 2-thienyl group, 4-pyridyl group, 2-furyl group). Group, 2-pyrimidinyl group, 1-pyridyl group, 2-benzothiazolyl group, 1-imidazolyl group, 1-pyrazolyl group, benzotriazol-1-yl group), silyl group (preferably having 3 to 38 carbon atoms, more preferably A silyl group having 3 to 18 carbon atoms such as trimethylsilyl group, triethylsilyl group, tributylsilyl group, t-butyldimethylsilyl group, t-hexyldimethylsilyl group), hydroxyl group, cyano group, nitro group, alkoxy group ( Preferably it is a C1-C48, More preferably, it is a C1-C24 alkoxy group, for example, a methoxy group, an ethoxy group, 1- Toxyl group, 2-butoxy group, isopropoxy group, t-butoxy group, dodecyloxy group, cycloalkyloxy group (for example, cyclopentyloxy group, cyclohexyloxy group)), aryloxy group (preferably having 6 to 48 carbon atoms, More preferably, it is an aryloxy group having 6 to 24 carbon atoms, for example, a phenoxy group or 1-naphthoxy group), a heterocyclic oxy group (preferably having 1 to 32 carbon atoms, and more preferably having 1 to 18 carbon atoms). Group, for example, 1-phenyltetrazol-5-oxy group, 2-tetrahydropyranyloxy group), silyloxy group (preferably a silyloxy group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, Trimethylsilyloxy group, t-butyldimethylsilyloxy group, diphenylmethylsilyloxy group) An acyloxy group (preferably an acyloxy group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, for example, an acetoxy group, a pivaloyloxy group, a benzoyloxy group, a dodecanoyloxy group), an alkoxycarbonyloxy group (preferably An alkoxycarbonyloxy group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, such as ethoxycarbonyloxy group, t-butoxycarbonyloxy group, cycloalkyloxycarbonyloxy group (for example, cyclohexyloxycarbonyloxy group)) An aryloxycarbonyloxy group (preferably an aryloxycarbonyloxy group having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms, such as a phenoxycarbonyloxy group), a carbamoyloxy group (preferably having 1 to 48 carbon atoms). More preferably, it is a carbamoyloxy group having 1 to 24 carbon atoms, for example, N, N-dimethylcarbamoyloxy group, N-butylcarbamoyloxy group, N-phenylcarbamoyloxy group, N-ethyl-N-phenylcarbamoyloxy group) A sulfamoyloxy group (preferably a sulfamoyloxy group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, such as N, N-diethylsulfamoyloxy group, N-propylsulfamoyl group). Oxy group), alkylsulfonyloxy group (preferably alkylsulfonyloxy group having 1 to 38 carbon atoms, more preferably 1 to 24 carbon atoms, such as methylsulfonyloxy group, hexadecylsulfonyloxy group, cyclohexylsulfonyloxy group). ,

An arylsulfonyloxy group (preferably an arylsulfonyloxy group having 6 to 32 carbon atoms, more preferably an arylsulfonyloxy group having 6 to 24 carbon atoms, such as a phenylsulfonyloxy group), an acyl group (preferably having 1 to 48 carbon atoms, more preferably C1-C24 acyl group, for example, formyl group, acetyl group, pivaloyl group, benzoyl group, tetradecanoyl group, cyclohexanoyl group), alkoxycarbonyl group (preferably C2-C48, more preferably An alkoxycarbonyl group having 2 to 24 carbon atoms, for example, a methoxycarbonyl group, an ethoxycarbonyl group, an octadecyloxycarbonyl group, a cyclohexyloxycarbonyl group, a 2,6-di-tert-butyl-4-methylcyclohexyloxycarbonyl group), Aryloxycarbonyl group (preferred Or an aryloxycarbonyl group having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms, such as a phenoxycarbonyl group, and a carbamoyl group (preferably having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms). Carbamoyl group such as carbamoyl group, N, N-diethylcarbamoyl group, N-ethyl-N-octylcarbamoyl group, N, N-dibutylcarbamoyl group, N-propylcarbamoyl group, N-phenylcarbamoyl group, N-methyl N-phenylcarbamoyl group, N, N-dicyclohexylcarbamoyl group), amino group (preferably an amino group having 32 or less carbon atoms, more preferably 24 or less carbon atoms, such as an amino group, a methylamino group, N, N-dibutylamino group, tetradecylamino group, 2-ethylhexylamino group, cyclohexyl A silamino group), an anilino group (preferably an anilino group having 6 to 32 carbon atoms, more preferably 6 to 24 carbon atoms, such as an anilino group and an N-methylanilino group), a heterocyclic amino group (preferably having 1 to 32 carbon atoms, More preferably, it is a heterocyclic amino group having 1-18, for example, 4-pyridylamino group), a carbonamido group (preferably a carbonamide group having 2 to 48 carbon atoms, more preferably 2-24, for example, an acetamide group, Benzamide group, tetradecanamide group, pivaloylamide group, cyclohexaneamide group), ureido group (preferably ureido group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, for example, ureido group, N, N-dimethylureido Group, N-phenylureido group), imide group (preferably having 36 or less carbon atoms, more preferably 2 carbon atoms). 4 or less imide groups, for example, N-succinimide group, N-phthalimide group), alkoxycarbonylamino group (preferably C2-48, more preferably C2-C24 alkoxycarbonylamino group, for example, Methoxycarbonylamino group, ethoxycarbonylamino group, t-butoxycarbonylamino group, octadecyloxycarbonylamino group, cyclohexyloxycarbonylamino group), aryloxycarbonylamino group (preferably having 7 to 32 carbon atoms, more preferably having 7 carbon atoms) An aryloxycarbonylamino group having ˜24, for example, a phenoxycarbonylamino group), a sulfonamide group (preferably a sulfonamide group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as a methanesulfonamide group). The Butans Honamide group, benzenesulfonamide group, hexadecanesulfonamide group, cyclohexanesulfonamide group), sulfamoylamino group (preferably sulfamoylamino group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, N, N-dipropylsulfamoylamino group, N-ethyl-N-dodecylsulfamoylamino group), azo group (preferably having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, For example, phenylazo group, 3-pyrazolylazo group),

An alkylthio group (preferably an alkylthio group having 1 to 48 carbon atoms, more preferably an alkylthio group having 1 to 24 carbon atoms, for example, methylthio group, ethylthio group, octylthio group, cyclohexylthio group), arylthio group (preferably having 6 to 48 carbon atoms). More preferably, it is an arylthio group having 6 to 24 carbon atoms, such as a phenylthio group, and a heterocyclic thio group (preferably having 1 to 32 carbon atoms, more preferably a heterocyclic thio group having 1 to 18 carbon atoms, 2-benzothiazolylthio group, 2-pyridylthio group, 1-phenyltetrazolylthio group), alkylsulfinyl group (preferably an alkylsulfinyl group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, Dodecanesulfinyl group), arylsulfinyl group (preferably having 6 to 32 carbon atoms, more preferably An arylsulfinyl group having 6 to 24 prime atoms, such as a phenylsulfinyl group, an alkylsulfonyl group (preferably an alkylsulfonyl group having 1 to 48 carbon atoms, more preferably an alkylsulfonyl group having 1 to 24 carbon atoms, such as a methylsulfonyl group, ethyl Sulfonyl group, propylsulfonyl group, butylsulfonyl group, isopropylsulfonyl group, 2-ethylhexylsulfonyl group, hexadecylsulfonyl group, octylsulfonyl group, cyclohexylsulfonyl group), arylsulfonyl group (preferably having 6 to 48 carbon atoms, more preferably An arylsulfonyl group having 6 to 24 carbon atoms, for example, a phenylsulfonyl group, 1-naphthylsulfonyl group), a sulfamoyl group (preferably a sulfamoyl group having 32 or less carbon atoms, more preferably 24 or less carbon atoms, Rufamoyl group, N, N-dipropylsulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, N-ethyl-N-phenylsulfamoyl group, N-cyclohexylsulfamoyl group), sulfo group, phosphonyl Groups (preferably phosphonyl groups having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, such as phenoxyphosphonyl group, octyloxyphosphonyl group, phenylphosphonyl group), phosphinoylamino groups (preferably A phosphinoylamino group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, such as a diethoxyphosphinoylamino group or a dioctyloxyphosphinoylamino group).

  When the above-described monovalent group is a further substitutable group, it may be further substituted with any of the above-described groups. In addition, when it has two or more substituents, those substituents may be the same or different.

In the general formula (I), R ¹ and R ² , R ² and R ³ , R ⁴ and R ⁵ , and R ⁵ and R ⁶ are each independently bonded to each other to form 5, 6 or 7 members. The ring may be formed. In addition, as a ring formed, there exists a saturated ring or an unsaturated ring. Examples of the 5-membered, 6-membered, or 7-membered saturated ring or unsaturated ring include a pyrrole ring, a furan ring, a thiophene ring, a pyrazole ring, an imidazole ring, a triazole ring, an oxazole ring, a thiazole ring, a pyrrolidine ring, Examples include a piperidine ring, a cyclopentene ring, a cyclohexene ring, a benzene ring, a pyridine ring, a pyrazine ring and a pyridazine ring, and preferably a benzene ring and a pyridine ring.
In addition, when the formed 5-membered, 6-membered, and 7-membered rings are further substitutable groups, they may be substituted with any of the substituents R, and two or more substituents In the case where the substituent is substituted, the substituents may be the same or different.

-Metal atom or metal compound-
Next, the metal atom or metal compound which comprises a specific complex is demonstrated.
The metal or metal compound used here may be any metal atom or metal compound capable of forming a complex, and may be any divalent metal atom, divalent metal oxide, divalent metal hydroxide. Or a divalent metal chloride. For example, Zn, Mg, Si, Sn , Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, in addition to Fe, such _{as, AlCl, InCl, FeCl, TiCl} 2, SnCl 2, SiCl 2, GeCl Also included are metal chlorides such as ₂ , metal oxides such as TiO and VO, and metal hydroxides such as Si (OH) ₂ .
Among these, Fe, Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO, or from the viewpoint of the stability, spectral characteristics, heat resistance, light resistance, and production suitability of the complex VO is preferred, Fe, Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, or VO is more preferred, and Fe, Zn, Cu, Co, or VO (V = O) is most preferred.

Preferred embodiments as a complex in which the compound represented by the general formula (I) is coordinated to a metal atom or a metal compound are shown below. A preferable number of carbon atoms in each group is in the range of number of carbon atoms described in the substituent R represented by R ¹ to R ^6.
That is, in general formula (I), R ¹ and R ⁶ are each independently a hydrogen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, silyl group, hydroxyl group, cyano group, alkoxy group, aryloxy Group, heterocyclic oxy group, acyl group, alkoxycarbonyl group, carbamoyl group, amino group, anilino group, heterocyclic amino group, carbonamido group, ureido group, imide group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfone An amide group, an azo group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, or a phosphinoylamino group, wherein R ² and R ⁵ are each independently a hydrogen atom, a halogen atom, Atoms, alkyl groups, alkenyl groups, aryl groups, heterocyclic groups, hydroxyl groups, Ano group, nitro group, alkoxy group, aryloxy group, heterocyclic oxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, imide group, alkoxycarbonylamino group, sulfonamide group, azo group, alkylthio group , An arylthio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, or a sulfamoyl group, wherein R ³ and R ⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, Heterocyclic group, silyl group, hydroxyl group, cyano group, alkoxy group, aryloxy group, heterocyclic oxy group, acyl group, alkoxycarbonyl group, carbamoyl group, anilino group, carbonamido group, ureido group, imide group, alkoxycarbonyl Amino group, sulfone De group, an azo group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, or a phosphinoylamino group, R ⁷ is a hydrogen atom, a halogen atom, an alkyl group, Examples include an aryl group or a heterocyclic group, wherein the metal atom or metal compound is Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO, or VO.

A more preferable embodiment as a complex in which the compound represented by the general formula (I) is coordinated to a metal atom or a metal compound is shown below. A preferable number of carbon atoms in each group is in the range of number of carbon atoms described in the substituent R represented by R ¹ to R ^6.
That is, in general formula (I), R ¹ and R ⁶ are each independently a hydrogen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, cyano group, acyl group, alkoxycarbonyl group, carbamoyl group, amino group. Group, heterocyclic amino group, carbonamido group, ureido group, imide group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamido group, azo group, alkylsulfonyl group, arylsulfonyl group, or phosphinoylamino group R ² and R ⁵ are each independently an alkyl group, alkenyl group, aryl group, heterocyclic group, cyano group, nitro group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, imide group An alkylsulfonyl group, an arylsulfonyl group, or a sulfamoyl group. R ³ and R ⁴ are each independently a hydrogen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, cyano group, acyl group, alkoxycarbonyl group, carbamoyl group, carbonamido group, ureido group, imide Group, alkoxycarbonylamino group, sulfonamido group, alkylthio group, arylthio group, heterocyclic thio group, alkylsulfonyl group, arylsulfonyl group, or sulfamoyl group, wherein R ⁷ is a hydrogen atom, a halogen atom, an alkyl group, an aryl group And an embodiment in which the metal atom or metal compound is Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, or VO.

Furthermore, the especially preferable aspect as a complex which the compound represented with general formula (I) coordinated to the metal atom or the metal compound is shown below. That is,
In general formula (I), R ¹ and R ⁶ are each independently a hydrogen atom, an alkyl group (preferably having 1 to 24 carbon atoms), an aryl group (preferably having 6 to 24 carbon atoms), a heterocyclic group (preferably Is a C1-C18), amino group (preferably C24 or less), heterocyclic amino group (preferably C1-C18), carbonamido group (preferably C2-C24), ureido group (preferably Has 1 to 24 carbon atoms, an imide group (preferably 24 or less carbon atoms), an alkoxycarbonylamino group (preferably 2 to 24 carbon atoms), a sulfonamide group (preferably 1 to 24 carbon atoms), an azo group (preferably Is a C1-24), alkylsulfonyl group (preferably C1-24), arylsulfonyl group (preferably C6-24), or phosphinoylamino group (preferably carbon). A 1-24), ^{R 2} and ^{R 5} each independently represents an alkyl group (preferably having 1 to 24 carbon atoms), an aryl group (preferably having 6 to 24 carbon atoms), a Hajime Tamaki (preferably a carbon 1-18), cyano group, acyl group (preferably 1-24 carbon atoms), alkoxycarbonyl group (preferably 2-24 carbon atoms), carbamoyl group (preferably 1-24 carbon atoms), alkylsulfonyl group ( Preferably it is C1-C24) or an arylsulfonyl group (preferably C6-C24), Comprising: R < ³ > and R < ⁴ > are respectively independently a hydrogen atom and an alkyl group (preferably C1-C24). ), An aryl group (preferably having 6 to 24 carbon atoms), or a heterocyclic group (preferably having 1 to 18 carbon atoms), wherein R ⁷ is a hydrogen atom, an alkyl group (preferably having 1 to 24 carbon atoms), aryl Group ( Mashiku is a number of 6 to 24), or a Hajime Tamaki having a carbon (preferably having 1 to 18 carbon atoms), a metal atom or a metal compound is Zn, Cu, Co, or aspects include a VO.

In particular, in general formula (I), it is preferable that R ³ and R ⁴ are each a phenyl group from the viewpoint of excellent fastness. This is because (1) R ³ and R ⁴ are each a phenyl group, the spectrum of this compound becomes longer, and the spectrum with the phthalocyanine pigment to be used together with the spectrum (near 550 nm) increases. It is thought that (2) the fastness of the compound itself increases due to the presence of a sterically bulky substituent because it becomes easier to move.
In general formula (I), R ² and / or R ⁵ are preferably 2,6-di-tert-butyl-4-methylcyclohexyloxycarbonyl groups from the viewpoint of excellent solvent solubility.

-Compound represented by general formula (II-1)-
As a specific complex in this invention, it is one of the preferable examples that it is a compound represented by the following general formula (II-1).

In the general formula (II-1), R ^{1 to} R ⁶ each independently represents a hydrogen atom or a substituent. R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. Ma represents a metal atom or a metal compound, X ² represents a group necessary for neutralizing the charge of Ma, and X ¹ represents a group capable of binding to Ma. X ¹ and X ² may be bonded to each other to form a 5-membered, 6-membered, or 7-membered ring.

R < ¹ > -R < ⁶ > in General formula (II-1) is synonymous with R < ¹ > -R < ⁶ > in General formula (I), and its preferable aspect is also the same.
Ma in the general formula (II-1) represents a metal atom or a metal compound, and is synonymous with the metal atom or metal compound constituting the specific complex described above, and the preferred range thereof is also the same.
^{R 7} in the general formula (II-1) has the same meaning as ^{R 7} in formula (I), preferable embodiments thereof are also the same.

X ¹ in the general formula (II-1) may be any group as long as it is a group capable of binding to Ma, such as water, alcohols (for example, methanol, ethanol, propanol), and further “metal chelate” [1 ] Groups derived from the compounds described in Takeichi Sakaguchi and Keihei Ueno (1995 Nanedou), [2] (1996), [3] (1997), and the like.

X ^{2 in the} general formula (II-1) represents a group necessary for neutralizing the charge of Ma, and examples thereof include a halogen atom, a hydroxyl group, a carboxylic acid group, a phosphoric acid group, and a sulfonic acid group.

X ¹ and X ² in formula (II-1) may be bonded to each other to form a 5-membered, 6-membered, or 7-membered ring together with Ma. The 5-membered, 6-membered and 7-membered rings formed may be saturated or unsaturated. The 5-membered, 6-membered, and 7-membered rings are heterocycles having at least one atom selected from a nitrogen atom, an oxygen atom, and a sulfur atom, which may be composed of only carbon atoms and hydrogen atoms. There may be.

-Compound represented by general formula (II-2)-
As a specific complex in this invention, it is one of the preferable examples that it is a compound represented by the following general formula (II-2).

In the general formula (II-2), R ^{1 to} R ⁶ and R ^{8 to} R ¹³ each independently represent a hydrogen atom or a substituent. R ⁷ and R ¹⁴ each independently represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. Ma represents a metal atom or a metal compound.

R < ¹ > -R < ⁶ > in General formula (II-2) is synonymous with R < ¹ > -R < ⁶ > in General formula (I), and its preferable aspect is also the same.
The substituent represented by R ^{8 to} R ¹³ in the general formula (II-2) has the same meaning as the substituent represented by R ^{1 to} R ⁶ of the compound represented by the general formula (I). The preferred embodiment is also the same. When the substituent represented by R ^{8 to} R ¹³ of the compound represented by the general formula (II-2) is a further substitutable group, it may be substituted with any of the substituents R described above. In the case of being substituted with two or more substituents, those substituents may be the same or different.

^{R 7} in the formula (II-2) has the same meaning as ^{R 7} in formula (I), preferable embodiments thereof are also the same.
R ¹⁴ in the general formula (II-2) represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group, and a preferable range of R ^{14 is} the same as the preferable range of R ⁷ . When R ¹⁴ is a further substitutable group, it may be substituted with any of the aforementioned substituents R, and when it is substituted with two or more substituents, those substituents are They may be the same or different.

  Ma in the general formula (II-2) represents a metal or a metal compound, and is synonymous with the metal atom or metal compound constituting the specific complex described above, and its preferred range is also the same.

R ⁸ and R ⁹ , R ⁹ and R ¹⁰ , R ¹¹ and R ¹² , R ¹² and R ^{13 in the} general formula (II-2) are bonded to each other to form a 5-membered, 6-membered, or 7-membered saturated ring. Or may form an unsaturated ring. The saturated ring or unsaturated ring formed is synonymous with the saturated or unsaturated ring formed by R ¹ and R ² , R ² and R ³ , R ⁴ and R ⁵ , and R ⁵ and R ^6. The preferred examples are also the same.

-Compound represented by the general formula (III)-
As a specific complex in this invention, it is one of the preferable examples that it is a compound represented by the following general formula (III).

In the general formula (III), R ^{2 to} R ⁵ each independently represents a hydrogen atom or a substituent. R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. Ma represents a metal atom or a metal compound, and X ³ represents NR (R represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group. ), A nitrogen atom, an oxygen atom, or a sulfur atom, and X ⁴ represents NRa (Ra represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group. represents.), an oxygen atom or a sulfur atom, Y ¹ is, NRc (Rc represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group .), or a group containing a carbon atom, Y ² is a nitrogen atom, or a group containing a carbon atom, R ⁸ and R ⁹ each independently represent an alkyl group An alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylamino group, an arylamino group, or a heterocyclic amino group. R ⁸ and Y ¹ may be bonded to each other to form a 5-membered, 6-membered, or 7-membered ring, and R ⁹ and Y ² are bonded to each other to form a 5-membered, 6-membered, or 7-membered ring. A ring may be formed. X ⁵ represents a group capable of binding to Ma, and a represents 0, 1, or 2.

R < ² > -R < ⁵ > and R < ⁷ > in General formula (III) are synonymous with R < ² > -R < ⁵ > and R < ⁷ > in General formula (I), A preferable aspect is also the same.
Ma in the general formula (III) represents a metal or a metal compound, and is synonymous with the metal atom or metal compound constituting the specific complex described above, and its preferred range is also the same.

In the general formula (III), R ⁸ and R ⁹ are each independently an alkyl group (preferably a linear, branched or cyclic alkyl group having 1 to 36 carbon atoms, more preferably 1 to 12 carbon atoms. , Methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, hexyl group, 2-ethylhexyl group, dodecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, 1-adamantyl group) An alkenyl group (preferably an alkenyl group having 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, such as a vinyl group, an allyl group or a 3-buten-1-yl group), an aryl group (preferably having a carbon number of 6 to 36, more preferably an aryl group having 6 to 18 atoms, such as a phenyl group or a naphthyl group, or a heterocyclic group (preferably having 1 to 24 carbon atoms, more preferably 1 to 1 carbon atoms). 2 heterocyclic groups such as 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyridyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, Triazol-1-yl group), an alkoxy group (preferably an alkoxy group having 1 to 36 carbon atoms, more preferably 1 to 18 carbon atoms such as methoxy group, ethoxy group, propyloxy group, butoxy group, hexyloxy group, 2 -Ethylhexyloxy group, dodecyloxy group, cyclohexyloxy group), aryloxy group (preferably an aryloxy group having 6 to 24 carbon atoms, more preferably 1 to 18 carbon atoms, such as phenoxy group or naphthyloxy group), alkylamino A group (preferably an alkylamino group having 1 to 36 carbon atoms, more preferably 1 to 18 carbon atoms such as Ruamino group, ethylamino group, propylamino group, butylamino group, hexylamino group, 2-ethylhexylamino group, isopropylamino group, t-butylamino group, t-octylamino group, cyclohexylamino group, N, N-diethylamino Group, N, N-dipropylamino group, N, N-dibutylamino group, N-methyl-N-ethylamino group), arylamino group (preferably C6-C36, more preferably 6-18 aryl) Amino group, for example, phenylamino group, naphthylamino group, N, N-diphenylamino group, N-ethyl-N-phenylamino group), or heterocyclic amino group (preferably having 1 to 24 carbon atoms, more preferably 1-12 heterocyclic amino groups such as 2-aminopyrrole group, 3-aminopyrazole group, 2-aminopyridine Down group, a 3-aminopyridine group).

In general formula (III), an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylamino group, an arylamino group, or a heterocyclic amino group represented by R ⁸ and R ⁹ Further, when it is a substitutable group, it may be substituted with any of the above substituents R, and when it is substituted with two or more substituents, those substituents are the same. May be different.

In general formula (III), X ³ represents NR, a nitrogen atom, an oxygen atom, or a sulfur atom, X ⁴ represents NRa, an oxygen atom, or a sulfur atom, and R and Ra are each independently a hydrogen atom. An alkyl group (preferably a linear, branched or cyclic alkyl group having 1 to 36 carbon atoms, more preferably 1 to 12 carbon atoms, such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl Group, t-butyl group, hexyl group, 2-ethylhexyl group, dodecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, 1-adamantyl group), alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 2 carbon atoms). 12 alkenyl groups, for example, vinyl group, allyl group, 3-buten-1-yl group), aryl group (preferably having 6 to 36 carbon atoms, more preferably 6 to 1). An aryl group of, for example, a phenyl group, a naphthyl group), a heterocyclic group (preferably a heterocyclic group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, such as a 2-thienyl group, a 4-pyridyl group, 2-furyl group, 2-pyrimidinyl group, 1-pyridyl group, 2-benzothiazolyl group, 1-imidazolyl group, 1-pyrazolyl group, benzotriazol-1-yl group), acyl group (preferably having 1 to 24 carbon atoms, More preferably, it is an acyl group having 2 to 18, for example, acetyl group, pivaloyl group, 2-ethylhexyl group, benzoyl group, cyclohexanoyl group), alkylsulfonyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 2 carbon atoms). 18 alkylsulfonyl groups such as methylsulfonyl group, ethylsulfonyl group, isopropylsulfonyl group, cyclohexylsulfur A sulfonyl group), an arylsulfonyl group (preferably an arylsulfonyl group having 6 to 24 carbon atoms, more preferably 6 to 18 carbon atoms, such as a phenylsulfonyl group or a naphthylsulfonyl group).
The alkyl group, alkenyl group, aryl group, heterocyclic group, acyl group, alkylsulfonyl group, and arylsulfonyl group of R and Ra may be further substituted with any of the substituents R, and a plurality of substituents When substituted with a group, the substituents may be the same or different.

In General Formula (III), Y ¹ represents NRc or a group containing a carbon atom, Y ² represents a nitrogen atom or a group containing a carbon atom, and Rc has the same meaning as R in X ³ . . The “group containing carbon atom” represented by Y ¹ and Y ² is preferably an alkylene group having 1 to 8 carbon atoms, more preferably an alkylene group having 1 to 2 carbon atoms. Specific examples include a methylene group, an ethylene group, a propylene group, a butylene group, and an isobutylene group, and a methylene group or an ethylene group is preferable.

In the general formula (III), R ⁸ and Y ¹ are bonded to each other, and together with R ⁸ , Y ¹ and the carbon atom, a 5-membered ring (for example, cyclopentane, pyrrolidine, tetrahydrofuran, dioxolane, tetrahydrothiophene, pyrrole, furan) Thiophene, indole, benzofuran, benzothiophene), 6-membered ring (eg, cyclohexane, piperidine, piperazine, morpholine, tetrahydropyran, dioxane, pentamethylene sulfide, dithiane, benzene, piperidine, piperazine, pyridazine, quinoline, quinazoline), or A 7-membered ring (eg, cycloheptane, hexamethyleneimine) may be formed.

In general formula (III), R ⁹ and Y ² may be bonded to each other to form a 5-membered, 6-membered, or 7-membered ring together with R ⁹ , Y ² , and the carbon atom. 5-membered to be formed, 6-membered, and 7-membered ring, the ring one bond in the ring formed by the above R ⁹ and Y ² and carbon atoms is changed to the double bond.

In the general formula (III), when the 5-membered, 6-membered, and 7-membered rings formed by combining R ⁸ and Y ¹ and R ⁹ and Y ² are further substitutable rings, When substituted with two or more substituents, the substituents may be the same or different from each other.

In General Formula (III), X ⁵ represents a group capable of binding to Ma, and examples thereof include the same groups as X ¹ in General Formula (II-1).
a represents 0, 1, or 2.

Preferred embodiments of the compound represented by the general formula (III) are shown below. That is,
R ^{2 to} R ⁵ , R ⁷ , and Ma are the above-described preferred embodiments (embodiments a to d) of the complex in which the compound represented by the general formula (I) is coordinated to the metal atom or the metal compound. X ³ is NR (R is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms) or an oxygen atom, X ⁴ is NRa (Ra is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, carbon A heterocyclic group having a number of 3 to 6) or an oxygen atom, Y ¹ is NRc (Rc is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms) or a group containing a carbon atom, and Y ² is a nitrogen atom Or a group containing a carbon atom, X ⁵ is a group bonded through an oxygen atom (for example, anion of carboxylic acid or sulfonic acid), and R ⁸ and R ⁹ are each independently a group having 1 to 18 carbon atoms. Alkyl groups, aryl groups having 6 to 10 carbon atoms, and those having 3 to 10 carbon atoms A heterocyclic group, an alkoxy group having 1 to 18 carbon atoms, or an alkyl amino group having 1 to 18 carbon atoms, bonded with ^{R 8} and ^{Y 1} are together represent a 5- or 6-membered ring, and ^{R 9} Y ² is bonded to each other to represent a 5-membered or 6-membered ring, and a is an embodiment represented by 0 or 1.

The more preferable aspect of the compound represented by general formula (III) is shown below. That is,
R ^{2 to} R ⁵ , R ⁷ and Ma are the above-described preferred embodiments (embodiments a to d) of the complex in which the compound represented by the general formula (I) is coordinated to a metal atom or a metal compound, and X ³ and X ⁴ are oxygen atoms, Y ¹ is NH, Y ² is a nitrogen atom, X ⁵ is a group bonded via an oxygen atom (for example, an anion of carboxylic acid or sulfonic acid), R ⁸ and R ⁹ are each independently an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 10 carbon atoms, a heterocyclic group having 3 to 10 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or carbon. Represents an alkylamino group of 1 to 18, or R ⁸ and Y ¹ are bonded to each other to represent a 5-membered or 6-membered ring (preferably a benzene ring or a pyridine ring), and R ⁹ and Y ² are bonded to each other. 5 or 6 membered ring (preferably benzene ring, pyridine ) Represents a, a is an aspect represented by 0 or 1.

  Hereinafter, although the specific example of the specific complex in this invention is shown, this invention is not limited to these.

The molar extinction coefficient of the specific complex in the present invention is preferably as high as possible from the viewpoint of film thickness. The maximum absorption wavelength λ _max is preferably 520 nm to 580 nm, and more preferably 530 nm to 570 nm, from the viewpoint of improving color purity. The maximum absorption wavelength and molar extinction coefficient are measured with a spectrophotometer UV-2400PC (manufactured by Shimadzu Corporation).
The melting point of the specific complex in the present invention is preferably not too high from the viewpoint of solubility, and is preferably 300 to 1000 ° C.

Specific complexes in the present invention are disclosed in U.S. Pat. Nos. 4,774,339, 5,433,896, JP-A Nos. 2001-240761, 2002-155502, JP-A-3614586, Aust. J. et al. Chem, 1965, 11, 1835-1845, J. Am. H. Boger et al, Heteroatom Chemistry, Vol. 1, No. 1 5,389 (1990) and the like.
Specifically, the method described in paragraphs [0131] to [0157] of JP-A-2008-292970 can be applied to the method for synthesizing the specific complex in the present invention.

  In the colored curable composition of the present invention, the specific complex may be used alone or in combination of two or more.

  The content of the specific complex in the colored curable composition of the present invention varies depending on the molecular weight and the molar extinction coefficient, but is preferably 10% by mass to 70% by mass with respect to the total solid component of the colored curable composition. 10 mass%-50 mass% are more preferable, and 15 mass%-30 mass% are the most preferable.

[(A-2) Phthalocyanine pigment]
The colored curable composition of the present invention contains at least one phthalocyanine pigment.
The phthalocyanine pigment is not particularly limited as long as it is a pigment having a phthalocyanine skeleton. The central metal contained in the phthalocyanine pigment is not particularly limited as long as it is a metal that can form a phthalocyanine skeleton. Among these, magnesium, titanium, iron, cobalt, nickel, copper, zinc, and aluminum are preferably used as the central metal.

  Specific examples of the phthalocyanine pigment include C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 2, C.I. I. Pigment blue 15: 3, C.I. I. Pigment Blue 15: 4, C.I. I. Pigment blue 15: 5, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 16, C.I. I. Pigment blue 17: 1, C.I. I. Pigment blue 75, C.I. I. Pigment blue 79, C.I. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment green 37, chloroaluminum phthalocyanine, hydroxyaluminum phthalocyanine, aluminum phthalocyanine oxide, and zinc phthalocyanine. Among these, from the viewpoint of light resistance and coloring power, C.I. I. Pigment blue 15, C.I. I. Pigment Blue 15: 6, Pigment Blue 15: 1, C.I. I. Pigment Blue 15: 3 is preferable. I. Pigment Blue 15: 6 is preferred.

  The content of the phthalocyanine pigment in the colored curable composition is preferably 10% by mass to 70% by mass, more preferably 20% by mass to 60% by mass, with respect to the total solid content component of the colored curable composition. 35 mass%-50 mass% is the most preferable.

  The content ratio of the specific complex to the phthalocyanine pigment in the present invention is preferably phthalocyanine pigment: specific complex = 100: 5 to 100: 100, more preferably 100: 15 to 100: 75, and 100: 25. 100: 50 is more preferable.

[(B) Dispersant]
The colored curable composition of the present invention contains at least one dispersant. As the dispersant, a known pigment dispersant or surfactant is used.
As the dispersant, many kinds of compounds are used. For example, a phthalocyanine derivative (commercial product: EFKA-745 (manufactured by Efka)), Solsperse 5000 (manufactured by Nippon Lubrizol); organosiloxane polymer KP341 (Shin-Etsu Chemical) Manufactured by Kogyo Kogyo), (meth) acrylic acid (co) polymer polyflow No. 75, no. 90, no. 95 (above, manufactured by Kyoeisha Yushi Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.), and the like; polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether Nonionic surfactants such as polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester; anionic surfactants such as W004, W005, W017 (manufactured by Yusho); EFKA -46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (manufactured by Morishita Sangyo Co., Ltd.), Disperse Aid 6 Polymer dispersants such as Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 (manufactured by San Nopco); Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000, etc. Various Solsperse dispersants (manufactured by Nippon Lubrizol); Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P- 123 (manufactured by Asahi Denka Co., Ltd.) and Isonet S-20 (manufactured by Sanyo Chemical Industries).

  (B) 1 mass%-80 mass% are preferable with respect to a pigment, and, as for content in the colored curable composition of a dispersing agent, 5 mass%-70 mass% are more preferable, and 10 mass%-60 mass%. Is most preferred.

[(C) Crosslinker that crosslinks by the action of acid]
The colored curable composition of the present invention contains at least one crosslinking agent that is crosslinked by the action of an acid (hereinafter referred to as “acid crosslinking agent”).

  The acid crosslinking agent is not particularly limited as long as it causes a crosslinking reaction by the action of an acid and can cure the film. For example, (a) an epoxy resin, (b) a methylol group, an alkoxymethyl group, and an acyloxy group. At least one substitution selected from a melamine compound, a guanamine compound, a glycoluril compound, a urea compound, (c) a methylol group, an alkoxymethyl group, and an acyloxymethyl group, which is substituted with at least one substituent selected from a methyl group Phenol compounds, naphthol compounds or hydroxyanthracene compounds substituted with groups.

  The epoxy resin (a) may be any epoxy resin as long as it has an epoxy group and has crosslinkability, for example, bisphenol A diglycidyl ether, ethylene glycol diglycidyl ether, butanediol diglycidyl ether. Divalent glycidyl group-containing low molecular weight compounds such as hexanediol diglycidyl ether, dihydroxybiphenyl diglycidyl ether, diglycidyl phthalate, N, N-diglycidyl aniline, trimethylolpropane triglycidyl ether, Trivalent glycidyl group-containing low molecular weight compounds represented by methylolphenol triglycidyl ether, TrisP-PA triglycidyl ether, etc., as well as pentaerythritol tetraglycidyl ether, tetramethylol vinyl Phenol A tetravalent glycidyl ether-containing tetravalent glycidyl group-containing low molecular compounds, polyvalent glycidyl group-containing low molecular compounds such as dipentaerythritol pentaglycidyl ether, 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 acid crosslinking agent (b) is 2 to 6 for melamine compounds, 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).

  The methylol group-containing compound according to (b) uses melamine / guanamine / glycoluril / urea as a raw material in the presence of a basic catalyst such as sodium hydroxide, potassium hydroxide, ammonia or tetraalkylammonium hydroxide. Obtained by condensation reaction with formaldehyde. The alkoxymethyl group-containing compound according to (b) can be obtained by heating the methylol group-containing compound according to (b) in the presence of an acid catalyst such as hydrochloric acid, sulfuric acid, nitric acid, methanesulfonic acid or the like in alcohol. The acyloxymethyl group-containing compound according to (b) can be obtained by mixing and stirring the methylol group-containing compound according to (b) with an acyl chloride in the presence of a basic catalyst.

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

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

  Examples of the glycoluril compound include tetramethylol glycoluril, tetramethoxymethylglycoluril, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylolglycoluril or a mixture thereof, and a methylol group of tetramethylolglycoluril. Examples thereof include compounds in which 1 to 3 are acyloxymethylated or a mixture thereof.

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

  The acid 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 collectively represented by (c). Such a compound (methylol group-containing compound, alkoxymethyl group-containing compound, or acyloxymethyl group-containing compound) is sometimes referred to.

The number of methylol groups, acyloxymethyl groups or alkoxymethyl groups contained in the crosslinking agent (c) is at least two per molecule, and from the viewpoint of acid crosslinkability and storage stability, phenol as a skeleton Compounds in which the 2nd and 4th positions of the compound are all substituted are preferred. Further, the naphthol compound and hydroxyanthracene compound as the skeleton are preferably compounds in which all of the ortho-position and para-position of the OH group are substituted. The 3-position or 5-position of the phenol compound may be unsubstituted or may have a substituent.
The naphthol compound may be unsubstituted or substituted except for the ortho position of the OH group.

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

Examples of the skeletal compound in the crosslinking agent (c) include phenol compounds, naphthols, hydroxyanthracene compounds, 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 (manufactured by Honshu Chemical Industry Co., Ltd.) ), Naphthol, dihydroxynaphthalene, 2,7-dihydroxyanthracene, etc. are used.
Specific examples of the crosslinking agent (c) include, as a phenol compound or a naphthol compound, for example, a compound obtained by methoxymethylating one or two methylol groups of trimethylolphenol, tri (methoxymethyl) phenol, trimethylolphenol, Methylol-3-cresol, tri (methoxymethyl) -3-cresol, a compound obtained by methoxymethylating one or two methylol groups of trimethylol-3-cresol, dimethylol such as 2,6-dimethylol-4-cresol Compounds obtained by methoxymethylating 1 to 3 methylol groups of cresol, tetramethylol bisphenol A, tetramethoxymethyl bisphenol A, tetramethylol bisphenol A, tetramethylol-4,4′-bishydroxybiphenyl, tetramethoxy A compound obtained by methoxymethylating 1-5 methylol groups of til-4,4′-bishydroxybiphenyl, hexamethylol of TrisP-PA, hexamethoxymethyl of TrisP-PA, hexamethylol of TrisP-PA, Bishydroxymethyl naphthalene diol, etc. are mentioned. Examples of the hydroxyanthracene compound include 1,6-dihydroxymethyl-2,7-dihydroxyanthracene. Examples of the acyloxymethyl group-containing compound include compounds obtained by partially or fully acyloxymethylating the methylol group of the methylol group-containing compound.

Among these compounds, preferred are trimethylolphenol, bishydroxymethyl-p-cresol, tetramethylolbisphenol A, trisP-PA (manufactured by Honshu Chemical Industry Co., Ltd.) or a methylol group thereof. 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.

  As the acid crosslinking agent used in the colored curable composition of the present invention, among the compounds according to the above (a) to (c), it is preferable to use the compound according to (a) or the compound according to (b). Further, it is more preferable to use the compound according to (b), and it is most preferable to use the melamine compound according to (b).

  The content of the (C) acid crosslinking agent in the total solid content of the colored curable composition (total content in the case of 2 or more types) is not particularly limited, and is a viewpoint for obtaining the effect of the present invention more effectively. 10 mass% to 80 mass% is preferable, 15 mass% to 75 mass% is more preferable, and 20 mass% to 60 mass% is particularly preferable.

[(D) Photoacid generator]
The colored curable composition of the present invention contains at least one photoacid generator.
The photoacid generator is a compound that generates an acid upon irradiation with light, and (D) the acid generated from the photoacid generator is used as a catalyst in the exposure region, and (B) the crosslinking reaction of the acid crosslinking agent proceeds to expose the photoacid generator. The area is cured, and the exposed area is insolubilized in the developer, whereby a negative image is obtained. At this time, preferably, a post-heating step (Post Exposure Bake = PEB step) is provided before post-exposure development, and in this PEB step, the cross-linking reaction of the (B) acid cross-linking agent can proceed efficiently. From this point, it is preferable to use a photoacid generator that generates sulfonic acid or a strong acid higher than that upon irradiation with light.

  As a photo-acid generator, the oxime sulfonate compound represented by the following general formula (C-1) or (C-2) is preferable.

In the general formulas (C-1) and (C-2), n is 1 or 2, and m is 0 or 1. In the following, “C” represents carbon, for example, “C ₈ ” represents 8 carbon atoms.
When n = 1, R ₁ is a hydrogen atom (wherein R ₂ is not simultaneously hydrogen), phenyl, naphthyl, anthracyl, phenanthryl or heteroaryl (all of which are optionally one or more C ₁ -C _{18. alkyl,} C 1 -C _{8 haloalkyl,} C 3 _{-C 30} cycloalkyl, one or more _{-O -, - S -, -} NR 23 -, - O (CO) - or _NR 23 (CO) - is interrupted by Substituted with C ₃ -C ₃₀ cycloalkyl, or halogen, —NO ₂ , —CN, —Ar ₁ , — (CO) R ₁₉ , — (CO) OR ₂₀ , — (CO) NR ₂₁ R _{22, -O (CO) R 19} , -O (CO) OR 20, -O (CO) NR 21 R 22, -NR 23 (CO) R 19, -NR 23 (CO) OR 20, -OR 20, -N _{21 R 22, -SR 23, -SOR} 19, is substituted with -SO _{2 R 19} and / or _OSO 2 _{R 19,} optionally substituted group _{- (CO) R 19, -} (CO) OR 20, - ( _{CO) NR 21 R 22, -O} (CO) R 19, -O (CO) OR 20, -O (CO) NR 21 R 22, -NR 23 (CO) R 19, -NR 23 (CO) OR 20 , —OR ₂₀ , —NR ₂₁ R ₂₂ , —SR ₂₃ , —SOR ₁₉ , —SO ₂ R ₁₉ and / or —OSO ₂ R ₁₉ represent a group R ₁₉ , R ₂₀ , R ₂₁ , R ₂₂ and / or R. ₂₃ , further substituents on the phenyl, naphthyl, anthracyl, phenanthryl or heteroaryl ring, or phenyl, naphthyl, anthracyl, phenanthryl or heteroaryl Or a 5-, 6- or 7-membered ring with one of the carbon atoms of the ring; or

R ₁ is C ₁ -C ₁₈ alkyl, or one or more C ₃ -C ₃₀ cycloalkylene, —O—, —S—, —NR ₂₃ —, — (CO) —, —O (CO )-, -S (CO)-, -NR ₂₃ (CO)-, -SO-, -SO ₂ -or OSO _2- interrupted by C ₂ -C ₁₈ alkyl (optionally C ₁ -C ₁₈ alkyl) And C ₂ -C ₁₈ alkyl is one or more C ₁ -C ₈ haloalkyl, C ₃ -C ₃₀ cycloalkyl, halogen, —NO ₂ , —CN, —Ar ₁ , — (CO) R ₁₉ , — ( _{CO) OR 20, - (CO} ) NR 21 R 22, -O (CO) R 19, -O (CO) OR 20, -O (CO) NR 21 R 22, -NR 23 (CO) R 19, - _{NR 23 (CO) OR 20,} -OR 20, -NR 2 ₁ R ₂₂ , —SR ₂₃ , —SOR ₁₉ , —SO ₂ R ₁₉ and / or OSO ₂ R ₁₉ ); or R ₁ is C ₃ -C ₃₀ cycloalkyl (optionally 1 Interrupted by one or more —O—, —S—, —NR ₂₃ —, — (CO) —, —O (CO) — or —NR ₂₃ (CO) —, unsubstituted, or one or more _C 1 _{-C 18 alkyl,} C 1 -C _{8 haloalkyl,} C 3 _{-C 30} cycloalkyl, _halogen, -NO _{2 of, -CN, -Ar 1, - (} CO) R 19, - (CO) OR 20, _{- (CO) NR 21 R 22} , -O (CO) R 19, -O (CO) OR 20, -O (CO) NR 21 R 22, -NR 23 (CO) R 19, -NR 23 (CO) _{OR 20, -OR 20, -NR 21} R 2 ₂ , substituted with —SR ₂₃ , —SOR ₁₉ , —SO ₂ R ₁₉ and / or OSO ₂ R ₁₉ ; or R ₁ is C ₁ -C ₈ haloalkyl, C ₂ -C ₁₂ alkenyl. , _C 4 _{-C 30} cycloalkenyl, or a camphoryl; or,

When m = 0, R ₁ is further CN, C ₂ -C ₆ alkoxycarbonyl or phenoxycarbonyl (wherein C ₂ -C ₆ alkoxycarbonyl and phenoxycarbonyl are optionally one or more C ₁ -C _{18 alkyl,} C 1 -C _{8 haloalkyl,} C 3 _{-C 30} cycloalkyl, one or more _{-O -, - S -, -} NR 23 -, - O (CO) - or _NR 23 (CO) - by interrupted Substituted with C ₃ -C ₃₀ cycloalkyl, or halogen, —NO ₂ , —CN, —Ar ₁ , — (CO) R ₁₉ , — (CO) OR ₂₀ , — (CO) NR _{21 R 22, -O (CO) R} 19, -O (CO) OR 20, -O (CO) NR 21 R 22, -NR 23 (CO) R 19, -NR 23 (CO) OR 20, -OR ₂₀ , -NR ₂₁ R ₂₂ , -SR ₂₃ , -SOR ₁₉ , -SO ₂ R ₁₉ and / or OSO ₂ R ₁₉ ).

In the general formulas (C-1) and (C-2), when n = 2,
R ₁ is phenylene, naphthylene, the following formula:

Diphenylene, oxydiphenylene, or the following formula:

In it or (where these groups are unsubstituted, or one or more _C 1 _{-C 18 alkyl,} C 1 -C _{8 haloalkyl,} C 3 _{-C 30} cycloalkyl, halogen, -NO ₂ , —CN, —Ar ₁ , — (CO) R ₁₉ , — (CO) OR ₂₀ , — (CO) NR ₂₁ R ₂₂ , —O (CO) R ₁₉ , —O (CO) OR ₂₀ , —O ( _{CO) NR 21 R 22, -NR} 23 (CO) R 19, -NR 23 (CO) oR 20, -OR 20, -NR 21 R 22, -SR 23, -SOR 19, -SO 2 R 19 and / Or substituted with OSO ₂ R ₁₉ ); or

R ₁ is a single bond, the following formula:

There is a group represented by
Here, R ₁ may be further substituted with a group having an —O—C— bond or an —O—Si— bond that is cleaved by the action of an acid, except when all of R ₁ are hydrogen and a single bond. it can.
A ₁ is a single bond, C _{1 to} C ₁₈ alkylene, —O—, —S—, —NR ₂₃ —, —O (CO) —, —S (CO) —, —NR ₂₃ (CO) —, — SO -, - SO ₂ - or -OSO ₂ - is.
A ₂ is a single bond, C _{1 to} C ₁₈ alkylene, or one or more C _{3 to} C ₃₀ cycloalkylene, —O—, —S—, —NR ₂₃ —, — (CO) —, — C ₂ -C ₁₈ alkylene (interrupted by O (CO) —, —S (CO) —, —NR ₂₃ (CO) —, —SO—, —SO ₂ —, —OSO ₂ — or Ar ₂ — ( Optionally substituted with the same group as the substituent when C ₁ -C ₁₈ alkyl represented by R ₁ or C ₂ -C ₁₈ alkyl interrupted by cycloalkylene or the like is substituted) Or A ₂ is C ₃ -C ₃₀ cycloalkylene (optionally substituted with the same group as the substituent when C ₃ -C ₃₀ cycloalkyl represented by R ₁ is substituted) ); or a ₂ is phenylene Naphthylene (where these groups are, optionally one or more _C 1 _{-C 18 alkyl,} C 1 -C _{8 haloalkyl,} C 3 _{-C 30} cycloalkyl, _halogen, -NO 2, -CN, -Ar ₁ ,-(CO) R ₁₉ ,-(CO) OR ₂₀ ,-(CO) NR ₂₁ R ₂₂ , -O (CO) R ₁₉ , -O (CO) OR ₂₀ , -O (CO) NR ₂₁ R ₂₂ , _{-NR 23 (CO) R 19,} -NR 23 (CO) oR 20, substituted with _{-OR 20, -NR 21 R 22,} -SR 23, -SOR 19, -SO 2 R 19 and / or _OSO 2 _{R 19} Is).

R ₂ has _one of the meanings of R ₁ or is C ₂ -C ₁₈ alkanoyl, unsubstituted or one or more C ₁ -C ₁₈ alkyl, C ₁ -C ₈ haloalkyl, C _{3 to} C ₃₀ cycloalkyl, halogen, —NO ₂ , —CN, —Ar ₁ , — (CO) R ₁₉ , — (CO) OR ₂₀ , — (CO) NR ₂₁ R ₂₂ , —O (CO) R _{19 , -O (CO) OR 20,} -O (CO) NR 21 R 22, -NR 23 (CO) R 19, -NR 23 (CO) OR 20, -OR 20, -NR 21 R 22, -SR 23 , -SOR ₁₉ , -SO ₂ R ₁₉ and / or OSO ₂ R ₁₉ ; or R ₂ is NO ₂ or R ₂ is S (O) _p C ₁ ~ _C18 alkyl, S (O) _p- C ₆ -C _{12 aryl, SO 2 O-C 1 ~C} 18 _{alkyl, SO 2 O-C 6 ~C} 10 aryl, diphenyl - phosphinoyl (optionally all these, _C 2 -C ₆ represented by _{R 1} Substituted with the same group as the substituent when alkoxycarbonyl or phenoxycarbonyl is substituted; or

R ₁ and R _{2 taken} together are 5-membered, 6-membered or 7-membered rings (which are unsubstituted or substituted by C ₂ -C ₆ alkoxycarbonyl or phenoxycarbonyl represented by R ₁ The 5-, 6- or 7-membered ring is C ₁ -C ₁₈ alkylene, C ₃ -C ₃₀ cycloalkylene, C ₁ -C ₈ halo. Alkylene, C ₂ -C ₁₂ alkenylene, C ₄ -C ₃₀ cycloalkenylene, phenylene, naphthalene, —O—, —S—, —NR ₂₃ —, — (CO) —, —O (CO) —, —NR ₂₃ (CO) -, - S ( CO) -, - SO -, - SO 2 - or -OSO ₂ - it may be further interrupted by, the 5-membered to 6-membered or 7-membered ring, optionally one More than one benzo group is condensed) Tooth;
p is 1 or 2.

X is phenyl, naphthyl, anthracyl, phenanthryl or heteroaryl (all of which are the same groups as the substituent when C ₂ -C ₆ alkoxycarbonyl or phenoxycarbonyl represented by R ₁ is optionally substituted) Optionally substituted, optionally substituted-(CO) R ₁₉ ,-(CO) OR ₂₀ ,-(CO) NR ₂₁ R ₂₂ , -O (CO) R ₁₉ , -O (CO) OR ₂₀ , -O _{(CO) NR 21 R 22,} -NR 23 (CO) R 19, -NR 23 (CO) oR 20, -OR 20, -NR 21 R 22, -SR 23, -SOR 19, and -SO _{2 R 19} And / or —OSO ₂ R ₁₉ is substituted with phenyl, naphthyl, anthracyl, phenant through the groups R ₁₉ , R ₂₀ , R ₂₁ , R ₂₂ and / or R _23. A further substituent on the aryl or heteroaryl ring, or a 5-, 6- or 7-membered ring with one of the carbon atoms of the phenyl, naphthyl, anthracyl, phenanthryl or heteroaryl ring) ; or _X, C 1 _{-C 18} alkyl, or one or more _C 3 _{-C 30 cycloalkylene, -O -, - S -,} - NR 23 -, - (CO) -, - O ( _{CO) -, - S (CO} ) -, - NR 23 (CO) -, - SO -, - SO 2 - or OSO ₂ -, optionally _C 2 _{-C 18} alkyl interrupted (by represented by _{R 1} C ₁ -C ₁₈ alkyl or cycloalkyl C ₂ -C ₁₈ alkyl interrupted by an alkylene or the like is substituted with the same groups as the substituents when substituted) that; or X, C _{3 to} C ₃₀ cycloalkyl (optionally substituted with the same group as the substituent when C ₃ -C ₃₀ cycloalkyl represented by R ₁ is substituted); or X is C _1- C ₈ haloalkyl, C ₂ -C ₁₂ alkenyl, C ₄ -C ₃₀ cycloalkenyl, camphoryl;

R ₃ has _one of the meanings indicated for R ₁ , or R ₃ is a C ₂ -C ₁₈ alkanoyl or optionally one or more C ₁ -C ₁₈ alkyl, C ₁ -C _{8 haloalkyl,} C 3 _{-C 30} cycloalkyl, _{halogen, -NO 2, -CN, -Ar 1} , - (CO) R 19, - (CO) OR 20, - (CO) NR 21 R 22, - _{O (CO) R 19, -O} (CO) OR 20, -O (CO) NR 21 R 22, -NR 23 (CO) R 19, -NR 23 (CO) OR 20, -OR 20, -NR 21 R ₂₂ , —SR ₂₃ , —SOR ₁₉ , —SO ₂ R ₁₉ and / or OSO ₂ R ₁₉ is benzoyl substituted; or R ₃ is NO ₂ , or R ₃ is S _{(O) p C} 1 ~C ₁₈ alkyl Table with _{R 1} phosphinoyl (optionally all these _{-, S (O) p -C} 6 ~C 12 _{aryl, SO 2 O-C 1 ~C} 18 _{alkyl, SO 2 O-C 6 ~C} 10 aryl, diphenyl It is C ₂ -C ₆ alkoxycarbonyl or phenoxycarbonyl is substituted with the same groups as the substituents when substituted) is;

R ₄ has one of the meanings indicated for R ₂ , or R ₃ and R _{4 taken} together are a 5-membered, 6-membered or 7-membered ring (this is optionally R ₁ is substituted with the substituent in the case where in C ₂ -C ₆ alkoxycarbonyl or phenoxycarbonyl represented are substituted with the same group, the 5-membered, 6-membered or 7-membered ring, optionally C ₁ ~ C _{18 alkylene,} C 3 _{-C 30 cycloalkylene,} C 1 -C _{8 haloalkylene,} C 2 _{-C 12 alkenylene,} C 4 _{-C 30} cycloalkenylene, phenylene, naphthalene, -O -, - S -, - NR 23 _{-, - (CO) -,} - O (CO) -, - NR 23 (CO) -, - S (CO) -, - SO -, - SO 2 - or -OSO ₂ - are further interrupted, Optionally one or more benzo groups Serial 5-membered, fused to 6-membered or 7-membered ring) to form a.

R ₅ and R ₆ are independently of each other hydrogen, C ₁ -C ₁₈ alkyl, C ₁ -C ₈ haloalkyl, C ₃ -C ₃₀ cycloalkyl, one or more —O—, —S—, —NR. _{23 -, - O (CO)} - or _NR 23 (CO) - or is _C 3 _{-C 30} cycloalkyl which is interrupted by,
Or R ₅ and R ₆ are halogen, —NO ₂ , —CN, —Ar ₁ , — (CO) R ₁₉ , — (CO) OR ₂₀ , — (CO) NR ₂₁ R ₂₂ , —O (CO) R; ₁₉ , —O (CO) OR ₂₀ , —O (CO) NR ₂₁ R ₂₂ , —NR ₂₃ (CO) R ₁₉ , —NR ₂₃ (CO) OR ₂₀ , —OR ₂₀ , —NR ₂₁ R ₂₂ , —SR ₂₃ , —SOR ₁₉ , —SO ₂ R ₁₉ and / or OSO ₂ R ₁₉ ; or R ₅ and R ₆ together represent —C (R ₃₀ ) ═C (R ₃₁ ) —C ( R ₃₂ ) = C (R ₃₃ ) — or (CO) NR ₂₃ (CO) —;

G represents —S—, —O—, —NR ₂₃ —, or the following formula Z ₁ , Z ₂ , Z ₃ or Z ₄ :

A group represented by:

R ₁₉ is a hydrogen atom, phenyl, _naphthyl, C 3 _{-C 30 cycloalkyl,} C 1 _{-C 18 alkyl,} C 1 -C _{8 haloalkyl,} C 2 _{-C 12 alkenyl,} C 4 _{-C 30} cycloalkenyl, one C ₂ -C ₁₈ alkyl interrupted by —O— or interrupted by one or more —O—, —S—, —NR ₂₃ —, —O (CO) — or NR ₂₃ (CO) —. Represented by C ₃ -C ₃₀ cycloalkyl (all of which are optionally one or more Ar ₁ , OH, C ₁ -C ₁₈ alkyl, C ₁ -C ₈ haloalkyl, C ₃ -C ₃₀ cycloalkyl, Halogen, —NO ₂ , —CN, C ₁ -C ₁₂ alkoxy, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, —NR ₂₁ R ₂₂ , C _{1 to} C ₁₂ a _Alkylthio, C 2 _{-C 12 alkoxycarbonyl,} C 2 -C ₈ haloalkanoyl, _halobenzoyl, C 1 _{-C 12} alkylsulfonyl, phenylsulfonyl, (4-methylphenyl) _sulfonyl, C 1 _{-C 12} alkylsulfonyloxy, phenyl sulfonyloxy, substituted with (4-methylphenyl) _sulfonyloxy, C 2 _{-C 12 alkanoyl,} C 2 _{-C 12} alkanoyloxy, benzoyl and / or benzoyloxy).

R ₂₀ is hydrogen, phenyl, _naphthyl, C 3 _{-C 30 cycloalkyl,} C 1 _{-C 18 alkyl,} C 1 -C _{8 haloalkyl,} C 2 _{-C 12 alkenyl,} C 4 _{-C 30} cycloalkenyl, one or more C ₂ -C ₁₈ alkyl interrupted by —O—, interrupted by one or more —O—, —S—, —NR ₂₃ —, —O (CO) — or NR ₂₃ (CO) —. C ₃ -C ₃₀ cycloalkyl, C ₂ -C ₁₈ alkanoyl, benzoyl, C ₁ -C ₁₈ alkylsulfonyl (all of which are optionally the same as the substituents when R ₁₉ is substituted) Substituted), phenylsulfonyl, (4-methylphenyl) sulfonyl, naphthylsulfonyl, anthracylsulfonyl or phenanthrylsulfonyl.

R ₂₁ , R ₂₂ and R ₂₃ are independently of each other hydrogen, phenyl, naphthyl, C ₃ -C ₃₀ cycloalkyl, C ₁ -C ₁₈ alkyl, C ₁ -C ₈ haloalkyl, C ₂ -C ₁₂ alkenyl, C ₄ -C ₃₀ cycloalkenyl, or C ₂ -C ₁₈ alkyl interrupted by one or more —O—, or one or more —O—, —S—, —NR _23. C ₃ -C ₃₀ cycloalkyl interrupted by —, —O (CO) — or NR ₂₃ (CO) —; or C _{2 to} C ₁₈ alkanoyl, benzoyl or C _{1 to} C ₁₈ alkylsulfonyl. or (all optionally R ₁₉ are substituted with the same groups as the substituents when substituted); or R _21, R ₂₂ and R ₂₃ are, independently of one another, phenylene Sulfonyl, (4-methylphenyl) sulfonyl, naphthylsulfonyl, or is anthracyl sill sulfonyl or phenanthryl sulfonyl; or R ₂₁ and R _22, together with the nitrogen atom to which they are attached, optionally - O- or _{-NR 23} - which is interrupted by 5- to form a 6-membered or 7-membered ring.

R ₃₀ , R ₃₁ , R ₃₂ and R ₃₃ are independently of each other hydrogen, halogen, C ₁ -C ₁₈ alkyl, C ₁ -C ₁₈ alkoxy, C ₁ -C ₈ haloalkyl, CN, NO ₂ , C _2. -C ₁₈ alkanoyl, benzoyl, phenyl, -S- _{phenyl, OR 20, SR 23, NR} 21 R 22, C 2 ~C 6 alkoxycarbonyl, _{phenoxycarbonyl, S (O) p C 1} ~C 18 alkyl, unsubstituted or be a _C 1 _{-C 18} alkyl-substituted _{S (O) p -C 6 ~C} 12 _{aryl, SO 2 O-C 1 ~C} 18 _{alkyl, SO 2 O-C 6 ~C} 10 aryl or NHCONH _2;
R ₃₄ and R ₃₅ independently of one another have one of the meanings indicated for R ₅ ; or R ₃₄ and R _{35 taken} together are —CO—NR ₂₃ CO—. Or R ₃₄ and R _{35 taken} together are —C (R ₃₀ ) ═C (R ₃₁ ) —C (R ₃₂ ) ═C (R ₃₃ ) —;

Ar ₁ is phenyl, naphthyl, anthracyl, phenanthryl or heteroaryl (which are all the same as the substituents when C ₂ -C ₆ alkoxycarbonyl or phenoxycarbonyl represented by R ₁ is optionally substituted) Substituted with a group (except for -Ar ₁ ) or -phenyl, optionally with the substituents-(CO) R ₁₉ ,-(CO) OR ₂₀ ,-(CO) NR ₂₁ R ₂₂ , -O (CO) R ₁₉ , —O (CO) OR ₂₀ , —O (CO) NR ₂₁ R ₂₂ , —NR ₂₃ (CO) R ₁₉ , —NR ₂₃ (CO) OR ₂₀ , —OR ₂₀ , —NR ₂₁ R ₂₂ , —SR ₂₃ , —SOR ₁₉ , —SO ₂ R ₁₉ and / or —OSO ₂ R ₁₉ are bonded to the phenyl via the groups R ₁₉ , R ₂₀ , R ₂₁ , R ₂₂ and / or R _23. A further substituent of a ru, naphthyl, anthracyl, phenanthryl or heteroaryl ring, or one of the carbon atoms of a phenyl, naphthyl, anthracyl, phenanthryl or heteroaryl ring and a 5-, 6- or 7-membered ring. Forming);

Ar ₂ is phenylene, naphthylene, or the following formula:

Diphenylene, oxydiphenylene or the following formula:

(Wherein these groups are optionally substituted by one or more _C 1 _{-C 18 alkyl,} C 1 -C _{8 haloalkyl,} C 3 _{-C 30} cycloalkyl, _halogen, -NO 2, -CN, _-Ar 1, -(CO) R ₁₉ ,-(CO) OR ₂₀ ,-(CO) NR ₂₁ R ₂₂ , -O (CO) R ₁₉ , -O (CO) OR ₂₀ , -O (CO) NR ₂₁ R ₂₂ ,- Substituted with NR ₂₃ (CO) R ₁₉ , —NR ₂₃ (CO) OR ₂₀ , —OR ₂₀ , —NR ₂₁ R ₂₂ , —SR ₂₃ , —SOR ₁₉ , —SO ₂ R ₁₉ and / or —OSO ₂ R ₁₉ In some cases, the substituents — (CO) R ₁₉ , — (CO) OR ₂₀ , — (CO) NR ₂₁ R ₂₂ , —O (CO) R ₁₉ , —O (CO) OR ₂₀ , — (CO _{) NR 21 R 22, -NR 23} ( _{O) R 19, -NR 23 (} CO) OR 20, -OR 20, -NR 21 R 22, -SR 23, -SOR 19, -SO 2 R 19 and / or -OSO ₂ R ₁₉ is a group _{R 19} , R ₂₀ , R ₂₁ , R ₂₂ and / or R ₂₃ , further substituents of these groups, or one of these groups, 5 members, 6 members or 7 members Forming a ring);

Q ₁ is —CR ₃₅ — or —N—;
Q ₂ is —CH ₂ —, —S—, —O— or —NR ₂₃ —. ]

  Examples of the oxime sulfonate photoacid generator represented by the general formula (C-1) or (C-2) include Japanese Patent No. 3875271, Japanese Patent No. 3975411, and Special Table No. 2004-510189, These compounds are known in JP-T-2005-504013, JP-T-2005-517026, JP-T-2006-517950, and the like, and can be synthesized by the methods described in these documents.

  As the oxime sulfonate photoacid generator represented by the general formula (C-1) or (C-2), particularly preferred compounds are shown below.

  In the above formula, R represents a C1-C12 alkyl, C1-C8 fluoroalkyl, carbonyl, phenyl, tolyl, nitrophenyl, chlorophenyl, trifluoromethylphenyl, alkoxyphenyl, 2,4,6-trimethylphenyl, pentafluorophenyl group. To express. “C” represents carbon, and “C1” represents 1 carbon.

  Examples of the acid generator that can be used in the colored curable composition of the present invention include a sulfonium salt represented by the following general formula (ZI) and a general formula (ZII) below, in addition to the oxime sulfonate-based compounds described above. In addition, a diazodisulfone compound represented by the following general formula (ZIII) can also be used.

In the general formula (ZI), R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represents an organic group. The carbon number of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is generally 1 to 30, preferably 1 to 20. Two of R _{201 to} R ₂₀₃ may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. Examples of the group formed by combining two of R _{201 to} R ₂₀₃ include an alkylene group (eg, butylene group, pentylene group).
Z ⁻ represents a sulfonate anion. Z ^- as sulfonic acid anion represented by, for example, an aliphatic sulfonate anion, aromatic sulfonate anion, and a camphorsulfonate anion.

In the general formulas (ZII) and (ZIII), R _{204 to} R ₂₀₇ each independently represents an aryl group, an alkyl group, or a cycloalkyl group. The aryl group represented by R ₂₀₄ to R _207, a phenyl group, a naphthyl group, more preferably a phenyl group.
The alkyl group and cycloalkyl group represented by R _{204 to} R ₂₀₇ are preferably a linear or branched alkyl group having 1 to 10 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group). ), And a cycloalkyl group having 3 to 10 carbon atoms (cyclopentyl group, cyclohexyl group, norbornyl group). The aryl group, alkyl group and cycloalkyl group represented by R _{204 to} R ₂₀₇ may have a substituent.
Z ⁻ represents a sulfonate anion, and examples thereof include the same as the non-nucleophilic anion of Z ⁻ in the general formula (ZI).

  The compounds preferably used as photoacid generators represented by the general formulas (ZI) to (ZIII) are shown below.

  Photoacid generators that can be used in the colored curable composition of the present invention include known triazine compounds, acetophenone derivative compounds, orthonitrobenzyl sulfonate compounds, triarylphosphonium salts, iron arene complexes in addition to the above-mentioned compounds. It is also possible to use a photoacid generator.

(D) A photo-acid generator can contain the above compounds individually by 1 type or in combination of 2 or more types.
The content (D) of the photoacid generator in the total solid content of the colored curable composition (total content in the case of two or more) is 1% by mass from the viewpoint of obtaining the effect of the present invention more effectively. -20% by mass is preferable, 2% by mass to 12% by mass is more preferable, and 4% by mass to 10% by mass is particularly preferable.

[(E) Organic solvent]
The colored curable composition of the present invention contains at least one organic solvent.
The organic solvent is basically not particularly limited as long as it can satisfy the solubility of each of the coexisting components and the coating property when the colored curable composition is formed, and particularly the solubility, coating property, and safety of the binder. It is preferable to select in consideration of the properties.

  Examples of organic solvents 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, methyl lactate, and ethyl lactate. Oxyacetic acid alkyl esters (eg, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (specific examples include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate). )), 3-oxypropionic acid alkyl esters (eg, methyl 3-oxypropionate, ethyl 3-oxypropionate and the like (specifically, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3- Methyl ethoxypropionate, 3-ethoxy Ethyl propionate, etc.)), 2-oxypropionic acid alkyl esters (eg, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc. (specifically, 2 -Methyl methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, etc.)), 2-oxy-2-methylpropionic acid Methyl, ethyl 2-oxy-2-methylpropionate (specifically, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, Ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate , Methyl 2-oxobutanoate, ethyl 2-oxobutanoate, and the like.

Examples of ethers include 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 monomethyl ether. Propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate and the like.
Examples of ketones include methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone.
Preferable examples of aromatic hydrocarbons include toluene and xylene.

  It is also preferable to mix two or more of these organic solvents from the viewpoints of the solubility of each of the above-mentioned components, and the solubility and the improvement of the coating surface state when an alkali-soluble binder is included. In this case, particularly preferably, 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 It is a mixed solution composed of two or more selected from acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate.

  The content of the organic solvent in the colored curable composition is preferably such that the total solid concentration in the composition is 10% by mass to 80% by mass, and more preferably 15% by mass to 60% by mass. .

[(F) Other ingredients]
The colored curable composition of the present invention may further contain other components such as an alkali-soluble binder as long as the effects of the present invention are not impaired in addition to the above-described components.

-Alkali-soluble binder-
The alkali-soluble binder is not particularly limited except that it has alkali solubility, and can be preferably selected from the viewpoints of heat resistance, developability, availability, and the like.

  The alkali-soluble binder is preferably a linear organic high molecular polymer that is soluble in an organic solvent and can be developed with a weakly alkaline aqueous solution. Examples of such a linear organic high molecular polymer include the polymers described in paragraphs [0227] to [0234] of JP-A-2008-292970.

  Among the alkali-soluble binders, from the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferable, and from the viewpoint of developability control, Acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferred. Examples of the acrylic resin include copolymers composed of monomers selected from benzyl (meth) acrylate, (meth) acrylic acid, hydroxyethyl (meth) acrylate, (meth) acrylamide, and the like, and commercially available KS resist 106 (Osaka). Organic Chemical Industry Co., Ltd.), Cyclomer P Series (manufactured by Daicel Chemical Industries, Ltd.) and the like are preferable.

Alkali-soluble binder, developability, from the viewpoint of liquid viscosity, weight average molecular weight (measured in terms of polystyrene by GPC method) is preferably a polymer of 1,000 to 2 × 10 ^5, the weight of the 2000-1 × 10 ⁵ A coalescence is more preferable, and a polymer of 5000 to 5 × 10 ⁴ is particularly preferable.

-Other additives-
For the colored curable composition, various additives, for example, a filler, a polymer compound other than the above, a nonionic, cationic, anionic or other surfactant, adhesion promoter, antioxidant UV absorbers, anti-aggregation agents, and the like can be blended. Examples of these additives include those described in paragraphs [0155] to [0156] of JP-A No. 2004-295116.
The colored curable composition of the present invention contains a sensitizer and a light stabilizer described in paragraph [0078] of JP-A No. 2004-295116, and a thermal polymerization inhibitor described in paragraph [0081] of the same publication. can do.

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

-Preparation method of colored curable composition-
In preparing the colored curable composition of the present invention, the above-described components of the composition may be combined at once, or may be sequentially added after each component is dissolved in a solvent. In addition, there are no particular restrictions on the charging order and working conditions when blending. A composition may be prepared by dissolving all the components in a solvent at the same time. If necessary, each component is appropriately made into two or more solutions, and these solutions are mixed at the time of use (at the time of application). And may be prepared as a composition.
The composition prepared as described above is preferably subjected to use after being filtered using a Millipore filter or the like having a pore size of 0.01 to 3.0 μm, more preferably 0.05 to 0.5 μm. You can also.

  Since the colored curable composition of the present invention is excellent in storage stability and can form a colored cured film with excellent light resistance, a liquid crystal display element (LCD) or a solid-state imaging element (for example, CCD, CMOS) Etc.) can be suitably used for forming colored pixels such as color filters and for producing printing inks, inkjet inks, paints, and the like. In particular, it can be suitably used for forming colored pixels for solid-state imaging devices such as CCDs and CMOSs.

The colored curable composition of the present invention is a combined system of pigment and dye as a colorant, and is a thin film with a very small color pattern, particularly by using a composition in which a phthalocyanine pigment and a specific complex are used in combination as a pigment and a dye. A colored pattern having excellent color reproducibility can be obtained. Therefore, it is suitable for forming a color filter for a solid-state imaging device that requires a fine and good rectangular cross-sectional profile.
Specifically, when the pixel pattern size (side length of the pixel pattern viewed from the substrate normal direction) constituting the color filter is 2 μm or less (for example, 0.5 to 2.0 μm), the amount of the colorant increases. In addition, since the hue is blue, the line width sensitivity is deteriorated and the DOF margin is narrowed. As a result, the pattern formability is easily impaired. This is particularly noticeable when the pixel pattern size is 1.0 to 1.7 μm (further 1.2 to 1.5 μm). In addition, in the case of a thin film having a thickness of 1 μm or less, the amount of components that contribute to photolithographic properties excluding the colorant in the film is relatively reduced, and the amount of other components is further reduced by the increase in the amount of colorant. Sensitivity is increased and the pattern is easily peeled off in the low exposure area. In this case, heat sagging is likely to occur when heat treatment such as post-baking is performed. These are particularly remarkable when the film thickness is 0.005 μm to 0.9 μm (further 0.1 μm to 0.7 μm).
On the other hand, when the colored curable composition of the present invention is used, a color filter having a good cross-sectional profile can be produced with excellent pattern formation even with the pixel pattern size of 2 μm or less as described above.

-Color filter and manufacturing method thereof-
The color filter of the present invention is prepared using the above-described colored curable composition of the present invention. Specifically, the colored curable composition of the present invention described above is applied onto a support. Forming a colored curable composition layer, exposing the colored curable composition layer formed on the support through a mask, and developing to form a pattern image; Are produced by a method (a method for producing a color filter of the present invention) constituted by providing the above.

<Layer formation process>
In the layer forming step, the colored curable composition of the present invention is applied on a support to form a colored curable composition layer. For example, 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 photosensitive or radiation-sensitive colored curable composition layer. Then, if necessary, preliminary curing (pre-baking) is performed, and the colored curable composition is dried.

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

  In addition, when spin-coating the colored curable composition on the support, in order to reduce the amount of dripping of the liquid, before dropping the colored curable composition, by dropping and rotating an appropriate organic solvent, The familiarity of the colored curable composition with the support can be improved.

  Examples of the prebaking condition include a condition of heating at 70 ° C. to 130 ° C. for about 0.5 minutes to 15 minutes using a hot plate or an oven.

  The thickness of the colored curable composition layer formed by coating with the colored curable composition is appropriately selected according to the purpose, but is generally 0.2 μm to 5.0 μm, preferably 0.3 μm to 2 μm. 0.5 μm is more preferable, and 0.3 μm to 1.5 μm is most preferable. Here, the thickness of the colored curable composition layer refers to the thickness after pre-baking.

<Pattern formation process>
In the pattern forming step, after performing an exposure step of exposing the colored curable composition layer formed on the support through a mask, a developing step of developing is performed to form a desired colored pattern. The colored curable composition layer formed in the layer forming step is exposed through a predetermined mask pattern, and developed with a developer to form a negative colored pattern.

As light or radiation used in the exposure, g-line, h-line, i-line, KrF light, ArF light is particularly preferable, and i-line is particularly preferable. When using the i-line to the irradiation light is ^preferably irradiated at an exposure dose of ^{100mJ / cm 2 ~10000mJ / cm 2} .
The exposure can be performed while flowing nitrogen gas in the chamber in order to suppress oxidation fading of the colorant in the colored curable composition layer.

The exposure may be performed by any of the proximity method, the mirror projection method, and the stepper method, but the exposure is particularly preferably performed by the stepper method (reduced projection exposure method using a reduced projection exposure machine). . In the stepper method, a pattern is formed by performing exposure while varying the exposure amount stepwise, and the rectangularity of the pattern can be particularly improved when performing stepper exposure.
Moreover, as an exposure apparatus used for stepper exposure, for example, an i-line stepper (trade name: FPA-3000i5 +, manufactured by Canon Inc.) can be used.

  When pattern formation is performed using the colored curable composition of the present invention, a mode in which a post-heating step using a hot plate or an oven is performed before development after exposure is preferable (post exposure baking). Process = PEB process). In the PEB process, the acid generated in the exposed region is used as a catalyst to cause the crosslinking reaction of the acid crosslinking agent (B) to cure the exposed region. The temperature and time of the PEB step are not particularly limited as long as they are sufficient to cause the crosslinking reaction of the (B) acid crosslinking agent in the exposed area, but are usually 70 ° C. to 180 ° C. for 0.5 minutes to 15 minutes. It is preferable that it is a grade.

After the exposure, the exposed colored curable composition layer is developed with a developer. Thereby, a negative colored pattern (resist pattern) can be formed.
As the developer, a developer having a composition that dissolves the colored curable composition (uncured portion) of the present invention but does not dissolve the irradiated cured portion can be used. Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used. As said organic solvent, the above-mentioned organic solvent used when preparing the colored curable composition of this invention is mentioned. Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, Concentration of an alkaline compound such as choline, pyrrole, piperidine, 1,8-diazabicyclo- [5.4.0] -7-undecene is 0.001 to 10% by mass, preferably 0.01 to 1% by mass. An alkaline aqueous solution obtained by dissolution is preferred. For example, when the developer is an alkaline aqueous solution, the pH is preferably adjusted to 11 to 13, more preferably 11.5 to 12.5. In particular, an alkaline aqueous solution in which tetraethylammonium hydroxide is adjusted so as to have a concentration of 0.001% by mass to 10% by mass, preferably 0.01% by mass to 5% by mass can be used.

  The development time is preferably 30 seconds to 300 seconds, more preferably 30 seconds to 120 seconds. The development temperature is preferably 20 ° C to 40 ° C, more preferably 23 ° C. Development can be performed by a paddle method, a shower method, a spray method, or the like.

  Moreover, after developing using alkaline aqueous solution, it is preferable to wash | clean with water. The cleaning method is also appropriately selected according to the purpose. While the support body such as a silicon wafer is rotated at a rotation speed of 10 rpm to 500 rpm, pure water is supplied from the upper part of the rotation center in a shower shape and rinsed. Processing can be performed.

In the present invention, if necessary, the pattern formed through the coating step, the exposure step, the PEB step and the development step using the colored curable composition is further subjected to post-heating and post-curing steps. A post-exposure may be performed to promote pattern curing.
The post-heating is preferably performed at 100 ° C to 300 ° C using a hot plate or an oven, and more preferably 150 ° C to 250 ° C. The post-heating time is preferably 30 seconds to 30000 seconds, more preferably 60 seconds to 1000 seconds.
On the other hand, the post-exposure can be performed with g-line, h-line, i-line, KrF, ArF, UV light, electron beam, X-ray, etc., but g-line, h-line, i-line, UV light is preferable. UV light is preferred. When performing UV light irradiation (UV cure), it is preferably performed at a low temperature of 20 ° C. to 50 ° C. (preferably 25 ° C. to 40 ° C.). The wavelength of the UV light preferably includes a wavelength in the range of 200 nm to 300 nm. As the light source, for example, a high pressure mercury lamp, a low pressure mercury lamp, or the like can be used. The irradiation time is 10 seconds to 180 seconds, preferably 20 seconds to 120 seconds, and more preferably 30 seconds to 60 seconds.
Either post-exposure or post-heating may be performed first, but post-exposure is preferably performed prior to post-heating. By promoting the curing by post-exposure, it is possible to suppress deformation of the shape due to thermal sagging and soaking of the pattern seen in the post-heating process.

The colored pattern thus obtained constitutes a pixel of the color filter.
In the production of a color filter having a plurality of hue pixels, the aforementioned coating process, exposure process, and development process (a curing process as necessary) may be repeated in accordance with the desired number of colors.

  The color filter obtained by the method for producing a color filter of the present invention (the color filter of the present invention) prevents the occurrence of color loss due to the use of the colored curable composition of the present invention. Is excellent. Therefore, the color filter of the present invention includes a liquid crystal display element, a solid-state imaging element such as a CCD image sensor and a CMOS image sensor used for a digital camera, a digital video camera, an endoscope, a mobile phone, and a camera using the same. Can be used in the system. Above all, it is suitable for use in solid-state imaging devices where a colored pattern is formed in a thin film with a very small size and a good rectangular cross-sectional profile is required, especially for high-resolution CCD devices exceeding 1 million pixels, CMOS, etc. It is.

≪Solid-state imaging device≫
The solid-state imaging device of the present invention includes the color filter of the present invention. The color filter of the present invention is one in which occurrence of color loss is prevented, and a solid-state imaging device provided with this color filter can obtain excellent color reproducibility.

  The configuration of the solid-state imaging device is not particularly limited as long as it includes the color filter of the present invention and functions as a solid-state imaging device. For example, the following configuration can be given. That is, a transfer electrode made of a plurality of photodiodes and polysilicon constituting a light receiving area of a CCD image sensor (solid-state imaging device) is provided on a support, and the color filter of the present invention is provided on the transfer electrode. The microlenses are stacked.

  In addition, the camera system including the color filter of the present invention includes a cover lens, a microlens, and the like in which a camera lens and an IR cut film are dichroically coated from the viewpoint of light fading of a color material. It is desirable that the optical characteristics absorb part or all of UV light of 400 nm or less. Further, the structure of the camera system is preferably such that the oxygen permeability to the color filter is reduced in order to suppress oxidation fading of the color material. For example, a part or the whole of the camera system Is preferably sealed with nitrogen gas.

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

Example 1
-1. Preparation of colored curable composition
Each component in the following composition was mixed, dispersed and dissolved to obtain a colored curable composition.
<Composition>
Propylene glycol monomethyl ether acetate (PGMEA) 34.250 parts Melamine resin (acid crosslinking agent) 3.571 parts (Poly (melamine-co-formaldehyde), methylated 84 mass% 1-butanol solution, (Aldrich)
・ Fluorosurfactant (CW-1, manufactured by Zeneca) 1% by mass PGMEA solution: 2.500 parts ・ The following photoacid generator (A) (manufactured by Ciba Specialty Chemicals): 0.600 Part Specific complex in the present invention: 3.000 parts (Exemplary Compound Ia-8 of a complex in which the compound represented by the general formula (I) is coordinated to a metal atom or a metal compound)
Pigment Blue-15: 6 dispersion ... 56.075 parts (containing acrylic polymer dispersant, solid content concentration 14.98% by mass, pigment concentration 10.70% by mass)

-2. Evaluation of color loss-
Above 1. The colored curable composition obtained in the above was applied on a glass substrate so that the dry film thickness was 0.6 μm to form a coating layer (colored curable composition layer). The glass substrate on which the coating layer was formed was heat-treated (prebaked) for 120 seconds using a 100 ° C. hot plate. Thereafter, the entire surface of the coating layer on the glass substrate was exposed with an exposure apparatus at a light of 365 nm at an exposure amount of 1000 mJ / cm ² . The coated layer after exposure was heated (PEB) for 120 seconds using a 110 ° C. hot plate. Then, the coating film after PEB was heated (post-baked) for 5 minutes using a 200 degreeC hotplate. The coating layer after post-baking was naturally cooled to room temperature, and a color filter for color loss evaluation was produced.
On the produced color filter for color loss evaluation, 0.1 ml of cyclohexanone was dropped and left for 5 minutes. The color filter chromaticity difference (ΔE * ab) before and after the cyclohexanone was dropped was measured and used as an index for evaluating the resistance to color loss with respect to cyclohexanone. Note that the smaller the value of ΔE * ab, the better the color loss resistance. The evaluation results are shown in Table 1 below.

(Examples 2-51)
In Example 1, the specific complex (Exemplary Compound Ia-8) in the composition of the colored curable composition is shown as an exemplary compound shown in Table 1 below or a pigment for comparison, and Pigment Blue-15: 6 is shown in Table 1 below. In addition to the pigment, the melamine resin is replaced with the acid crosslinking agent shown in Table 1 below, the photoacid generator (A) is replaced with the photoacid generator shown in Table 1 below, and the blending amount of each component is shown in Table 1 below. A colored curable composition was prepared in the same manner as in Example 1 except that the amount was changed. Further, the obtained colored curable composition was evaluated for color loss in the same manner as in Example 1. The evaluation results are summarized in Table 1 below.

  Here, PigmentBlue-15 and PigmentBlue-15: 3 used in Example 14, Example 15, Example 31, Example 32, Example 48, and Example 49 are PigmentBlue-15 described in Example 1: A dispersion having the same concentration as in No. 6 was used.

Details of the components in Table 1 below are as follows.
Photo acid generator (B): photo acid generator having the above structure. Epoxy resin: acid cross-linking agent having the following structure (EHPE 3150, manufactured by Daicel Chemical Industries; 1 of 2,2-bis (hydroxymethyl) -1-butanol , 2-epoxy-4- (2-oxiranyl) cyclohexane adduct)
-Phenol-based crosslinking agent: Acid crosslinking agent having the following structure (TrisP-PA, a hexamethoxymethyl compound manufactured by Honshu Chemical Industry Co., Ltd.)

(Comparative Example 1)
In Example 12, except that the melamine resin and the photoacid generator (A) were replaced with the monomer (A) and the photopolymerization initiator (A), and the composition system was such that the film was cured by radical polymerization reaction. Similarly, a colored curable composition was prepared. Further, the color loss evaluation of the obtained colored curable composition was performed in the same manner as in Example 1 except that the PEB process was omitted from the color loss evaluation procedure of Example 1. The evaluation results are shown in Table 1 below.

Monomer (A): Dipentaerythritol hexaacrylate Photoinitiator (A):

(Comparative Example 2)
In Example 11, the specific complex (Exemplary Compound III-47) was synthesized from C.I. I. A colored curable composition was prepared in the same manner as in Example 11 except that it was replaced with Acid Violet-17. Further, the color loss evaluation of the obtained colored curable composition was performed in the same manner as the color loss evaluation procedure of Example 1. The evaluation results are shown in Table 1 below.

  As is apparent from Table 1, in the examples in which the specific complex according to the present invention was used in combination with the photoacid generator and the acid crosslinking agent, the color loss resistance to cyclohexanone (organic solvent) was excellent.

(Example 52)
The 6 inch silicon wafer was heat-treated in an oven at 200 ° C. for 30 minutes. Next, on this silicon wafer, a resist solution prepared by mixing and dissolving each component in the following composition is applied so as to have a dry film thickness of 1.0 μm, and further dried in an oven at 220 ° C. for 1 hour to form an undercoat layer. Formed. Thus, a silicon wafer with an undercoat layer was obtained.

<Composition>
Propylene glycol monomethyl ether acetate (PGMEA) ... 19.20 partsEthyl lactate ... 36.67 partsBinder: benzyl methacrylate / methacrylic acid / -2-hydroxyethyl methacrylate copolymer (molar ratio = 60/20/20) 41% EL solution: 30.51 parts dipentaerythritol hexaacrylate 12.20 parts p-methoxyphenol (polymerization inhibitor) 0.0061 parts fluorine -Based surfactant: 0.83 parts TAZ-107 (manufactured by Midori Chemical Co .; photopolymerization initiator): 0.586 parts

The colored curable composition prepared in Examples 1 to 51 was applied on the undercoat layer of the obtained silicon wafer with an undercoat layer so that each dry film thickness was 0.6 μm, and a photocurable coating film was formed. (Colored curable composition layer) was formed. And this coating film was heat-processed (prebaked) for 120 second using a 100 degreeC hotplate. Next, using an i-line stepper (FPA-3000i5 +, Canon Inc. exposure apparatus), light having a wavelength of 365 nm is passed through an island pattern mask having a pattern of 1.2 μm square to 100 mJ / cm ^{2 to} 2500 mJ / cm. ^In the range of ² , irradiation was performed while changing the exposure amount by 100 mJ / cm ² . Then, PEB (Post Exposure Bake) was performed for 120 seconds using a 110 degreeC hotplate. Then, after waiting for the coating film to cool to room temperature, the silicon wafer on which the coating film is formed is placed on a horizontal rotary table of a spin shower developing machine (DW-30 type; manufactured by Chemtronics Co., Ltd.). Then, paddle development was performed at 23 ° C. for 60 seconds using CD-2000 (manufactured by Fuji Film Electronics Materials Co., Ltd.).
In this way, a blue pattern was formed on the silicon wafer.

A silicon wafer on which a blue pattern is formed is fixed to the horizontal rotary table by a vacuum chuck method, and the silicon wafer is rotated at a rotational speed of 50 rpm by a rotating device, and pure water is ejected from above the rotation center from a jet nozzle. And rinsed. Then, it spray-dried and produced the color filter.
The produced color filter has a blue pattern in which the exposure amount is 200 to 600 mJ / cm ² , and the shape seen from the normal direction of the silicon wafer is square, and the plane parallel to the normal direction is cut in a plane. The cross section showed a good rectangular profile. Thus, the obtained color filter was suitable for a solid-state image sensor application.

Claims (11)

(A-1) A compound represented by the following general formula (I) is coordinated to a metal atom or a metal compound, (A-2) a phthalocyanine pigment, (B) a dispersant, and (C) an acid. A colored curable composition comprising at least a crosslinking agent for crosslinking, (D) a photoacid generator, and (E) an organic solvent.

[In General Formula (I), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ each independently represent a hydrogen atom or a substituent. R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. ] 2. The complex according to (A-1), wherein the compound represented by the general formula (I) is coordinated to a metal atom or a metal compound, and is a compound represented by the following general formula (II-1). Colored curable composition.

[In General Formula (II-1), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ each independently represent a hydrogen atom or a substituent. R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. Ma represents a metal atom or a metal compound. X ² represents a group necessary for neutralizing the electric charge of Ma, and X ¹ represents a group capable of binding to Ma. X ¹ and X ² may be bonded to each other to form a 5-membered, 6-membered, or 7-membered ring. ] 2. The complex according to claim 1, wherein the compound represented by (A-1) the general formula (I) is coordinated to a metal atom or a metal compound is a compound represented by the following general formula (II-2). Colored curable composition.

[In General Formula (II-2), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ , and R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , and R ¹³ are Each independently represents a hydrogen atom or a substituent. R ⁷ and R ¹⁴ each independently represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. Ma represents a metal atom or a metal compound. ] The colored curing according to claim 1, wherein the complex represented by (A-1) the compound represented by the general formula (I) is coordinated to a metal atom or a metal compound is a compound represented by the following general formula (III). Sex composition.

[In General Formula (III), R ² , R ³ , R ⁴ , and R ⁵ each independently represent a hydrogen atom or a substituent. R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. Ma represents a metal atom or a metal compound, and X ³ represents NR (R represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group. ), A nitrogen atom, an oxygen atom, or a sulfur atom, and X ⁴ represents NRa (Ra represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group. Represents an oxygen atom or a sulfur atom. Y ¹ represents NRc (Rc represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group) or a group containing a carbon atom; ² represents a nitrogen atom or a group containing a carbon atom. R ⁸ and R ⁹ each independently represents an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylamino group, an arylamino group, or a heterocyclic amino group. R ⁸ and Y ¹ may be bonded to each other to form a 5-, 6-, or 7-membered ring, and R ⁹ and Y ² are bonded to each other to form a 5-, 6-, or 7-membered ring. The ring may be formed. X ⁵ represents a group capable of binding to Ma, and a represents 0, 1, or 2. ]   The colored curable composition according to any one of claims 1 to 4, wherein the metal atom or metal compound is any one of Fe, Zn, Co, V = O, and Cu. The colored curable composition according to any one of claims 1 to 5, wherein each of R ³ and R ⁴ is a phenyl group. At least one of the colored curable composition according to any one of claims 1 to 6 is 2,6-di -tert- butyl-4-methyl cyclohexyloxy carbonyl group of the ^{R 2} and the ^{R 5} object. A layer forming step of forming a colored curable composition layer by applying the colored curable composition according to any one of claims 1 to 7 on a support;
A pattern forming step of exposing the colored curable composition layer through a mask and developing to form a colored pattern; and
The manufacturing method of the color filter which has.   The method for producing a color filter according to claim 8, wherein the pattern forming step includes a step of heating the colored curable composition layer before development after exposure.   A color filter manufactured by the method for manufacturing a color filter according to claim 8.   A solid-state imaging device comprising the color filter according to claim 10.