KR101768981B1 - Colored composition, colored curable composition, color filter, method of producing color filter, solid-state imaging device, and liquid crystal display device - Google Patents

Abstract

(PROBLEMS) To provide a colored composition which is capable of forming a colored film having high heat resistance and light resistance and excellent in storage stability.
(B) a phthalocyanine-based pigment; (C) a dispersing agent; and (D) at least one compound selected from the group consisting of (D) a compound represented by the following general formula ) Organic solvent. In the general formula (1), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ each independently represent a hydrogen atom or a monovalent substituent, and R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, , Or a heterocyclic group.

Description

TECHNICAL FIELD [0001] The present invention relates to a coloring composition, a coloring curable composition, a color filter, a method of manufacturing a color filter, a solid-state image pickup device, and a liquid crystal display device using the color filter. DISPLAY DEVICE}

The present invention relates to a colored composition, a colored curable composition, a color filter, a production method of a color filter, a solid-state image pickup device, and a liquid crystal display device.

BACKGROUND ART [0002] A pigment dispersion method is widely known as a method for producing a color filter used in a liquid crystal display device (LCD or the like) or a solid-state image pickup device (CCD, CMOS, etc.).

In the pigment dispersion method, a colored curable composition obtained by dispersing a pigment in a curable composition is used, and a color filter is produced by photolithography. Specifically, a colored curable composition is applied on a glass substrate by a spin coater, roll coater or the like to form a coated film, the coated film is pattern-exposed and then developed to form colored pixels, and this operation is repeated for each color A color filter is produced. Since the pigment dispersion method is applied by photolithography, the position accuracy is high, and it is a preferable method for manufacturing a large-sized or high-definition color filter.

As a color-curable composition containing a pigment, a blue coloring composition for a color filter containing a phthalocyanine-based pigment is known (see, for example, Patent Document 1).

A pigment having a smaller particle size has been required from the viewpoint of improving the contrast of a display element with respect to a color filter used in a liquid crystal display device or a solid-state image pickup device. If the fineness of the pigment is insufficient, light is scattered by the pigment, birefringence is caused and the polarization axis is rotated, the light transmittance is lowered, and the contrast is lowered. Further, if the fineness of the pigment is insufficient, the curing sensitivity of the colored curable composition is lowered.

In response to such a situation, a technique of using dyes instead of pigments has been proposed. However, it is known that dyes generally have poor light resistance and heat resistance as compared with pigments, which is a problem in view of the performance of color filters. Further, the dye has a low solubility in the curable composition, and in the state of the liquid preparation or the coating film, stability with time is low and the dye is precipitated. In addition, the dye in which the molecules are dispersed has a high polymerization inhibiting ability, and the curing sensitivity of the colored curable composition is lowered.

To solve such a problem, there is proposed a colored curable composition capable of forming a color filter having excellent storage stability and high light resistance by using a dipyrromethene dye and a phthalocyanine dye in combination (see, for example, Patent Document 2). Further, there is known a technique of performing color correction of a pigment with a dye, and a colored curable composition in which a dye and a pigment are combined is disclosed (for example, see Patent Document 3).

Japanese Patent Application Laid-Open No. 2001-33616 Japanese Patent Application Laid-Open No. 2008-292970 U.S. Patent Application Publication No. 2008/0171271

The colored curable composition comprising a dye can provide a color filter having excellent storage stability and a high light resistance by the selection of a dye to be used but has a better effect for a better high definition of a color filter and a performance improvement Development of a colored curable composition is desired.

Accordingly, it is an object of the present invention to provide a colored composition excellent in storage stability capable of forming a colored film having high heat resistance and light resistance, and a first object of the present invention is to achieve this object.

Another object of the present invention is to provide a colored curable composition capable of forming a colored cured film having high curing sensitivity to pattern exposure and high heat resistance and light resistance, and achieving this object is a second object.

It is still another object of the present invention to provide a color filter having a high transmittance and excellent heat resistance and light resistance, a method of manufacturing the color filter, and a solid-state image pickup device and a liquid crystal display device provided with the color filter. The third task.

Specific means for achieving the above object are as follows.

(B) a phthalocyanine-based pigment, (C) a dispersant, and (D) at least one compound selected from the group consisting of a compound represented by the following general formula (1) A coloring composition comprising an organic solvent.

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

<2> A colored composition according to <1>, wherein the (A-1) dipyrammethene metal complex compound is (A-2) a dipyrammethene metal complex compound represented by the following general formula (2)

In the general formula (2), R ² , R ³ , R ⁴ and R ⁵ each independently represent a hydrogen atom or a monovalent substituent, and R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group. 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. And Ma represents a metal atom or a metal compound. X ³ and X ⁴ each independently represent NR a (wherein R a 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), an oxygen atom or a sulfur atom. Y ¹ and Y ² each independently represent NRb (Rb 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 carbon atom. X ⁵ represents a group capable of bonding to Ma, and a represents 0, 1 or 2; 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 may be bonded to each other to form a 5-membered, 6-membered or 7-membered ring.

(3) The colored composition according to (1), wherein the (A-1) dipyrammethene metal complex compound is (A-3) a dipyrammethene metal complex compound represented by the following general formula (3)

In the general formula (3), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ each independently represent a monovalent substituent, M represents a metal or a metal compound, A substituted or unsubstituted alkylsulfonyloxy group, a substituted or unsubstituted arylsulfonyloxy group, or a halogen atom; n1 and n2 each independently represent an integer of 0 to 5 , And n3 and n4 each independently represent an integer of 0 to 3;

<4> A colored composition according to <1>, wherein the (A-1) dipyrammethene metal complex compound is (A-4) a dipyrammethene metal complex compound represented by the following general formula (4)

In the general formula (4), R ¹³ and R ¹⁴ each independently represents a monovalent substituent, and X represents a substituted or unsubstituted acyloxy group having 2 to 3 carbon atoms, a substituted or unsubstituted alkylsulfonyloxy group, A substituted arylsulfonyloxy group, or a halogen atom.

<5> A colored composition according to any one of <1> to <4>, wherein the phthalocyanine pigment (B) is Pigment Blue 15: 6.

(6) A colored curable composition comprising the coloring composition according to any one of (1) to (5), (E) a polymerizable compound, and (F) a polymerization initiator.

<7> The colored curable composition according to <6>, wherein the (E) polymerizable compound is a (meth) acrylate-based polyfunctional monomer.

<8> The colored curable composition according to <6> or <7>, wherein the polymerization initiator (F) is a oxime-based compound.

<9> A color filter having a colored layer formed by using the colored composition according to any one of <1> to <5>, or the colored curable composition according to any one of <6> to <8>

&Lt; 10 > A process for producing a colored layer, comprising the steps of: forming a colored layer by applying the colored curable composition according to any one of < 6 > to & And a developing step of developing the colored layer on which the latent image is formed to form a pattern.

&Lt; 11 > A color filter produced by the method of manufacturing a color filter according to < 10 >.

&Lt; 12 > A solid-state imaging device comprising the color filter according to < 9 > or < 11 >.

&Lt; 13 > A liquid crystal display device comprising the color filter according to <9> or <11>.

(Effects of the Invention)

According to the present invention, it is possible to provide a coloring composition excellent in storage stability capable of forming a colored film having high heat resistance and light resistance.

Further, according to the present invention, it is possible to provide a colored curable composition capable of forming a colored cured film having high curing sensitivity to pattern exposure and high heat resistance and light resistance.

Further, according to the present invention, it is possible to provide a color filter having a high transmittance and excellent heat resistance and light resistance, a method of manufacturing the color filter, and a solid-state image pickup device and a liquid crystal display device provided with the color filter.

The description of the constitution of the present invention described below may be made based on a representative embodiment of the present invention, but the present invention is not limited to such embodiment. In the present specification, the numerical range indicated by using &quot; ~ &quot; means a range including numerical values before and after &quot; ~ &quot; as a lower limit value and an upper limit value.

<Coloring composition>

The coloring composition of the present invention comprises (A-1) a dipyrammethene metal complex compound containing a compound represented by the general formula (1) and a metal atom or a metal compound, (B) a phthalocyanine pigment, (C) (D) an organic solvent.

(A-1) A dipyrammethene metal complex compound containing a compound represented by the above general formula (1) and a metal atom or a metal compound includes (A-2) a dipyrammethene metal complex represented by the general formula (2) (A-3) a dipyrammethene metal complex compound represented by the general formula (3) is more preferable, and (D-4) a dipyrammethene metal complex compound represented by the general formula (4) Is more preferable.

Hereinafter, a dipyrammethene metal complex compound containing a compound represented by the above general formula (1) and a metal atom or a metal compound is sometimes referred to as a &quot; specific dipyramethane metal complex compound &quot;. In a specific dipyrammethene metal complex compound, NH of the compound represented by the general formula (1) may be deprotonated. Therefore, the specific dipyrammethene metal complex compound includes (A-2) the dipyrammethene metal complex compound represented by the general formula (2), (A-3) the dipyrammethene metal complex represented by the general formula (3) (A-4) a dipyrammethene metal complex compound represented by the above general formula (4). In some cases, (A-1), (A-2), (A-3) and (A-4) are collectively referred to as (A).

The coloring composition of the present invention is used in combination with a specific dipyramethane metal complex compound and a phthalocyanine-based pigment. The combination of a specific dipyramethylene metal complex compound and a phthalocyanine-based pigment has heretofore not been known.

The coloring composition of the present invention exhibits the following remarkable effects of (i) to (iii) by using a specific dipyrammethene metal complex compound in combination with a phthalocyanine-based pigment.

(i) The coloring composition of the present invention has a higher transmittance of blue light than a coloring composition prepared by using a phthalocyanine-based dye in combination with a dipyrammethene metal complex compound.

(ii) The coloring composition of the present invention is high in heat resistance and light fastness to the same extent as the coloring composition obtained by using the diphyromethane metal complex compound in combination with the phthalocyanine-based dye.

(iii) The colored curable composition prepared by using the coloring composition of the present invention has a higher curing sensitivity by exposure than the colored curable composition prepared by using a coloring composition comprising a dipyrammethene metal complex compound and a phthalocyanine-based dye in combination. Particularly, the use of the dipyrammethene metal complex compound represented by the general formula (2) (more preferably the general formula (3), particularly preferably the general formula (4)) has a higher curing sensitivity.

Hereinafter, the specific dipyrammethene metal complex compound (A), the phthalocyanine pigment (B), the dispersant (C) and the organic solvent (D) contained in the coloring composition of the present invention will be described in detail.

[(A) Specific Dipyrromethene Metal Complex Compound]

Hereinafter, the dipyrammethene metal complex compound containing a compound represented by the following general formula (1) and a metal atom or a metal compound will be described in detail.

Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a monovalent substituent and R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group , Or a heterocyclic group.

Examples of the monovalent substituent represented by R ¹ to R ⁶ in the general formula (1) include a halogen atom (for example, a fluorine atom, a chlorine atom and a bromine atom), an alkyl group (preferably having a carbon number of 1 to 48, More preferably a straight chain, branched chain or cyclic alkyl group having 1 to 24 carbon atoms, and examples thereof include a methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, pentyl group, Cyclohexyl group, 1-norbornyl group, 1-adamantyl group), an alkenyl group (preferably a cycloalkyl group having 1 to 20 carbon atoms An allyl group, a 3-buten-l-yl group), an aryl group (preferably having 6 to 48 carbon atoms, more preferably an alkenyl group having 2 to 48 carbon atoms, Is an aryl group having 6 to 24 carbon atoms, for example, a phenyl group or a naphthyl group), a heterocyclic group (preferably having 1 to 32 carbon atoms, Preferably 1 to 18 carbon atoms, and examples thereof include a 2-thienyl group, a 4-pyridyl group, a 2-furyl group, a 2-pyrimidinyl group, a 1-pyridyl group, a 2-benzothiazolyl group, An imidazolyl group, a 1-pyrazolyl group, a benzotriazol-1-yl group), a silyl group (preferably a silyl group having 3 to 38 carbon atoms, more preferably 3 to 18 carbon atoms, Butylsilyl group, t-butyldimethylsilyl group), a hydroxyl group, a cyano group, a nitro group, an alkoxy group (preferably having 1 to 48 carbon atoms, more preferably a silyl group Is an alkoxy group having 1 to 24 carbon atoms and includes, for example, methoxy, ethoxy, 1-butoxy, 2-butoxy, isopropoxy, (For example, a cyclopentyloxy group, a cyclohexyloxy group), an aryloxy group (preferably having 6 to 48 carbon atoms, more preferably a carbon number An aryloxy group having 6 to 24 carbon atoms such as a phenoxy group and a 1-naphthoxy group), a heterocyclic oxy group (preferably having 1 to 32 carbon atoms, more preferably a heterocyclic oxy group having 1 to 18 carbon atoms (For example, 1-phenyltetrazole-5-oxy group, 2-tetrahydropyranyloxy group), a silyloxy group (preferably having 1 to 32 carbon atoms, more preferably a silyloxy group having 1 to 18 carbon atoms For example, a trimethylsilyloxy group, a t-butyldimethylsilyloxy group, a diphenylmethylsilyloxy group), an acyloxy group (preferably an acyloxy group having 2 to 48 carbon atoms, more preferably an acyloxy group having 2 to 24 carbon atoms (For example, an acetoxy group, a pivaloyloxy group, a benzoyloxy group, a dodecanoyloxy group), an alkoxycarbonyloxy group (preferably having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, And examples thereof include an ethoxycarbonyloxy group, a t-butoxycarbonyloxy group, (For example, a cyclohexyloxycarbonyloxy group), an aryloxycarbonyloxy group (preferably having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms, such as aryloxy (Preferably phenoxycarbonyloxy group), carbamoyloxy group (preferably having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as N , N-dimethylcarbamoyloxy group, N-butylcarbamoyloxy group, N-phenylcarbamoyloxy group and N-ethyl-N-phenylcarbamoyloxy group), sulfamoyloxy group (preferably having 1 to 32 carbon atoms, More preferably a sulfamoyloxy group having 1 to 24 carbon atoms, for example, N, N-diethylsulfamoyloxy group, N-propylsulfamoyloxy group)

An alkylsulfonyloxy group (preferably having 1 to 38 carbon atoms, more preferably an alkylsulfonyloxy group having 1 to 24 carbon atoms, such as a methylsulfonyloxy group, a hexadecylsulfonyloxy group, a cyclohexylsulfonyloxy group) An arylsulfonyloxy group (preferably 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, Preferably an acyl group having 1 to 24 carbon atoms, such as a formyl group, an acetyl group, a pivaloyl group, a benzoyl group, a tetradecanoyl group and a cyclohexanoyl group), an alkoxycarbonyl group (preferably having 2 to 48 carbon atoms, More preferably an alkoxycarbonyl group having 2 to 24 carbon atoms, and examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group, an octadecyloxycarbonyl group, a cyclohexyloxycarbonyl group, 2,6-di-tert-butyl- Silk Oxica An aryloxycarbonyl group (preferably an aryloxycarbonyl group having 7 to 32 carbon atoms, more preferably a carbon number 7 to 24, such as a phenoxycarbonyl group), a carbamoyl group (preferably having 1 to 48 carbon atoms , More preferably a carbamoyl group having 1 to 24 carbon atoms, such as a carbamoyl group, an N, N-diethylcarbamoyl group, an N-ethyl-N-octylcarbamoyl group, An N-phenylcarbamoyl group, an N-methylcarbamoyl group, an N, N-dicyclohexylcarbamoyl group), an amino group (preferably having a carbon number of not more than 32, Preferably an amino group having 24 or less carbon atoms, and examples thereof include an amino group, a methylamino group, an N, N-dibutylamino group, a tetradecylamino group, a 2-ethylhexylamino group and a cyclohexylamino group) An anilino group having 6 to 32, more preferably 6 to 24 , An anilino group, an N-methylanilino group), a heterocyclic amino group (preferably a heterocyclic amino group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, for example, 4-pyridyl An amino group), a carbonamido group (preferably a carbonamido group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, such as an acetamide group, a benzamide group, a tetradecanamide group, a pivaloylamide group , Cyclohexanamide group), an ureido group (preferably a ureido group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, such as an ureido group, an N, N-dimethyl ureido group, (Preferably an imido group having not more than 36 carbon atoms, more preferably not more than 24 carbon atoms, such as an N-succinimide group and an N-phthalimide group), an alkoxycarbonylamino group Preferably 2 to 48 carbon atoms, more preferably 2 to &lt; RTI ID = 0.0 &gt; An alkoxycarbonylamino group having 1 to 24 carbon atoms, for example, a methoxycarbonylamino group, an ethoxycarbonylamino group, a t-butoxycarbonylamino group, an octadecyloxycarbonylamino group, a cyclohexyloxycarbonylamino group) An oxycarbonylamino group (preferably an aryloxycarbonylamino group having 7 to 32 carbon atoms, more preferably a carbon number 7 to 24, such as a phenoxycarbonylamino group), a sulfonamide group (preferably having 1 to 20 carbon atoms, A sulfonamido group having from 1 to 48 carbon atoms, more preferably from 1 to 24 carbon atoms, and examples thereof include a methanesulfonamide group, a butanesulfonamide group, a benzenesulfonamide group, a hexadecanesulfonamide group and a cyclohexanesulfonamide group) An amino group (preferably a C 1-48, more preferably a C 1-24 sulfamoylamino group, for example, an N, N-dipropylsulfamoylamino group, N-ethyl-N-dodecylsulfamoylamino An azo group (preferably an azo group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, such as a phenyl azo group and a 3-pyrazolyl azo group)

An alkylthio group (preferably an alkylthio group having 1 to 48 carbon atoms, more preferably a carbon number 1 to 24, such as methylthio group, ethylthio group, octylthio group, cyclohexylthio group) (Preferably an arylthio group having from 6 to 48 carbon atoms, and more preferably from 6 to 24 carbon atoms, such as a phenylthio group), a heterocyclic thio group (preferably having 1 to 32 carbon atoms, Benzothiazolylthio group, 2-pyridylthio group, 1-phenyltetrazolylthio group), an alkylsulfinyl group (preferably having 1 to 32 carbon atoms, preferably 1 to 30 carbon atoms, More preferably an alkylsulfinyl group having 1 to 24 carbon atoms, such as a dodecansulfinyl group), an arylsulfinyl group (preferably an arylsulfinyl group having 6 to 32 carbon atoms, more preferably a carbon number 6 to 24, For example, a phenylsulfinyl group), an alkylsulfonyl group (preferably having 1 to 48 carbon atoms, Preferably an alkylsulfonyl group having 1 to 24 carbon atoms, and examples thereof include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, a butylsulfonyl group, an isopropylsulfonyl group, a 2-ethylhexylsulfonyl group, a hexadecylsulfonyl group, An arylsulfonyl group (preferably an arylsulfonyl group having 6 to 48 carbon atoms, and more preferably a carbon number of 6 to 24, such as phenylsulfonyl group, 1-naphthylsulfonyl group, ), A sulfamoyl group (preferably a sulfamoyl group having not more than 32 carbon atoms, more preferably not more than 24 carbon atoms, such as sulfamoyl group, N, N-dipropylsulfamoyl group, (Preferably having 1 to 32 carbon atoms, more preferably 1 to 8 carbon atoms, more preferably 1 to 10 carbon atoms, more preferably 1 to 20 carbon atoms, A phosphonyl group having from 1 to 24 carbon atoms, for example, a phenoxyphosphonyl group, octyloxyphospho group And a phosphinoylamino group (preferably a phosphinoylamino group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, such as diethoxyphosphinoylamino group, dioctyloxy group, Phosphinoylamino group).

When the above-mentioned monovalent group is a substitutable group, it may be further substituted by any one of the above-mentioned groups. On the other hand, when two or more substituents are present, these substituents may be the same or different.

In the general formula (1), 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 form a 5-membered, 6-membered or 7-membered ring It may be. As the ring formed, there can be mentioned a phthalocyanine ring or an unsaturated ring. Examples of the 5-membered, 6-membered or 7-membered ring or unsaturated ring include a furan ring, a furan ring, a thiophene ring, a pyrazole ring, an imidazole ring, a triazolene ring, an oxazole ring, a thiazole ring, a pyrrolidine ring, A cyclopentene ring, a cyclohexane ring, a benzene ring, a pyridine ring, a pyrazine ring and a pyridazin ring, and preferred examples thereof include a benzene ring and a pyridine ring.

When the five-membered, six-membered and seven-membered rings formed are further substitutable groups, they may be substituted with any of the monovalent substituents described above for R ¹ to R ⁶ , and when they are substituted with two or more substituents These substituents may be the same or different.

As the monovalent substituent represented by R ¹ and R ⁶ in the general formula (1), among the above, an alkylamino group, an arylamino group, an anilino group, a heterocyclic amino group, a carbonamido group, an ureido group, an imide group, an alkoxycarbonylamino group , An aryloxycarbonylamino group and a sulfonamide group are preferable, and a carnamide group, an ureido group, an alkoxycarbonylamino group and a sulfonamide group are more preferable, and a carbonamide group, an ureido group, an alkoxycarbonylamino group and a sulfonamide group are more preferable And a carbonamido group and a ureido group are particularly preferable.

The monovalent substituent represented by R ² and R ⁵ in the general formula (1) is preferably a halogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a hydroxy group, a cyano group, a nitro group, an alkoxy group, A heterocyclic oxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylcarbamoyl group, an arylcarbamoyl group, an alkoxycarbonylamino group, a sulfonamide group, an azo group, an alkylthio group, an arylthio group, A sulfonyl group, an arylsulfonyl group, a sulfamoyl group, a nitrile group, an imide group, a carbamoyl sulfonyl group and a cyano group are preferable and an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a cyano group, a nitro group, An aryloxycarbonyl group, an alkylcarbamoyl group, an arylcarbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, a nitrile group, an imide group, a carbamoyl sulfonyl group and a cyano group More preferred are an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a nitrile group, an imide group, a carbamoylsulfonyl group and a cyano group, and particularly preferably an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group or a cyano group .

The monovalent substituent represented by R ³ and R ⁴ in the general formula (1) is preferably a halogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a silyl group, a hydroxyl group, a cyano group, an alkoxy group, An acyl group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, an anilino group, a carbonamido group, an ureido group, an imide group, an alkoxycarbonylamino group, a sulfonamide group, an azo group, More preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, and more preferably a substituted or unsubstituted heterocyclic group , More preferably a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group.

The alkyl group when R ³ and R ⁴ in the general formula (1) represent an alkyl group is preferably a linear, branched or cyclic substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, and more specifically, , A methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclopropyl group, an n-butyl group, an i-butyl group, a t-butyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, have. More preferably a branched or cyclic substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, and more specifically, an isopropyl group, a cyclopropyl group, an i-butyl group, a t-butyl group, A cyclopentyl group, and a cyclohexyl group. More preferably a secondary or tertiary substituted or unsubstituted alkyl group having 1 to 12 carbon atoms. More specifically, examples thereof include an isopropyl group, a cyclopropyl group, an i-butyl group, a t-butyl group, A butyl group, and a cyclohexyl group.

In the general formula (1), when R ³ and R ⁴ represent an aryl group, the aryl group is preferably a substituted or unsubstituted phenyl group or a substituted or unsubstituted naphthyl group, more preferably a substituted or unsubstituted phenyl group to be.

The heterocyclic group when R ³ and R ⁴ in the general formula (1) represent a heterocyclic group is preferably a substituted or unsubstituted 2-thienyl group, a substituted or unsubstituted 4-pyridyl group, a substituted or unsubstituted Substituted or unsubstituted 2-pyridyl groups, substituted or unsubstituted 2-pyridyl groups, substituted or unsubstituted 1-pyridyl groups, substituted or unsubstituted 2-furyl groups, substituted or unsubstituted 2-pyrimidinyl groups, Benzothiazolyl group, a substituted or unsubstituted 1-imidazolyl group, a substituted or unsubstituted 1-pyrazolyl group, or a substituted or unsubstituted benzotriazol-1-yl group, more preferably a substituted Or a substituted or unsubstituted 2-thienyl group, a substituted or unsubstituted 4-pyridyl group, a substituted or unsubstituted 1-pyridyl group, a substituted or unsubstituted 2-furyl group, or a substituted or unsubstituted 2-pyrimidinyl group .

In the general formula (1), R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group (preferably having 1 to 24 carbon atoms, more preferably an alkyl group having 1 to 12 carbon atoms such as methyl, ethyl, Cyclohexyl, adamantyl), an aryl group (preferably having 6 to 24 carbon atoms, more preferably aryl having 6 to 12 carbon atoms, such as methyl, ethyl, propyl, isopropyl, (For example, phenyl, naphthyl) or a heterocyclic group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, such as 2-thienyl, 2-pyridyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, benzotriazol-1-yl). Among the above R ⁷ , a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group is preferable, a hydrogen atom or an alkyl group is more preferable, and a hydrogen atom is more preferable.

The alkyl group, aryl group and heterocyclic group of R ⁷ may be substituted with the substituents described above for R ¹ to R ⁶ , and when they are substituted with two or more substituents, these substituents may be the same or different good.

Next, the metal atom or metal compound in which the compound represented by the general formula (1) is coordinated to form a dipyrammethene metal complex compound will be described.

The metal or metal compound may be any metal atom or metal compound capable of forming a complex, and includes a divalent metal atom, a divalent metal oxide, a divalent metal hydroxide, or a divalent metal chloride. For example, AlCl ₃ , InCl ₃ , FeCl ₂ , TiCl ₂ , SnCl ₂ , and the like may be used in addition to Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Metal chlorides such as SiCl ₂ and GeCl ₂ , metal oxides such as TiO ₂ and VO, and metal hydroxides such as Si (OH) ₂ . Of these, preferred are Fe, Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO, B, or VO in view of stability of the complex, spectral characteristics, heat resistance, light resistance, And most preferably Fe, Zn, Cu, Co, B, or VO (V = O), and most preferably Fe, Zn, Mg, Si, Pt, Pd, Cu, Ni, . Of these, Zn is particularly preferable.

Preferred forms of the dipyrammethene metal complex compound in which the compound represented by the above general formula (1) is coordinated with a metal atom or a metal compound are shown below.

That is, in the general formula (1), R ¹ and R ⁶ each independently represents a hydrogen atom, an alkylamino group, an arylamino group, an anilino group, a heterocyclic amino group, a carbonamido group, an ureido group, An aryloxycarbonylamino group, a sulfonamide group,

R ² and R ⁵ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a hydroxy group, a cyano group, a nitro group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, An aryloxycarbonyl group, an alkylcarbamoyl group, an arylcarbamoyl group, an alkoxycarbonylamino group, a sulfonamido group, an azo group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, A nitro group, a nitrile group, an imide group, a carbamoyl sulfonyl group, or a cyano group,

R ³ and R ⁴ each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a silyl group, a hydroxy group, a cyano group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, An aryl group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, an arylsulfonyl group, an arylsulfonyl group, an arylsulfonyl group, an arylsulfonyl group, an arylsulfonyl group, an arylsulfonyl group, an arylsulfonyl group, A sulfamoyl group, a sulfamoyl group, or a phosphinoylamino group,

R ⁷ is a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group,

The metal atom or the metal compound may be Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO, B or VO.

More preferable forms of the dipyramethylene metal complex compound are shown below.

That is, in the general formula (1), R ¹ and R ⁶ each independently represents a hydrogen atom, an alkylamino group, an arylamino group, an anilino group, a heterocyclic amino group, a carbonamido group, an ureido group, an imide group, an alkoxycarbonylamino group , An aryloxycarbonylamino group, a sulfonamide group,

R ² and R ⁵ are each independently selected from the group consisting of alkyl, alkenyl, aryl, heterocyclic, cyano, nitro, acyl, alkoxycarbonyl, aryloxycarbonyl, alkylcarbamoyl, arylcarbamoyl, An arylsulfonyl group, a sulfamoyl group, a nitrile group, an imide group, a carbamoylsulfonyl group and a cyano group,

R ³ and R ⁴ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a cyano group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, a carbonamido group, an ureido group, An amino group, a sulfonamide group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, or a sulfamoyl group,

R ⁷ is a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group,

The metal atom or the metal compound may be Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, B or VO.

A particularly preferred form of the dipyrammethene metal complex compound in which the compound represented by the general formula (1) is coordinated to a metal atom or a metal compound is a dipyramethanemethine complex compound represented by the following general formula (2).

[(A-2) Dipyrromethene metal complex compound represented by general formula (2)] [

Hereinafter, the dipyrammethene metal complex compound represented by the following general formula (2) will be described in detail.

In the general formula (2), R ² , R ³ , R ⁴ and R ⁵ each independently represent a hydrogen atom or a monovalent substituent, and R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group . 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. And Ma represents a metal atom or a metal compound. X ³ and X ⁴ each independently represent NR a (wherein R a 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), an oxygen atom or a sulfur atom. Y ¹ and Y ² each independently represent NRb (Rb 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 carbon atom. X ⁵ represents a group capable of bonding to Ma, and a represents 0, 1 or 2; 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 may be bonded to each other to form a 5-membered, 6-membered or 7-membered ring. The dipyrammethene metal complex compound represented by the general formula (2) includes a tautomer.

Formula (2) of R ² ~R ⁵ and R ⁷ is R ² and R ⁵ ~R ⁷ and copper in the formula (1), as a preferred form.

Ma in the general formula (2) represents a metal or a metal compound and is in agreement with a metal atom or a metal compound in the dipyrammethene metal complex compound of the general formula (1), and preferable examples thereof are also the same.

In the general formula (2), R ⁸ and R ⁹ are each independently an alkyl group (preferably a straight chain, branched chain or cyclic alkyl group having 1 to 36 carbon atoms, more preferably a straight chain, branched chain or cyclic alkyl group having 1 to 12 carbon atoms, , Ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, hexyl group, 2-ethylhexyl group, dodecyl group, cyclopropyl group, cyclopentyl group, An allyl group, a 3-butene-1-yl group), an aryl group (preferably an alkenyl group having 2 to 12 carbon atoms, more preferably an alkenyl group having 2 to 24 carbon atoms, Preferably 6 to 36 carbon atoms, more preferably 6 to 18 carbon atoms, such as a phenyl group or a naphthyl group), a heterocyclic group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms Examples of the heterocyclic group include a 2-thienyl group, a 4-pyridyl group, a 2-furyl group, a 2-pyrimidinyl group, An alkoxy group (preferably an alkoxy group having 1 to 36 carbon atoms, more preferably an alkoxy group having 1 to 18 carbon atoms, such as a methoxy group, an ethoxy group, an isopropoxy group, an isopropoxy group, (For example, a methoxy group, an ethoxy group, a propyloxy group, a butoxy group, a hexyloxy group, a 2-ethylhexyloxy group, a dodecyloxy group and a cyclohexyloxy group) More preferably an alkyloxy group having 1 to 18 carbon atoms, more preferably an aryloxy group having 1 to 18 carbon atoms such as a phenoxy group and a naphthyloxy group), an alkylamino group (preferably an alkylamino group having 1 to 36 carbon atoms, Examples of the alkyl group include a methylamino group, an ethylamino group, a propylamino group, a butylamino group, a hexylamino group, a 2-ethylhexylamino group, an isopropylamino group, a t-butylamino group, a t-octylamino group, a cyclohexylamino group, , N, N-dipropylamino group, N, N-dibutylamino group, Ethylamino group), an arylamino group (preferably an arylamino group having 6 to 36 carbon atoms, more preferably 6 to 18 carbon atoms, such as a phenylamino group, a naphthylamino group, an N, N-di A phenylamino group, an N-ethyl-N-phenylamino group), or a heterocyclic amino group (preferably a heterocyclic amino group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, A 3-aminopyrazole group, a 2-aminopyridine group, and a 3-aminopyridine group).

When the alkyl group, alkenyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, alkylamino group, arylamino group, or heterocyclic amino group represented by R ⁸ and R ⁹ in the general formula (2) May be substituted with any one of the substituents described with respect to R ¹ to R ⁶ in the general formula (1), and when they are substituted with two or more substituents, these substituents may be the same or different.

In the general formula (2), X ³ and X ⁴ each independently represent NRa, an oxygen atom or a sulfur atom. Ra is a hydrogen atom, an alkyl group (preferably having 1 to 36 carbon atoms, more preferably a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl Cyclohexyl group, 1-adamantyl group), an alkenyl group (preferably a cycloalkyl group having 2 to 6 carbon atoms, such as a methyl group, an ethyl group, an isobutyl group, a t-butyl group, a hexyl group, An allyl group, a 3-butene-1-yl group), an aryl group (preferably having 6 to 36 carbon atoms, more preferably an alkenyl group having 2 to 12 carbon atoms, (Preferably an aryl group having 6 to 18 carbon atoms, such as a phenyl group or a naphthyl group), a heterocyclic group (preferably having 1 to 24 carbon atoms, more preferably a heterocyclic group having 1 to 12 carbon atoms, Pyridyl group, 2-furyl group, 2-pyrimidinyl group, 1-pyridyl group, 2-benzothiazolyl group, 1-imidazolyl group, 1- An acyl group (preferably an acyl group having 1 to 24 carbon atoms, more preferably a 2 to 18 carbon atoms, such as an acetyl group, a pivaloyl group, a 2- Ethylhexyl group, benzoyl group, cyclohexanoyl group), an alkylsulfonyl group (preferably an alkylsulfonyl group having 1 to 24 carbon atoms, more preferably 1 to 18 carbon atoms, such as a methylsulfonyl group, an ethylsulfonyl group, An arylsulfonyl group (preferably an arylsulfonyl group having 6 to 24 carbon atoms, and more preferably a carbon number of 6 to 18, such as phenylsulfonyl group and naphthylsulfonyl group), an arylsulfonyl group . When Ra is substitutable, it may be further substituted with a substituent, and when it is substituted with a plurality of substituents, these substituents may be the same or different.

X ³ and X ⁴ are preferably each independently NRa (Ra is a hydrogen atom, an alkyl group or a heterocyclic group), an oxygen atom or a sulfur atom, and particularly preferably all of X ³ and X ⁴ are oxygen atoms.

In the general formula (2), Y ¹ and Y ² each independently represent NRb or a carbon atom, Rb is the same as that of Ra in X ³ and X ⁴ , and the preferred form thereof is also the same.

Y ¹ and Y ² are preferably each independently NRb (Rb is a hydrogen atom or an alkyl group) or a carbon atom, and particularly preferably Y ¹ and Y ² are all NH.

In the general formula (2), R ⁸ and Y ¹ are bonded to each other to form a 5-membered ring together with R ⁸ , Y ¹ and a carbon atom (for example, cyclopentane, pyrrolidine, tetrahydrofuran, dioxolane, Benzene, thiophene), a 6-membered ring (e.g., cyclohexane, piperidine, piperazine, morpholine, tetrahydropyrane, dioxane, pentamethylene sulfide , Dithiane, benzene, piperidine, piperazine, pyridazine, quinoline, quinazoline), or a 7-membered ring (for example, cycloheptane, hexamethyleneimine).

In the general formula (2), R ⁹ and Y ² may be bonded to form a 5-membered, 6-membered or 7-membered ring together with R ⁹ , Y ² and a carbon atom. The 5-membered, 6-membered, and 7-membered rings formed may be rings in which one of the rings formed by R ⁸ and Y ¹ and the carbon atom is changed into a double bond.

When 5, 6, and 7-membered rings formed by combining R ⁸ and Y ¹ and R ⁹ and Y ² in the general formula (2) are more substitutable rings, R ¹ in the general formula (1) To R ⁶ , and when they are substituted with two or more substituents, these substituents may be the same or different.

In the general formula (2), X ⁵ may be any group capable of bonding to Ma, specifically, a group derived from water, alcohols (e.g., methanol, ethanol, propanol) (2) (1996), [3] (1997), Nanko et al.), All of which are incorporated herein by reference. Among them, a group derived from water, a carboxylic acid compound, a sulfonic acid compound or an alcohol is preferable in terms of production, and a group derived from water, a carboxylic acid compound or a sulfonic acid compound is more preferable. a represents 0, 1 or 2; When a is 2, X5 may be the same or different.

Preferable forms of the compound represented by the above general formula (2) are shown below. That is, in the general formula (2)

R ² to R ⁵ , R ⁷ and Ma are each a preferred form of a dipyrammethene metal complex compound containing a compound represented by the above general formula (1) and a metal atom or a metal compound,

X ³ and X ⁴ are each independently NRa (Ra is a hydrogen atom, an alkyl group or a heterocyclic group), an oxygen atom or a sulfur atom,

Y ¹ and Y ² are each independently NRb (Rb is a hydrogen atom or an alkyl group), a nitrogen atom or a carbon atom,

X &lt; ⁵ &gt; is a group bonded through an oxygen atom or a nitrogen atom, a is 0 or 1,

R ⁸ and R ⁹ are each independently an alkyl group, an aryl group, a heterocyclic group, an alkoxy group or an alkylamino group, or R ⁸ and Y ¹ and R ⁹ and Y ² are bonded to each other to form a 5-membered or 6-membered ring.

More preferred forms of the compound represented by the above general formula (2) are shown below. That is, in the general formula (2)

R ² to R ⁵ , R ⁷ and Ma are each a preferred form of a complex containing a compound represented by the general formula (1) and a metal atom or a metal compound,

X ³ and X ⁴ are both oxygen atoms,

Y ¹ and Y ² are both NH,

X &lt; ⁵ &gt; is a group bonded through an oxygen atom or a nitrogen atom, a is 0 or 1,

R ⁸ and R ⁹ are each independently an alkyl group, an aryl group, a heterocyclic group, an alkoxy group or an alkylamino group, or R ⁸ and Y ¹ and R ⁹ and Y ² are bonded to each other to form a 5-membered or 6-membered ring.

A particularly preferred form of the dipyrammethene metal complex compound represented by the above general formula (2) is a dipyrammethene metal complex compound represented by the following general formula (3).

[(A-3) Dipyrromethene metal complex compound represented by the general formula (3)] [

Hereinafter, the dipyrammethene metal complex compound represented by the following general formula (3) will be described in detail.

In the general formula (3), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ each independently represent a monovalent substituent, M represents a metal or a metal compound, X Represents a substituted or unsubstituted acyloxy group having 2 to 3 carbon atoms, a substituted or unsubstituted alkylsulfonyloxy group, a substituted or unsubstituted arylsulfonyloxy group, or a halogen atom, n1 and n2 each independently represents an integer of 0 to N3 and n4 each independently represent an integer of 0 to 3; When n1 is an integer of 2 or more, two or more R &lt; ¹⁵ &gt; s may be the same or different. When n2 is 2 or more integer 2 or R ¹⁶ is or different gatahdo. When n3 is an integer of 2 or more, R &lt; ¹⁷ &gt; of 2 or more may be the same or different. when n4 is 2 or more integer 2 or R ¹⁸ is or different gatahdo. The dipyrammethene metal complex compound represented by the general formula (3) includes a tautomer.

R ¹¹ and R ¹² in the general formula (3) correspond to R ² and R ^{5 in} the general formula (1), respectively.

In the general formula (3), R ¹¹ and R ¹² each independently preferably represent a substituted or unsubstituted alkoxycarbonyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, An arylsulfonyl group having 6 to 10 carbon atoms, a substituted or unsubstituted alkylcarbamoyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylcarbamoyl group having 7 to 11 carbon atoms, or a cyano group, Or an unsubstituted alkoxycarbonyl group having 6 to 30 carbon atoms, a substituted or unsubstituted alkylsulfonyl group having 1 to 12 carbon atoms, a substituted or unsubstituted phenylsulfonyl group, or a cyano group, particularly preferably an unsubstituted C6- An alkoxycarbonyl group having 1 to 30 carbon atoms, or a cyano group.

R ¹³ and R ¹⁴ in the general formula (3) are each independently a monovalent substituent and are, for example, the substituents described for R ¹ to R ⁶ in the general formula (1). When R ¹³ and R ¹⁴ are further substitutable groups, they may be further substituted by any of the substituents described for R ¹ to R ⁶ in the general formula (1). When two or more substituents are present, these substituents may be the same or different.

In the general formula (3), R ¹³ and R ¹⁴ each independently represent preferably a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, a substituted or unsubstituted carbon number A substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 10 carbon atoms, a substituted or unsubstituted amino group, or a halogen atom, more preferably a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, A substituted or unsubstituted alkoxy group having 1 to 12 carbon atoms, a substituted or unsubstituted phenoxy group, a chlorine atom, or a bromine atom, particularly preferably an unsubstituted alkyl group having 1 to 12 carbon atoms, A substituted alkoxy group having 1 to 12 carbon atoms, or a chlorine atom.

R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ in the general formula (3) are each independently a monovalent substituent, and examples thereof include a substituent described in relation to R ¹ to R ⁶ in the general formula (1) to be. When R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are further substitutable groups, they may be further substituted by any of the substituents described for R ¹ to R ⁶ in the general formula (1). When two or more substituents are present, these substituents may be the same or different.

In the general formula (3), R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are each independently preferably a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, A substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 10 carbon atoms, a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, Or an unsubstituted arylthio group having 6 to 10 carbon atoms, a substituted or unsubstituted acyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms A substituted or unsubstituted amino group having 0 to 30 carbon atoms, a cyano group, a halogen atom, a hydroxy group, a carboxyl group, a sulfo group or a phosphono group, more preferably a substituted or unsubstituted amino group having 1 to 30 carbon atoms Substituted &lt; RTI ID = 0.0 &gt; A substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted phenyl group, a substituted or unsubstituted alkoxy group having 1 to 18 carbon atoms, a substituted or unsubstituted phenoxy group, a substituted or unsubstituted alkylthio group having 1 to 18 carbon atoms, A substituted or unsubstituted alkylthio group having 1 to 18 carbon atoms, a substituted or unsubstituted arylthio group having 1 to 18 carbon atoms, a substituted or unsubstituted arylthio group having 1 to 18 carbon atoms, A substituted or unsubstituted amino group having 0 to 18 carbon atoms, a cyano group, a fluorine atom, a chlorine atom, a bromine atom, a hydroxyl group, a carboxyl group, a sulfo group or a phosphono group, Preferably an unsubstituted alkyl group having 1 to 12 carbon atoms, an unsubstituted phenyl group, an unsubstituted alkoxy group having 1 to 12 carbon atoms, an unsubstituted acyl group having 2 to 12 carbon atoms, an unsubstituted alkoxycarbonyl group having 2 to 18 carbon atoms , The number of unsubstituted carbon atoms is 1 A fluorine atom, a chlorine atom, a bromine atom, a hydroxyl group, or a carboxy group.

Wherein in the general formula (3) and may further, if n1 is an integer of 2 or more adjacent R ¹⁵ are bonded to each other to form a ring of 5-, 6- or 7-membered. Examples of the ring to be formed include a benzene ring, a naphthalene ring, a pyridine ring and a thiophene ring, preferably a benzene ring. When n2, n3 and n4 are each an integer of 2 or more, the same as the above is applied to adjacent R ¹⁶ , adjacent R ¹⁷ , and adjacent R ¹⁸ .

When R ¹³ and R ¹⁷ are adjacent to each other, R ¹³ and R ¹⁷ may be bonded to each other to form a 5-membered, 6-membered or 7-membered ring. Examples of the ring formed include a benzene ring, a naphthalene ring, a pyridine ring and a thiophene ring, preferably a benzene ring. R ¹⁴ and R ¹⁸ are adjacent to each other.

When the five-membered, six-membered, and seven-membered rings to be formed are further substitutable groups, they may be substituted with any of the above-described monovalent substituents, and when they are substituted with two or more substituents, these substituents may be the same or different .

In the general formula (3), n1 and n2 are each independently an integer of 0 to 5, preferably 0 to 3, more preferably 0 to 2, and particularly preferably 0 or 1.

In the general formula (3), n3 and n4 are each independently an integer of 0 to 3, preferably 0 to 2, and particularly preferably 0 or 1.

M in the general formula (3) represents a metal or a metal compound, which is the same as the metal atom or the metal compound in the dipyrammethene metal complex compound of the general formula (1), and the preferable examples are also the same.

In the general formula (3), X represents a substituted or unsubstituted acyloxy group having 2 to 3 carbon atoms, a substituted or unsubstituted alkylsulfonyloxy group, a substituted or unsubstituted arylsulfonyloxy group, or a halogen atom. X is preferably a substituted or unsubstituted acyloxy group having 2 to 3 carbon atoms, a substituted or unsubstituted alkylsulfonyloxy group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonyloxy group having 6 to 30 carbon atoms, More preferably a substituted or unsubstituted acyloxy group having 2 to 3 carbon atoms, an unsubstituted alkylsulfonyloxy group having 1 to 18 carbon atoms, an unsubstituted aryl group having 6 to 12 carbon atoms A sulfonyloxy group, a fluorine atom, or a chlorine atom, and particularly preferably a substituted or unsubstituted acyloxy group having 2 to 3 carbon atoms.

Preferable forms of the dipyrammethene metal complex compound represented by the above general formula (3) are shown below. That is, in the general formula (3)

R ¹¹ and R ¹² are each independently a substituted or unsubstituted alkoxycarbonyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonyl group having 6 to 10 carbon atoms, A substituted or unsubstituted alkylcarbamoyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylcarbamoyl group having 7 to 11 carbon atoms, or a cyano group,

R ¹³ and R ¹⁴ are each independently a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, An aryloxy group having 6 to 10 carbon atoms, a substituted or unsubstituted amino group, or a halogen atom,

R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are each independently a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, a substituted or unsubstituted heterocyclic group, An unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 10 carbon atoms, a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms A substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted acyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, A substituted or unsubstituted amino group having 0 to 30 carbon atoms, a cyano group, a halogen atom, a hydroxyl group, a carboxyl group, a sulfo group, or a phosphono group,

n1, n2, n3 and n4 are each independently 0 to 3,

M is Fe, Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO, B,

X is a substituted or unsubstituted acyloxy group having 2 to 3 carbon atoms, a substituted or unsubstituted alkylsulfonyloxy group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonyloxy group having 6 to 30 carbon atoms, a fluorine atom, a chlorine Atom, or bromine atom.

A more preferable form of the dipyrammethene metal complex compound represented by the above general formula (3) is shown below. That is, in the general formula (3)

R ¹¹ and R ¹² are both a substituted or unsubstituted alkoxycarbonyl group having 6 to 30 carbon atoms, a substituted or unsubstituted alkylsulfonyl group having 1 to 12 carbon atoms, a substituted or unsubstituted phenylsulfonyl group, or a cyano group,

R ¹³ and R ¹⁴ are both a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted phenyl group, a substituted or unsubstituted alkoxy group having 1 to 12 carbon atoms, a substituted or unsubstituted phenoxy group, Or a bromine atom,

R ¹⁵ and R ¹⁶ are both a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted phenyl group, a substituted or unsubstituted alkoxy group having 1 to 18 carbon atoms, a substituted or unsubstituted phenoxy group, A substituted or unsubstituted alkylthio group having 1 to 18 carbon atoms, a substituted or unsubstituted phenylthio group, a substituted or unsubstituted acyl group having 2 to 18 carbon atoms, a substituted or unsubstituted alkoxycarbonyl group having 2 to 18 carbon atoms, A substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted carbamoyl group having 1 to 18 carbon atoms, a substituted or unsubstituted amino group having 0 to 18 carbon atoms, a cyano group, a fluorine atom, a chlorine atom, a bromine atom, A carboxyl group, a sulfo group, or a phosphono group,

R ¹⁷ and R ¹⁸ are both a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted phenyl group, a substituted or unsubstituted alkoxy group having 1 to 18 carbon atoms, a substituted or unsubstituted phenoxy group, A substituted or unsubstituted alkylthio group having 1 to 18 carbon atoms, a substituted or unsubstituted phenylthio group, a substituted or unsubstituted acyl group having 2 to 18 carbon atoms, a substituted or unsubstituted alkoxycarbonyl group having 2 to 18 carbon atoms, A substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted carbamoyl group having 1 to 18 carbon atoms, a substituted or unsubstituted amino group having 0 to 18 carbon atoms, a cyano group, a fluorine atom, a chlorine atom, a bromine atom, A carboxyl group, a sulfo group, or a phosphono group,

n1 and n2 are all 0 to 2, n3 and n4 are all 0 to 2,

M is Fe, Zn, Mg, Si, Pt, Pd, Cu, Ni, Co,

X is a substituted or unsubstituted acyloxy group having 2 to 3 carbon atoms, an unsubstituted alkylsulfonyloxy group having 1 to 18 carbon atoms, an unsubstituted arylsulfonyloxy group having 6 to 12 carbon atoms, a fluorine atom, or a combination of chlorine atoms to be.

A particularly preferable form of the dipyrammethene metal complex compound represented by the above general formula (3) is shown below. That is, in the general formula (3)

R ¹¹ and R ¹² are both an unsubstituted alkoxycarbonyl group having 6 to 30 carbon atoms or a cyano group,

R ¹³ and R ¹⁴ are both an unsubstituted alkyl group having 1 to 12 carbon atoms, an unsubstituted alkoxy group having 1 to 12 carbon atoms, or a chlorine atom,

R ¹⁵ and R ¹⁶ are both an unsubstituted alkyl group having 1 to 12 carbon atoms, an unsubstituted phenyl group, an unsubstituted alkoxy group having 1 to 12 carbon atoms, an unsubstituted acyl group having 2 to 12 carbon atoms, An unsubstituted alkylsulfonyl group having 1 to 12 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, a hydroxyl group, or a carboxy group,

R ¹⁷ and R ¹⁸ are both an unsubstituted alkyl group having 1 to 12 carbon atoms, an unsubstituted phenyl group, an unsubstituted alkoxy group having 1 to 12 carbon atoms, an unsubstituted acyl group having 2 to 12 carbon atoms, An unsubstituted alkylsulfonyl group having 1 to 12 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, a hydroxyl group, or a carboxy group,

n1 and n2 are all 0 or 1, n3 and n4 are both 0 or 1,

M is Zn,

And X is a substituted or unsubstituted acyloxy group having 2 to 3 carbon atoms.

The most preferred form of the dipyrammethene metal complex compound represented by the general formula (3) is a dipyrammethene metal complex compound represented by the following general formula (4).

[(A-4) Dipyrromethene metal complex compound represented by general formula (4)] [

Hereinafter, the dipyrammethene metal complex compound represented by the following general formula (4) will be described in detail.

In the general formula (4), R ¹³ and R ¹⁴ each independently represent a monovalent substituent, and X represents a substituted or unsubstituted acyloxy group having 2 to 3 carbon atoms, a substituted or unsubstituted alkylsulfonyloxy group, An unsubstituted arylsulfonyloxy group, or a halogen atom. The dipyrammethene metal complex compound represented by the general formula (4) includes a tautomer.

And the general formula (4) R ^13, R ¹⁴ and X are each R ^13, R ¹⁴ and X and agreement in the formula (3) in the, as preferred examples.

Preferable forms of the dipyrammethene metal complex compound represented by the above general formula (4) are shown below. That is, in the general formula (4)

R ¹³ and R ¹⁴ are each independently a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, An aryloxy group having 6 to 10 carbon atoms, a substituted or unsubstituted amino group, or a halogen atom,

X is a substituted or unsubstituted acyloxy group having 2 to 3 carbon atoms, a substituted or unsubstituted alkylsulfonyloxy group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonyloxy group having 6 to 30 carbon atoms, a fluorine atom, a chlorine Atom, or bromine atom. Here, R ¹³ and R ¹⁴ are preferably the same substituent.

A more preferable form of the dipyrammethene metal complex compound represented by the above general formula (4) is shown below. That is, in the general formula (4)

R ¹³ and R ¹⁴ each independently represents a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted phenyl group, a substituted or unsubstituted alkoxy group having 1 to 12 carbon atoms, a substituted or unsubstituted phenoxy group, An atom, or a bromine atom,

X is a substituted or unsubstituted acyloxy group having 2 to 3 carbon atoms, an unsubstituted alkylsulfonyloxy group having 1 to 18 carbon atoms, an unsubstituted arylsulfonyloxy group having 6 to 12 carbon atoms, a fluorine atom, or a combination of chlorine atoms to be. Here, R &lt; ¹³ &gt; and R &lt; ¹⁴ &gt; are preferably the same substituent.

The most preferable form of the dipyrammethene metal complex compound represented by the above general formula (4) is shown below. That is, in the general formula (4)

R ¹³ and R ¹⁴ are each independently an unsubstituted alkyl group having 1 to 12 carbon atoms, an unsubstituted alkoxy group having 1 to 12 carbon atoms, or a chlorine atom,

And X is a substituted or unsubstituted acyloxy group having 2 to 3 carbon atoms. Here, R &lt; ¹³ &gt; and R &lt; ¹⁴ &gt; are preferably the same substituent.

Specific examples of the specific dipyrammethene metal complex compound are shown below, but the present invention is not limited thereto. In addition, R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , M ¹ , and X ¹⁰¹ in Tables 1 to 6 represent substituents in the following general formula (5).

Exemplary Compounds (A1) to (A35) and Exemplary Compounds (B1) to (B25) in the Exemplary Compounds are specific examples of the dipyrammethene metal complex compounds represented by the general formula (2).

Exemplary compounds (A1) to (A35) among the above exemplified compounds are specific examples of the dipyrammethene metal complex compounds represented by the above general formula (3).

Exemplary compounds (A1) to (A10) among the above exemplified compounds are specific examples of the dipyrammethene metal complex compounds represented by the above general formula (4).

Exemplary compounds (Ia-3) to (Ia-83), (IIa-1) to (IIa-20), (I-1) to (I-36) described in JP-A-2008-292970 (I-1) to (I-35) described in Japanese Patent No. 3324279, and Japanese Patents (II-1) to (II-1) to (I-13) described in JP-A No. 3279035 and Exemplary Compounds (2-1) to (2-32) Exemplary compounds (I-1) to (3-32), (4-1) to (4-26), and (5-1) to (5-26) (1-1) to (1-45) described in JP-A-11-352686, JP-A-2000-19729 Exemplary compounds (1-1) to (1-50) described in JP-A No. 11-352685 and Exemplary Compounds (1-1) to (1-45) disclosed in JP-A No. 11-352685 also have a specific dipyrromethene metal complex As an example of the compound, there can be mentioned.

Specific dipyramethylene metal complex compounds are described in U.S. Patent Nos. 4,774,339, 5,433,896, JP-A-2001-240761, JP-A-2002-155052, JP-A-3614586, Aust. JH Boger et al., Heteroatom Chemistry, Vol. 1, No. 5, 389 (1990), Japanese Patent Application Laid-Open No. 2008-292970 Can be synthesized by reference.

The mole extinction coefficient of the specific dipyrammethene metal complex compound is preferably as high as possible from the viewpoint of the film thickness. The maximum absorption wavelength (? Max) of a specific dipyrammethene metal complex compound is preferably 520 nm to 580 nm, more preferably 530 nm to 570 nm from the viewpoint of improving color purity. Further, the maximum absorption wavelength (? Max) and the molar extinction coefficient are those measured by a spectrophotometer UV-2400PC (Shimadzu Corporation).

The content of the specific dipyrammethene metal complex compound in the coloring composition varies depending on the molecular weight and the molar extinction coefficient but is preferably from 10% by mass to 70% by mass, more preferably from 10% by mass to 50% by mass relative to the total solid component of the coloring composition, , And still more preferably from 15 mass% to 30 mass%. The specific dipyrammethene metal complex compound may be used singly or in combination of two or more.

[(B) Phthalocyanine Pigment]

The phthalocyanine-based pigment used in the coloring composition of the present invention is not particularly limited as long as it is a pigment having a phthalocyanine skeleton. The central metal contained in the phthalocyanine-based pigment is not particularly limited as long as it is a metal capable of forming a phthalocyanine skeleton. Among them, magnesium, titanium, iron, cobalt, nickel, copper, zinc and aluminum are preferably used as the central metal.

Specific examples of the phthalocyanine-based pigment in the present invention include C.I. Pigment Blue 15, C.I. Pigment Blue 15: 1, C.I. Pigment Blue 15: 2, C.I. Pigment Blue 15: 3, C.I. Pigment Blue 15: 4, C.I. Pigment Blue 15: 5, C.I. Pigment Blue 15: 6, C.I. Pigment Blue 16, C.I. Pigment Blue 17: 1, C.I. Pigment Blue 75, C.I. Pigment Blue 79, C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment Green 37, chloroaluminum phthalocyanine, hydroxy aluminum phthalocyanine, aluminum phthalocyanine oxide, and zinc phthalocyanine. Among them, C.I. Pigment Blue 15, C.I. Pigment Blue 15: 6, C.I. Pigment Blue 15: 1, C.I. Pigment Blue 15: 2 is preferable, and C.I. Pigment Blue 15: 6 is particularly preferred.

The content of the phthalocyanine-based pigment in the coloring composition of the present invention is preferably 10% by mass to 70% by mass, more preferably 20% by mass to 60% by mass, and still more preferably 35% by mass to 50% by mass relative to the total solid content of the colorant composition. % By mass is most preferable.

The content ratio of the specific dipyrammethene metal complex compound and the phthalocyanine pigment is preferably from 100: 5 to 100: 100, more preferably from 100: 15 to 100: 75, , More preferably from 100: 25 to 100: 50.

[(C) Dispersant]

As the dispersant to be used in the coloring composition of the present invention, a known pigment dispersant or a surfactant is used. As the dispersing agent, many kinds of compounds are known, and examples thereof include phthalocyanine derivatives (commercially available product EFKA-745, manufactured by EPC Corporation), Solspers 5000 (manufactured by Nihon Lubrizol Corporation), organosiloxane polymer KP341 (Available from Kyoeisha Chemical Co., Ltd.), W001 (produced by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Kyoeisha Chemical Co., Ltd.) ); Cationic surfactants such as; Polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol distearate, polyethylene glycol distearate, sorbitan fatty acid Nonionic surfactants such as esters; Anionic surfactants such as W004, W005 and W017 (manufactured by Yuso Co., Ltd.); (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, Disperse Aide 8, Aid 15, Disperse Aid 9100 (manufactured by Sanno Foucault Co., Ltd.); (Manufactured by Nippon Lubrizol Corporation) such as Sol Spurs 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000 and 28000; (Above, Adeka Fluoronics L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, ), And Isonet S-20 (manufactured by Sanyo Chemical Industries, Ltd.).

The content of the dispersing agent in the coloring composition of the present invention is preferably 1% by mass to 80% by mass, more preferably 5% by mass to 70% by mass, and most preferably 10% by mass to 60% by mass relative to the phthalocyanine pigment Do. The dispersant may be used alone or in combination of two or more.

[(D) Organic solvent]

The organic solvent to be used in the coloring composition of the present invention is not particularly limited as long as it can satisfy the solubility of each component in the coexistence, the coating property of the coloring composition and the coating property when the composition is colored and cured. In particular, it is preferably selected in consideration of the solubility, coating ability, and safety of the binder in the case of using the colored curable composition.

Examples of the organic solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, butyl butyrate, butyl lactate , Ethyl lactate, and oxyacetic acid alkyl esters such as methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (specifically, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, ethoxyacetate, ethoxyacetic acid Ethyl, etc.)), 3-oxypropionic acid alkyl esters such as methyl 3-oxypropionate, ethyl 3-oxypropionate (specifically methyl 3-methoxypropionate, ethyl 3-methoxypropionate, Methyl ethoxypropionate and ethyl 3-ethoxypropionate), 2-oxypropionic acid alkyl esters ( Examples thereof include methyl 2-oxypropionate, ethyl 2-oxypropionate and propyl 2-oxypropionate (specifically, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, Ethyl 2-ethoxypropionate), methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate (specifically, methyl 2-methoxy- Methyl propionate and the like), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate and the like .

Examples of the 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. Propylene glycol monomethyl ether acetate is preferable.

Examples of the ketone include methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, and the like.

As the aromatic hydrocarbons, for example, toluene, xylene and the like are preferably used.

These organic solvents are preferably mixed with two or more kinds in view of the solubility of each component in the case of using the coloring composition and the color-curable composition, the shape of the coated surface, and the like. In this case, particularly preferred examples thereof include methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethylcellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, , Cyclohexanone, ethylcarbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate.

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

[Other components]

In addition to the above-mentioned components, the coloring composition of the present invention may contain other components such as a surfactant, an antioxidant, and an anti-aggregation agent within a range not to impair the effects of the present invention. The surfactant that can be added to the coloring composition of the present invention is the same as the surfactant that can be added to the coloring and curing composition described later.

[Method for preparing coloring composition]

The coloring composition of the present invention is prepared by mixing the above-described essential components with optional components as necessary. Further, in the preparation of the coloring composition, the respective components constituting the coloring composition may be blended together, and the components may be dissolved and / or dispersed in a solvent and then blended sequentially. In addition, the order of injection and the working conditions at the time of compounding are not particularly limited. For example, the composition may be prepared by dissolving and / or dispersing the entire components in a solvent at the same time, and if necessary, the components may be appropriately mixed into two or more solutions or dispersions and mixed at the time of use (upon application) It may be prepared.

The coloring composition prepared as described above may preferably be used after filtration using a filter having a pore diameter of from 0.01 mu m to 3.0 mu m, more preferably a pore diameter of from 0.05 mu m to 0.5 mu m or the like.

The volume average particle diameter of the pigment in the dispersed state in the coloring composition is preferably 10 to 200 nm, more preferably 10 to 150 nm, and further preferably 10 to 100 nm.

The average particle diameter of the pigment in the dispersed state is determined by dynamic light scattering method using a nanotrac particle size distribution analyzer UPA-EX150 (manufactured by Nikkiso Co., Ltd.).

&Lt; Coloring curable composition >

The colored curable composition of the present invention contains the above-mentioned coloring composition, (E) a polymerizable compound, and (F) a polymerization initiator. The coloring composition contained in the colored curable composition of the present invention is as described above. The colored curable composition of the present invention can form a colored cured film having high curing sensitivity to pattern exposure and high heat resistance and light resistance by including the above-mentioned coloring composition. The specific dipyrammethene metal complex compound contained in the tinting curable composition of the present invention is preferably a dipyrammethene metal complex compound represented by the above general formula (2) from the viewpoints of curing sensitivity, heat resistance and light resistance, ) Is more preferable, and the dipyrammethene metal complex compound represented by the general formula (4) is particularly preferable.

Hereinafter, the (E) polymerizable compound and the (F) polymerization initiator contained in the colored curable composition of the present invention will be described in detail.

[(E) Polymerizable compound]

Examples of the polymerizable compound used in the color-curable composition of the present invention include addition polymerizable compounds having at least one ethylenic unsaturated double bond. Specifically, it is selected from compounds having at least one, and preferably two or more, terminal ethylenic unsaturated bonds. Such a group of compounds is widely known in the relevant industrial field, and in the present invention, these compounds can be used without any particular limitation. These may be, for example, any of chemical form such as monomer, prepolymer, that is, dimer, trimer and oligomer, or mixture thereof and (co) polymer thereof. In the present specification, acryloyl group and methacryloyl group are collectively referred to as (meth) acryloyl group, and acrylate and methacrylate are collectively referred to as (meth) acrylate.

Examples of the polymerizable compound include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters and amides thereof, An ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, and an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound are used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent group such as a hydroxyl group, an amino group or a mercapto group with a monofunctional or polyfunctional isocyanate or an epoxy group, and an addition reaction product of a monofunctional or polyfunctional carboxylic acid And a dehydration-condensation reaction product of the compound

In addition, an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group, an addition reaction product of mono- or polyfunctional alcohols, amines, and thiols, a halogen group, Substitution reaction products of unsaturated carboxylic acid esters or amides having a substituent with monofunctional or polyfunctional alcohols, amines and thiols are also preferable. As another example, it is also possible to use a group of compounds in which the unsaturated carboxylic acid is substituted with an unsaturated phosphonic acid, styrene, vinyl ether, or the like.

Specific examples of the monomer of the ester of the aliphatic polyhydric alcohol compound and the unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, tetramethylene glycol diacrylate, propylene glycol Diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylol ethane triacrylate, hexane diol diacrylate, 1,4 -Cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, tripentaerythritol Polyacrylate (Number of acrylates: 1 to 8), tetrapentaerythritol polyacrylate (number of acrylates: 1 to 10), pentapentaerythritol polyacrylate (number of acrylates: 1 to 12), sorbitol triacrylate, sorbitol tetra Acrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer, and isocyanuric acid EO-modified triacrylate.

Examples of the methacrylic ester include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylol ethane trimethacrylate, ethylene glycol di Methacrylate, 1,3-butanediol dimethacrylate, hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, Pentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacryloxy-2-hydroxypropoxy) phenyl] dimethylmethane, bis- [p- 2-methoxyethoxy) phenyl] dimethylmethane and the like.

Examples of itaconic acid esters include ethylene glycol diacetonate, propylene glycol diacetonate, 1,3-butanediol diacetonate, 1,4-butanediol diacetonate, tetramethylene glycol diacetonate, pentaerythritol diacetonate, sorbitol tetra- And Nate. Examples of the crotonic acid ester include ethylene glycol dichlonate, tetramethylene glycol dichlonate, pentaerythritol dichlonate, and sorbitol tetradecrhotonate. Examples of isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate. Examples of the maleic acid ester include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

Examples of other esters include aliphatic alcohol esters described in JP-A-51-47334 and JP-A-57-196231, JP-A 59-5240, JP-A- Those having an aromatic skeleton disclosed in JP-A-59-5241, JP-A-2-226149, and those containing an amino group described in JP-A-1-165613 are preferably used. The above-mentioned ester monomer can also be used as a mixture.

Specific examples of the monomer of the amide of the aliphatic polyvalent amine compound and the unsaturated carboxylic acid include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, Methacrylamide, diethylenetriamintris acrylamide, xylylene bisacrylamide, xylylene bismethacrylamide, and the like. Examples of other preferable amide-based monomers include those having a cyclohexylene structure described in JP-A-54-21726.

Also, a urethane-based addition polymerizable compound produced by the addition reaction of isocyanate and hydroxyl group is also preferable. As specific examples thereof, two or more isocyanate groups in a molecule described in Japanese Patent Publication No. 48-41708 And a vinyl urethane compound having at least two polymerizable vinyl groups in one molecule, which is obtained by adding a vinyl monomer containing a hydroxyl group represented by the following formula (1) to a polyisocyanate compound having a hydroxyl group.

R ⁴ and R ⁵ in the formula (1) each independently represent H or CH ₃ .

Also, urethane acrylates described in JP-A-51-37193, JP-A-2-32293, JP-A-2-16765, JP-A-58-49860, The urethane compounds having an ethylene oxide skeleton described in JP-A-56-17654, JP-A-62-39417 and JP-A-62-39418 are also preferable. Further, addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909 and JP-A-1-105238 A colored curable composition having a very high photosensitive speed can be obtained.

Other examples include polyester acrylates, epoxy resins and (meth) acrylic acid, which are described in Japanese Patent Application Laid-Open No. 48-64183, Japanese Patent Publication No. 49-43191, Japanese Patent Publication No. 52-30490, And polyfunctional acrylates and methacrylates such as epoxy acrylates prepared by dissolving or dispersing the above-mentioned components. Specific examples of the unsaturated compounds described in JP-A-46-43946, JP-A-1-40337 and JP-A-1-40336, vinyl compounds described in JP-A-2-25493 Phosphonic acid-based compounds and the like. In addition, in some cases, a structure containing the perfluoroalkyl group described in JP-A-61-22048 is preferably used. Also, those which have been introduced as photocurable monomers and oligomers in Japan Adhesion Society vol.20, No. 7, pp. 300-308 (1984) can be used.

The details of the structure, the use of the polymerizable compound, whether it is used alone, whether it is used alone or in combination, and the like can be arbitrarily set in accordance with the performance design of the final colored curable composition. For example, it is selected from the following viewpoints.

In view of sensitivity, a structure having a large number of unsaturated groups per molecule is preferable, and in most cases, a bifunctionality or more is preferable. Further, in order to increase the strength of the colored image portion, that is, the colored curable composition layer, it is preferable to use a trifunctional or higher functional group. In addition, it is also possible to use other functional groups and other polymerizable groups (e.g., acrylic acid ester, methacrylic acid ester, styrene group compound, ) Is used in combination to control both the sensitivity and the intensity. From the viewpoint of curing sensitivity, it is preferable to use a compound containing two or more (meth) acrylic acid ester structures ((meth) acrylate type multifunctional monomer), more preferably a compound containing three or more, It is most preferable to use a compound containing at least 4 groups. In addition, from the viewpoints of curing sensitivity and developability of the unexposed portion, it is preferable to contain an EO-modified product. Further, from the viewpoints of curing sensitivity and strength of the exposed portion, it is preferable to contain a urethane bond.

Further, regarding the compatibility with other components in the layer of the color-curable composition (for example, compatibility with an alkali-soluble resin and an initiator, an addition polymerization compound is selected and used in an important way. For example, use of a low purity compound, In addition, a specific structure may be selected for the purpose of improving adhesion with a substrate.

(Meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane tri (meth) acryloyloxypropyl trimethylol propane tri (meth) acrylate, (Meth) acrylate, trimethylol ethane tri (meth) acrylate, tetraethylene glycol di (meth) acrylate, pentaerythritol di (Meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethoxylated bisphenol A diacrylate, sorbitol tri (meth) acrylate, sorbitol tetra Acrylate, sorbitol penta (meth) acrylate, sorbitol hexa (meth) acrylate, tri (meth) acryloyloxyethyl) (Meth) acrylate EO-modified product, dipentaerythritol hexa (metha) acrylate EO-modified product, and the like. Examples of commercially available products include urethane oligomers UAS-10 and UAB-140 NK Ester A-TMPT, NK Ester A-TMM-3 (manufactured by Shin Nakamura Kagaku Kogyo Co., Ltd.), ARONIX M- (Manufactured by Toa Kosei Co., Ltd.), V # 802 (manufactured by Osaka Yuki Kagaku Kogyo Co., Ltd.), UA-306H, UA-309, Aronix M-309, Aronix M-450, Aronix M- -306T, UA-306I, AH-600, T-600, AI-600 (above, Kyocera Corporation).

Among them, bisphenol A di (meth) acrylate EO modified product, ethoxylated bisphenol A diacrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) (Meth) acrylate hexa (meth) acrylate, tri (meth) acryloyloxyethyl isocyanurate, pentaerythritol tetra (meth) acrylate EO modified product, dipentaerythritol hexa NK Ester A-TMPT, NK Ester A-TMM-3 (manufactured by Shin Nakamura Kagaku Kogyo Co., Ltd.), Aronix M-305, Aronix M-306, Aronix M-309, Aronix M-450, Aronix M-402 (manufactured by Toagosei Co., Ltd.) and V # 802 (Osaka Yuki Kagaku Kogyo Co., Ltd.) are more preferable.

The content of the polymerizable compound (total content in the case of two or more kinds) in the total solid content of the color-curable composition of the present invention is not particularly limited and is preferably 10% by mass to 80% by mass in view of more effectively obtaining the effects of the present invention , More preferably from 15% by mass to 75% by mass, and particularly preferably from 20% by mass to 60% by mass.

[(F) Polymerization initiator]

The polymerization initiator used in the color-curable composition of the present invention is not particularly limited as long as it can initiate polymerization of the polymerizable compound (E), and is preferably selected from the viewpoints of characteristics, initiation efficiency, absorption wavelength, availability, and cost Do.

Examples of the polymerization initiator include at least one active halogen compound selected from a halomethyloxadiazole compound and a halomethyl-s-triazine compound, a 3-aryl substituted coumarin compound, a ropin dimer, a benzophenone compound, an acetophenone compound And derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, oxime compounds, and the like. Specific examples of the polymerization initiator include those described in paragraphs 0069 to 0079 of Japanese Patent Application Laid-Open No. 2004-295116. Among them, oxime compounds are preferable in that polymerization reaction is quick.

The oxime-based compound (hereinafter also referred to as &quot; oxime-based photopolymerization initiator &quot;) is not particularly limited, and examples thereof include oxime compounds described in JP-A 2000-80068, WO 02/100903 A1, JP 2001-233842, Based compounds.

Specific examples include 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-butanedione, 2- -1,2-pentanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio) (Phenylthio) phenyl] -1,2-octanedione, 2- (O-benzoyloxime) -1- -1- [4- (ethylphenylthio) phenyl] -1,2-butanedione, 2 (O-benzoyloxime) (O-benzoyloxime) -1- [4- (butylphenylthio) phenyl] -1,2-butanedione, 1- Benzoyl) -9H-carbazol-3-yl] ethanone, 1- (9-methyl- 1- (9-propyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O- acetyloxime) (9-ethyl-6- (2-ethylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- -9H- Le carbazole-3-yl] ethanone, and the like. However, the present invention is not limited thereto.

(O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1 (phenylthio) phenyl] -1 O-acyl group such as 2-octanedione and 1- (O-acetyloxime) -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol- Compounds are particularly preferable. Specific examples thereof include CGI-124 and CGI-242 (manufactured by BASF Japan).

In the present invention, compounds represented by the following formulas (2) and (3) are more preferable as the oxime compounds from the viewpoints of sensitivity, stability with time, and coloration upon post heating.

In the formulas (2) and (3), R and X each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group. n represents an integer of 1 to 5;

The R is preferably an acyl group in view of high sensitivity, and specifically, an acetyl group, a propionyl group, a benzoyl group or a toluyl group is preferable.

The A is preferably an alkylene group substituted with an unsubstituted alkylene group, an alkyl group (e.g., methyl group, ethyl group, tert-butyl group or dodecyl group), an alkenyl group (E.g., a vinyl group, an allyl group), an aryl group (e.g., a phenyl group, a p-tolyl group, a xylyl group, a cumenyl group, a naphthyl group, an anthryl group, a phenanthryl group, ) Is preferable.

As the above-mentioned Ar, a substituted or unsubstituted phenyl group is preferable from the viewpoint of increasing the sensitivity and inhibiting coloration due to heating over time. In the case of a substituted phenyl group, the substituent is preferably a halogen group such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

Examples of the X include an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, a substituent An aryloxy group which may have a substituent, an alkyloxy group which may have a substituent, an aryloxy group which may have a substituent, and an amino group which may have a substituent are preferable.

In the formulas (2) and (3), n is preferably an integer of 1 to 2.

Specific examples of the compounds represented by the formulas (2) and (3) are shown below, but the present invention is not limited thereto.

The polymerization initiator may be contained singly or in combination of two or more. The content of the polymerization initiator (total content in the case of two or more kinds) in the total solid content of the colored curable composition of the present invention is preferably 3% by mass to 20% by mass, more preferably 4% by mass, By mass to 19% by mass, and particularly preferably 5% by mass to 18% by mass.

[Other components]

The colored curable composition of the present invention may contain, in addition to the above-mentioned respective components, an alkali soluble binder, a photosensitizer, a chain transfer agent, a polymerization inhibitor, a surfactant, a contact improver, a crosslinking agent, It may contain other 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 polymer, soluble in an organic solvent, and capable of being developed with a weakly alkaline aqueous solution. Examples of such linear organic polymer polymers include polymers having a carboxylic acid in the side chains such as Japanese Patent Application Laid-open No. 59-44615, Japanese Patent Publication No. 54-34327, Japanese Patent Publication No. 58-12577, Methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, maleic acid copolymers, and acrylic acid copolymers described in the respective publications of Japanese Patent Application Laid-Open No. 54-25957, Japanese Patent Application Laid-open No. 59-53836, Copolymers, partially esterified maleic acid copolymers and the like, and acidic cellulose derivatives having a carboxylic acid in the side chain are likewise useful.

Examples of the alkali-soluble binder in the present invention include those obtained by adding an acid anhydride to a polymer having a hydroxyl group and the like, a polyhydroxystyrene resin, a polysiloxane resin, a poly (2-hydroxyethyl (meth) acrylate ), Polyvinyl pyrrolidone, polyethylene oxide, polyvinyl alcohol and the like are also useful. The linear organic polymer may be a copolymer obtained by copolymerizing a monomer having hydrophilicity. Examples thereof include alkoxyalkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, glycerol (meth) acrylate, (meth) acrylamide, N-methylol acrylamide, secondary or tertiary alkyl acrylamide, di Vinyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, vinyltoluene, (Meth) acrylate, branched or straight chain propyl (meth) acrylate, branched or straight chain butyl (meth) acrylate, or phenoxy hydroxypropyl (meth) acrylate. Examples of the hydrophilic monomer include a tetrahydrofurfuryl group, a phosphoric acid group, a phosphoric acid ester group, a quaternary ammonium salt group, an ethyleneoxy chain, a propyleneoxy group, a group derived from a sulfonic acid group and a salt thereof, And the like.

Further, the alkali-soluble binder may have a polymerizable group in the side chain to improve the crosslinking efficiency, and for example, a polymer containing an allyl group, a (meth) acrylic group, an allyloxyalkyl group or the like in the side chain is also useful. Examples of the above-mentioned polymer containing a polymerizable group include commercially available products such as KS Resist-106 (manufactured by Osaka Yuki Kagaku Kogyo Co., Ltd.) and Sicroma P series (manufactured by Dai-ichi Kagaku Kogyo K.K.). Further, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, etc. are also useful for increasing the strength of the cured coating.

Among these various alkali-soluble binders, a polyhydroxystyrene resin, a polysiloxane resin, an acrylic resin, an acrylamide resin and an acryl / acrylamide copolymer resin are preferable from the viewpoint of heat resistance, and from the viewpoint of development control, Amide type resin, and acrylic / acrylamide copolymer resin are preferable.

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 products such as KS Resist-106 (Manufactured by Kagaku Kagaku Kogyo Co., Ltd.), and Sicroma P series (manufactured by Daicel Chemical Industries, Ltd.).

The alkali-soluble binder is preferably a polymer having a weight average molecular weight (polystyrene conversion value measured by GPC method) of 1000 to 2 x 10 ⁵ from the viewpoints of developability and liquid viscosity, more preferably 2000 to 1 x 10 ⁵ , And particularly preferably from 5000 to 5 x 10 &lt; ^{4 &} gt ;.

[Photosensitizer]

As a typical photosensitizer that can be used in the color-curable composition of the present invention, V. Crivello, Adv. in Polymer Sci, 62, 1 (1984), and specific examples thereof include pyrene, perylene, acridine, thioxanthone, 2-chlorothioxanthone, Carbazole, 9,10-dibutoxyanthracene, anthraquinone, benzophenone, coumarin, ketocoumarin, phenanthrene, camphorquinone, phenothiazine, and derivatives thereof. The photosensitizer is preferably added in a proportion of 50 to 200% by weight to the polymerization initiator.

[Chain transfer agent]

Examples of the chain transfer agent usable in the color-curable composition of the present invention include N, N-dialkylamino benzoic acid alkyl ester such as N, N-dimethylaminobenzoic acid ethyl ester, 2-mercaptobenzothiazole, 2-mercaptobenzoimidazole, N-phenylmercaptobenzoimidazole, 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine- Mercapto compounds having a heterocyclic ring such as 4,6 (1H, 3H, 5H) -trione and pentaerythritol tetrakis (3-mercaptobutyrate), 1,4-bis (3- ) Aliphatic polyfunctional mercapto compounds such as butane. The chain transfer agent may be used alone, or two or more kinds may be used in combination. The addition amount of the chain transfer agent is preferably from 0.1 to 10% by weight, more preferably from 0.5 to 5% by weight, from the viewpoint of reducing the sensitivity unevenness in the range of 0.01 to 15% by weight based on the total solid content of the colored curable composition of the present invention. Is particularly preferable.

[Polymerization inhibitor]

The polymerization inhibitor to be used in the color-curable composition of the present invention refers to a polymerization initiator such as a radical generated in the color-curable composition by light or heat. The polymerization inhibitor includes hydrogen donation (or hydrogen donation), energy donation (or energy donation) Or electron donating) to the polymerization initiator to deactivate the polymerization initiator to inhibit polymerization from being initiated unintentionally. Polymerization inhibitors described in paragraphs 0154 to 0173 of JP-A-2007-334322, and the like can be used. Of these, p-methoxyphenol is preferably used as the polymerization inhibitor.

The content of the polymerization inhibitor in the color-curable composition of the present invention is preferably from 0.0001 to 5% by weight, more preferably from 0.001 to 5% by weight, particularly preferably from 0.001 to 1% by weight, based on the total weight of the polymerizable compound Do.

〔Surfactants〕

The surfactant usable in the color-curable composition of the present invention may be any of anionic, cationic, nonionic, and amphoteric surfactants, but nonionic surfactants are preferred. Specifically, a nonionic surfactant described in paragraph 0058 of Japanese Patent Application Laid-Open No. 2009-098616 can be mentioned, and among these, a fluorinated surfactant is preferable.

Examples of other surfactants that can be used in the present invention include commercially available products such as Megapac F142D, F172, F173, F176, F177, F183, F479, F482, F554, F780, F781 (F), FC-135, FC-170C, FC (FC), FC-170, FC (FC) S-112, S-113, S-131, and S-131 (manufactured by Sumitomo Heavy Industries, Ltd.), Asahi Guard AG 7105, 7000, 950, 7600, Novec FC- S-141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC- (Trade name, manufactured by Mitsubishi Materials Corporation), Ftop EF351, Copper 352, Copper 801, Copper 802 (available from Mitsubishi Materials Denshi Kasei Co., Ltd.) and Ptagent 250 (available from Neos Corporation).

Further, the weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography using a THF as a solvent and containing the constituent unit A and the constituent unit B represented by the following formula (4) as a surfactant is 1,000 to 10,000 By weight or less.

In formula (4), R ¹ and R ³ each independently represent a hydrogen atom or a methyl group, R ² represents a straight chain alkylene group having 1 to 4 carbon atoms, R ⁴ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms P represents an integer of not less than 10% by weight and not more than 80% by weight, q represents an amount of not less than 20% by weight and not less than 90% by weight, and L represents an alkylene group having not less than 3 carbon atoms and not more than 6 carbon atoms, p and q are weight percentages indicating polymerization ratios, R represents an integer of 1 or more and 18 or less, and n represents an integer of 1 or more and 10 or less.

It is preferable that L is a branched alkylene group represented by the following formula (5). R ⁵ in the formula (5) represents an alkyl group having 1 to 4 carbon atoms and is preferably an alkyl group having 1 to 3 carbon atoms in terms of compatibility and wettability to a surface to be coated, more preferably an alkyl group having 2 or 3 carbon atoms Do. The sum (p + q) of p and q is preferably p + q = 100, i.e., 100% by weight.

The weight average molecular weight (Mw) of the copolymer is more preferably from 1,500 to 5,000.

The surfactants may be used alone or in combination of two or more. The amount of the surfactant added to the color-curable composition of the present invention is preferably 0.01 to 2.0% by weight, more preferably 0.02 to 1.0% by weight, based on the solid content. Within this range, the coating property and the uniformity of the cured film become good.

[Adhesion improver]

The adhesion improver that can be used in the colored curable composition of the present invention is a compound which improves the adhesion of an inorganic substance as a base material, for example, a silicone compound such as glass, silicon, silicon oxide, or silicon nitride, or gold, . Specific examples thereof include silane coupling agents and thiol compounds. The silane coupling agent as the adhesion improver is for the purpose of modifying the interface and is not particularly limited and a known silane coupling agent can be used.

As the silane coupling agent, a silane coupling agent described in paragraph 0048 of JP-A No. 2009-98616 is preferable, and among these,? -Glycidoxypropyltrialkoxysilane and? -Methacryloxypropyltrialkoxysilane are more preferable. These may be used alone, or two or more of them may be used in combination.

The content of the adhesion improver in the colored curable composition of the present invention is preferably 0.1 to 20% by weight, more preferably 0.2 to 5% by weight based on the total solid content.

[Crosslinking agent]

The hardness of the colored cured film obtained by curing the colored curable composition by using a crosslinking agent in addition to the colored curable composition of the present invention may be further increased. The crosslinking agent is not particularly limited as long as it can perform film curing by a crosslinking reaction. Examples thereof include (a) an epoxy resin, (b) at least one substituent selected from a methylol group, an alkoxymethyl group and an acyloxymethyl group A phenol compound substituted with at least one substituent selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group, a naphthol compound or a hydroxyanthracene compound, . Among them, a polyfunctional epoxy resin is preferable.

Specific examples of the crosslinking agent and the like can be found in paragraphs 0134 to 0147 of Japanese Patent Application Laid-Open No. 2004-295116.

[Development promoter]

In order to promote the alkali solubility of the non-exposed region to further improve the developability of the colored curable composition, a development accelerator may be added. The development accelerator is preferably a low molecular weight organic carboxylic acid compound having a molecular weight of 1000 or less, or a low molecular weight phenolic compound having a molecular weight of 1000 or less. Specific examples include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethylacetic acid, enanthic acid and caprylic acid; There may be mentioned oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassylic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, , Aliphatic dicarboxylic acids such as citraconic acid; Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid and camphoronic acid; Aromatic monocarboxylic acids such as benzoic acid, toluic acid, cuminic acid, hemellitic acid and mesitylene acid; Aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, melotropic acid and pyromellitic acid; Hydroxynaphthoic acid, phenylacetic acid, hydro atropic acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atrophic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylideneacetic acid, cumaric acid and umbellic acid.

[Other additives]

The colored curable composition of the present invention may contain various additives as needed such as fillers, polymer compounds other than the above, ultraviolet absorbers, antioxidants, and anti-aggregation agents. Examples of these additives include those described in paragraphs 0155 to 0156 of Japanese Patent Application Laid-Open No. 2004-295116.

In the colored curable composition of the present invention, the light stabilizer described in paragraph [0078] of Japanese Patent Application Laid-Open No. 2004-295116 and the thermal polymerization inhibitor described in paragraph [0081] of this publication may be contained.

[Process for preparing colored curable composition]

The colored curable composition of the present invention is prepared by mixing the above-mentioned essential components with optional components as required. Further, in the preparation of the colored curable composition, each component constituting the colored curable composition may be blended at one time, or each component may be dissolved and / or dispersed in a solvent and then blended sequentially. In addition, the order of injection and the working conditions at the time of compounding are not particularly limited. For example, the composition may be prepared by dissolving and / or dispersing the entire components in a solvent at the same time, and if necessary, each component may be suitably used as two or more solutions or dispersions and mixed at the time of use (upon application) It may be prepared.

The colored curable composition prepared as described above is preferably used after filtration using a filter having a pore diameter of from 0.01 mu m to 3.0 mu m, more preferably a pore diameter of from 0.05 mu m to 0.5 mu m or the like .

The colored curable composition of the present invention can form a colored cured film having high curing sensitivity, excellent in transparency and storage stability, and excellent in heat resistance and light resistance, and therefore can be used for a display device (for example, LCD) For example, a color filter used for a color filter used in a liquid crystal display (LCD), a liquid crystal display (LCD), a liquid crystal display (LCD), a CCD, or a CMOS). In particular, it can be suitably used as a coloring pixel forming solid-state imaging device such as CCD and CMOS, and a coloring pixel forming device for a display device.

<Color filter>

The color filter of the present invention is a color filter having a colored layer formed using the above-mentioned coloring composition or the above-mentioned colored curable composition.

Specifically, it is a color filter having a colored layer formed by applying the above-mentioned coloring composition or the above-mentioned colored curable composition on a substrate. The substrate or the coating method may be the same as the substrate or the coating method in a method of manufacturing a color filter to be described later.

It is preferable that the color filter of the present invention is produced by the method of producing a color filter described later by using the above-mentioned colored curable composition from the viewpoints of production efficiency and manufacturing precision.

The color filter of the present invention has a high transmittance and excellent heat resistance and light resistance in that it has a colored layer formed by using the above-mentioned coloring composition or the above-mentioned colored curable composition.

<Manufacturing Method of Color Filter>

The method for manufacturing a color filter of the present invention comprises a colored layer forming step of applying the above-mentioned colored curable composition on a substrate to form a colored layer, an exposure step of forming a latent image by exposing the colored layer to a pattern shape, And developing the colored layer on which the latent image is formed to form a pattern.

The method of manufacturing the color filter may include other steps as required, and it is preferable that the color filter further includes a step of irradiating the developed pattern with ultraviolet light and a step of performing heat treatment with respect to the pattern irradiated with ultraviolet light.

[Coloring layer forming step]

In the coloring layer forming step, the above-mentioned colored curable composition is applied on a substrate to form a colored layer. The application method may be rotational application, slit application, flex application, roll application, bar application, ink jet or the like.

The thickness of the colored layer is appropriately selected according to the purpose. In the color filter for a liquid crystal display device, the thickness after drying is preferably in the range of 0.2 탆 to 5.0 탆, more preferably in the range of 1.0 탆 to 4.0 탆. In the color filter for a solid-state imaging device, the film thickness after drying is preferably in the range of 0.2 탆 to 5.0 탆, more preferably in the range of 0.3 탆 to 2.5 탆.

Examples of the substrate include soda glass, alkali-free glass, borosilicate glass, quartz glass, silicon substrate, resin substrate and the like which are used for liquid crystal display devices and the like. On the substrate, a primer layer may be formed on the substrate in order to improve adhesion with the colored layer, prevent diffusion of the material, or planarize the surface, if necessary.

After the colored layer is formed, it is preferable that the colored layer is dried by, for example, heating (prebaking) or vacuum drying. As a prebaking condition, a condition of heating at 70 to 130 DEG C for 0.5 minute to 15 minutes using a hot plate or an oven can be mentioned.

[Exposure step]

The exposure process forms a latent image by exposing the colored layer to a pattern. The light or radiation usable for exposure is preferably g-line, h-line or i-line, and particularly preferably i-line. When the i-line is used as the irradiation light, it is preferable that the irradiation is performed at an exposure amount of 5 mJ / cm 2 to 500 mJ / cm 2. As the exposure light source, various kinds of laser light sources such as mercury lamps of high pressure, high pressure, medium pressure and low pressure, chemical lamp, carbon arc, xenon, metal halide and the like can be used.

~ Exposure process using laser light source ~

In the exposure method using a laser light source, the irradiation light is preferably an ultraviolet laser having a wavelength in the range of 300 nm to 410 nm, more preferably 300 nm to 360 nm. Concretely, the third harmonic (355 nm) of the Nd: YAG laser which is a relatively inexpensive solid laser with a large output, XeCl (308 nm) and XeF (353 nm) of the excimer laser can be preferably used. The exposure dose is preferably in the range of 1 mJ / cm 2 to 100 mJ / cm 2 from the viewpoint of productivity, and more preferably in the range of 1 mJ / cm 2 to 50 mJ / cm 2.

The exposure apparatus is not particularly limited, but a commercially available apparatus such as Callisto (manufactured by V Technology Corporation), EGIS (manufactured by V Technology Corporation) and DF2200G (manufactured by Dainippon Screen Corporation) can be used. Apparatuses other than those described above are also preferably used.

[Development step]

In the developing process, the colored layer on which the latent image is formed is developed to form a pattern. The exposure area is cured in a pattern, and in the development process, for example, an alkali developing process is performed to elute and remove the unirradiated area (uncured area) in the above-described exposure process to the alkaline aqueous solution to leave only the photo- Thereby forming a pattern.

As the developer, an organic alkali developer, an inorganic alkali developer or a mixture thereof is preferably used. The alkaline aqueous solution used for the developer is preferably adjusted to have an alkali concentration of preferably 10 to 13. Examples of the aqueous alkali solution include aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium silicate, sodium metasilicate, ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, An alkaline aqueous solution such as sodium hydroxide, potassium hydroxide, sodium hydroxide, potassium hydroxide, sodium hydroxide, potassium hydroxide, sodium hydroxide,

The development time is preferably 30 seconds to 300 seconds, more preferably 30 seconds to 120 seconds. The development temperature is preferably 20 to 40 캜, more preferably 23 캜. The development can be performed by a paddle method, a shower method, a spray method, or the like. Further, after development using an aqueous alkali solution, it is preferable to rinse with water.

[Post exposure step]

In the method of manufacturing a color filter according to the present invention, it is preferable to provide a post-exposure process for irradiating ultraviolet rays (post-exposure) on the developed pattern to further cure the pattern. The irradiation conditions of ultraviolet rays in the post-exposure process are the same as those in the above-described exposure process.

[Post baking process]

In the method of manufacturing a color filter of the present invention, it is preferable to further include a step of performing a heat treatment on a pattern on which post exposure is performed by the ultraviolet irradiation. The formed pattern can be further cured by heat treatment (so-called post-baking treatment). This heat treatment can be performed by, for example, a hot plate, various heaters, an oven, or the like. The temperature in the heat treatment is preferably 100 占 폚 to 300 占 폚, and more preferably 150 占 폚 to 250 占 폚. The heating time is preferably about 10 minutes to 120 minutes.

The coloring pattern thus obtained constitutes a pixel in the color filter. In the production of a color filter having pixels of a plurality of colors, the coloring layer forming step, the exposure step, the developing step, and the post-exposure step and the post-baking step, if necessary, may be repeated in accordance with the desired number of colors. The post-exposure process and the post-baking process may be performed each time the coloring layer formation, exposure and development of one color are completed, or may be performed once after completion of coloring layer formation, exposure and development of the entire desired color number.

The color filter obtained by the method for producing a color filter of the present invention is excellent in heat resistance and light resistance since the above-mentioned colored curable composition is used. Therefore, the color filter can be used for a solid-state image pickup device such as a CCD image sensor and a CMOS image sensor, and a camera system using the solid-state image pickup device. Among them, a colored pattern is formed into a thin film with a minute size, The use of a solid-state image pickup device, particularly, a high-resolution CCD element or CMOS exceeding 100 million pixels is preferable.

The color filter obtained by the method for producing a color filter of the present invention is excellent in durability (light and heat) and color in that the above-mentioned colored curable composition is used. It is possible to obtain a high brightness for obtaining a clear image or a power saving by reducing the light amount of the backlight light in view of excellent spectral characteristics (blue light transmittance) while achieving good color, .

<Solid-state image sensor>

The solid-state image pickup device of the present invention includes the color filter of the present invention. The color filter of the present invention has high heat resistance and light resistance, and a solid-state image pickup device having this color filter can obtain good color reproducibility.

The configuration of the solid-state image pickup device is not particularly limited as long as it includes the color filter of the present invention and functions as a solid-state image pickup device. For example, the following configuration can be given.

In other words, a plurality of photodiodes constituting a light receiving area of a CCD image sensor (solid-state image pickup device) and transfer electrodes made of polysilicon or the like are provided on a substrate, a color filter of the present invention is provided thereon, .

The camera system having the color filter of the present invention is provided with a camera lens, a cover glass coated with a dichroic coating film, a microlens, etc. from the viewpoint of light discoloration of the color material, It is preferable to absorb a part or all of the UV light. In addition, as the structure of the camera system, it is preferable that the structure of the camera system is such that the oxygen permeability to the color filter is reduced in order to suppress oxidation and discoloration of the color material. For example, a part or all of the camera system is sealed with nitrogen gas desirable.

<Image Display Device>

The image display apparatus of the present invention includes the color filter of the present invention. The color filter of the present invention is particularly preferable as a color filter for a liquid crystal display device because it has excellent coloring and also has coloring pixels free from missing, peeling, and kinking. The liquid crystal display device provided with the color filter of the present invention can display a high-quality image.

The definition of the display device and the description of each display device are described in, for example, "Electronic Display Device" (Sasaki Teruo Co., Ltd., Sakai, Kagoshima, 1990), "Display Device" (Ibuki Sumi Architect, , Published in 1989). The liquid crystal display device is described in, for example, &quot; Next Generation Liquid Crystal Display Technology &quot; (edited by Tatsuo Uchida, Sakai, Kagoshima, 1994). The liquid crystal display device to which the present invention can be applied is not particularly limited. For example, the present invention can be applied to various liquid crystal display devices described in the &quot; next generation liquid crystal display technology &quot;.

The color filter of the present invention is effective especially for a color TFT type liquid crystal display device. The color TFT type liquid crystal display device is described in, for example, &quot; color TFT liquid crystal display &quot; (published by Kyoritsu Shotpan Co., Ltd., 1996). The present invention can also be applied to a liquid crystal display device such as a transverse electric field driving system such as an IPS or a pixel division system such as an MVA or an STN, TN, VA, OCS, FFS and R-OCB .

Further, the color filter of the present invention can be provided in a bright and high-definition color-filter on array (COA) method. In the COA type liquid crystal display device, the required characteristics for the color filter layer are required for the interlayer insulating film, that is, the low dielectric constant and the peel liquid resistance, in addition to the usual required characteristics as described above. It is considered that the color filter of the present invention enhances the transparency of the ultraviolet laser as the exposure light by selecting the color or the film thickness of the pixel specified by the present invention in addition to the exposure method using the ultraviolet laser. As a result, the curing property of the colored pixel is improved to form a pixel free from the missing, peeled, or kinked, so that the coloring layer formed directly or indirectly on the TFT substrate is particularly improved in the peeling liquid resistance, . A resin film may be formed on the color filter layer in order to satisfy the requirement of low dielectric constant.

The coloring layer formed by the COA method has a rectangular through-hole or a C-shaped portion having a length of about 1 to 15 mu m in order to conduct the ITO electrode disposed on the colored layer and the terminal of the driving substrate below the colored layer, It is preferable to set the dimension of the conduction path (that is, the length of one side) to 5 mu m or less. However, by using the present invention, a conduction path of 5 mu m or less is formed It is also possible.

These image display methods are described in, for example, page 43 of "EL, PDP, and LCD display technology and the latest trend in the market" (issued by Toray Research Center Research Institute, 2001).

The liquid crystal display device of the present invention is composed of various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle compensation film in addition to the color filter of the present invention. The color filter of the present invention can be applied to a liquid crystal display device constituted by these known members.

These members are described in, for example, "The Market of Liquid Crystal Display Materials and Chemicals" (published by Shimashita Shimashita Co., Ltd. in 1994), "2003 Current Status and Future Prospects of LCD-related Markets" Yoshikichi, Fuji Chimera Soken Co., Ltd., published in 2003).

For the backlight, refer to SID meeting Digest 1380 (2005) (A.Konno et.al) or "Monthly Display" December 2005, pages 18-24 (Yoshihiro Shimaya), 25-30 pages (Yagi Takaaki) .

When the color filter of the present invention is used in a liquid crystal display device, a high contrast can be achieved when combined with a conventional three-wavelength tube of a cold cathode tube, and by using LED light sources (RGB-LEDs) of red, It is possible to provide a liquid crystal display device having high luminance, high color purity, and good color reproducibility.

(Example)

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples unless the present invention exceeds the conventional limit. Unless otherwise stated, &quot; part &quot; and &quot;% &quot; are based on mass.

&Lt; Example 1 >

[Color filters for image display devices]

- Preparation of coloring composition -

7 parts of the above-mentioned Exemplary Compound A1, which is a specific dipyrammethene metal complex compound, and C.I. Pigment Blue 15: 6 6 parts and an aerosol dispersion of an acrylic pigment dispersant (Macromonomer AA-6 (trade name) manufactured by Toagosei Co., Ltd.) and Light Ester HO-MS (trade name, manufactured by Kyoeisha Chemical Co., (Weight average molecular weight: 28,000, acid value: 79)) was mixed with 40 parts of propylene glycol monomethyl ether acetate, and the pigment was thoroughly dispersed using a bead mill to prepare a pigment dispersion (S-1). The volume average particle diameter of the pigment in the pigment dispersion (S-1) measured using a nano-track particle size distribution analyzer UPA-EX150 (manufactured by Nikkiso Co., Ltd.) was 48 nm.

Subsequently, 10 parts of the pigment dispersion (S-1) obtained above, 30 parts of polystyrene (weight average molecular weight 70,000) and 60 parts of methyl ethyl ketone / toluene (1/1 = v / v) were mixed to prepare a coloring composition.

- Preparation of color filter by coloring composition -

The colored composition obtained above was coated on a glass substrate by wire bar coating so as to have a thickness of 1 mu m at the time of drying to prepare a colored glass. This colored glass was a clear blue color filter.

The coloring composition obtained above was stored at room temperature for one month, and the degree of precipitation of foreign matter after storage was observed at the time of observation. As a result, precipitation of foreign matter was not observed.

&Lt; Example 101 >

[Color filters for image display devices]

- Preparation of colored curable composition 1 -

The following components used in the preparation of the colored curable composition 1 were prepared.

(S-2) Pigment dispersion liquid: C.I. 12.8 parts of Pigment Blue 15: 6 and 10 parts of a copolymer of an acrylic pigment dispersant (macromonomer AA-6 (trade name) manufactured by Toagosei Co., Ltd.) and light ester HO-MS (trade name: (Weight average molecular weight: 28,000, acid value: 79)) was mixed with 80.0 parts of propylene glycol monomethyl ether acetate, and the pigment was sufficiently dispersed using a bead mill to obtain a pigment dispersion

(T-1) Polymerizable compound: Kayalard DPHA (a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.)

(U-1) Propylene glycol monomethyl ether acetate solution (solid content 40.0%) of an alkali soluble binder: benzyl methacrylate / methacrylic acid copolymer (75/25 [mass ratio], weight average molecular weight 12,000)

(V-1) Polymerization initiator: 2- (benzoyloxyimino) -1- [4- (phenylthio) phenyl] -1-octanone

(V-2) Polymerization initiator: 2- (acetoxyimino) -4- (4-chlorophenylthio) -1- [9-ethyl-6- (2-methylbenzoyl) -9H- Yl] -1-butanone

(W-1) Photosensitizer: 4,4'-bis (diethylamino) benzophenone

(X-1) Organic solvent: Propylene glycol monomethyl ether acetate

(X-2) Organic solvent: ethyl 3-ethoxypropionate

(Y-1) Surfactant: Megafac F781-F (manufactured by Dainippon Ink and Chemicals, Inc.)

Each of the components was mixed according to the following composition to prepare a colored curable composition 1.

&Quot; Composition of Coloring Curable Composition 1 &

· Exemplified Compound A1 (dipyrromethene metal complex compound) 6.9 part

· (S-2) ... 43.0 parts

The above (T-1) ... 103.4 parts

The above (U-1) ... 212.2 parts (84.9 parts in terms of solid content)

- (V-1) 21.2 part

- (V-2) 3.8 part

The above (W-1) ... 3.5 parts

(X-1) 71.9 parts

- (X-2) 3.6 part

The above (Y-1) ... 0.06 part

-Preparation of Color Filter by Coloring Curable Composition 1 -

The colored curable composition 1 obtained above was applied onto a glass substrate (product number 1737, made by Corning Inc.) having a size of 100 mm x 100 mm so as to have an x value of 0.650 which is an index of color density and dried in an oven at 90 캜 for 60 seconds ). Thereafter, the resist film was exposed to light by a high-pressure mercury lamp through a photomask having a mask hole width of 10 to 100 mu m for evaluation of resolution, and the coated film after exposure was irradiated with an alkali developer CDK-1 (manufactured by FUJIFILM ELECTRONIC MATERIALS CO., LTD. % Aqueous solution, and allowed to stand for 60 seconds. After standing, pure water was dispersed in a shower and the developer was washed away. Then, the coated film having been subjected to the exposure and development as described above was heat-treated (post-baking) in an oven at 220 캜 for one hour to form a coloring pattern (colored resin film) for the color filter on the glass substrate, Of color filter.

-evaluation-

The following evaluation was made on the color filter obtained above. The evaluation results are shown in Table 9 below.

(Curing sensitivity)

After the pre-baking, the amount of exposure required to obtain the line width equal to the mask width when exposed to light with a high-pressure mercury lamp through a photomask was measured and evaluated according to the following criteria. The lower the exposure dose, the higher the sensitivity.

<Criteria>

?: Less than 200 mJ / cm 2

DELTA: 200 mJ / cm2 or more and less than 600 mJ / cm2

×: 600 mJ / cm 2 or more

(Heat resistance)

The color filter was heated at 230 캜 for 30 minutes using a hot plate, and the color difference (? E * ab value) before and after heating was measured with a colorimeter MCPD-1000 (manufactured by Otsuka Denshi) and evaluated according to the following criteria. The smaller the value of? E ^* ab, the better the heat resistance.

<Criteria>

?:? E ^* ab <3

?: 3?? E ^* ab <10

×: ΔE ^* ab≥10

(Light resistance)

The color difference (? E ^* ab value) before and after the irradiation was measured with a colorimeter MCPD-1000 (manufactured by OTSUKA DENKI CO., LTD.) With a xenon lamp irradiated with a color filter at 50,000 lux for 20 hours And evaluated according to the judgment criteria. The smaller the value of? E ^* ab, the better the light fastness.

<Criteria>

⊚: ΔE ^* ab <1

?: 1?? E ^* ab <3

?: 3?? E ^* ab <10

×: ΔE ^* ab≥10

(Luminance)

The luminance (Y value) of the color filter was measured with a brown spectrophotometer OSP-SP200 (manufactured by Olympus Corporation) and evaluated according to the following criteria. The higher the Y value, the better the performance as a color filter for a liquid crystal display.

<Criteria>

○: Y value ≥10

?: 9? Y value <10

×: Y value <9

(Storage stability)

The colored curable composition used in the production of the color filter was stored at room temperature for one month, and the degree of precipitation of the foreign matter after storage was observed at the time of observation and evaluated according to the following criteria.

<Criteria>

○: Precipitation was not confirmed.

B: A little precipitation was confirmed.

X: precipitation was confirmed.

&Lt; Examples 102 to 115 and Comparative Examples 101 to 109 >

In Example 101, the Exemplary Compound A1 was substituted with the above-mentioned Exemplary Compound (dipyromethane metal complex compound) described in the following Table 9 or a comparative dye, respectively. Pigment Blue 15: 6 was replaced with the phthalocyanine pigment or the comparative pigment described in the following Table 9, and the ratio of the exemplified compound and the (S-2) pigment dispersion was adjusted so as to be in the same color as in Example 101 Thereby producing the color filters of Examples 102 to 115 and Comparative Examples 101 to 109, respectively. In addition, in Comparative Examples 101 to 103 and 106, the Exemplary Compound A1 in Example 101 was replaced with a dye shown in Table 9 in the same mass, and C.I. Pigment Blue 15: 6 was not added. In addition, Comparative Example 109 was prepared by not adding the Exemplary Compound A1 in Example 101.

Phthalocyanine dye A and phthalocyanine dye B in Table 9 are the following compounds, respectively.

Since Comparative Examples 101, 102, 103, 106 and 109 use a single dye, they can not be adjusted to the same color as Example 101 and can not be compared. Therefore, &quot; - &quot; . Here, the same color means that the x value and the y value of Yxy in the color space RGB color system are coincident with each other.

By comparing Examples 101 to 115 and Comparative Examples 101 to 103, it was found that the light resistance of a color filter was improved by using a specific dipyrammethene metal complex compound and a phthalocyanine-based pigment in combination.

A color filter produced by using the colored curable composition of the present invention by comparison of Examples 101 to 115 and Comparative Examples 104, 105, 107 and 108 (a colored curable composition containing a conventionally known coloring matter mixture) Y value).

From the viewpoint that the light resistance of Examples 101 to 105 is particularly good, it has been found that the specific dimpyromethene metal complex compound is a dipyromethane metal complex compound represented by the general formula (3), and the light resistance is remarkably improved.

The colored curable composition of the present invention has a high curing sensitivity, even though it contains a dipyrromethene metal complex compound as a dye.

It is also clear that all of the colored curable compositions of the present invention are excellent in storage stability.

Claims (13)

(A-1) a coloring composition characterized by containing a dipyrammethene metal complex compound represented by the following general formula (3), (B) a phthalocyanine-based pigment, (C) a dispersant, and (D) an organic solvent.

[Wherein R ¹¹ and R ¹² each independently represents an alkoxycarbonyl group having 6 to 30 carbon atoms, R ¹³ and R ^{14 each} represent a methyl group, and R ¹⁵ , R ¹⁶ , R ¹⁷ , and R ¹⁸ each represents And X represents a substituted or unsubstituted acyloxy group having 2 to 3 carbon atoms, a substituted or unsubstituted alkylsulfonyloxy group, a substituted or unsubstituted arylsulfo group N1 and n2 each independently represent an integer of 0 to 5, and n3 and n4 each independently represent an integer of 0 to 3, delete delete The method according to claim 1,
(A-1) the dipyrammethene metal complex compound is (A-4) a dipyrromethene metal complex compound represented by the following general formula (4).

[Wherein R ¹³ and R ¹⁴ each independently represents a methyl group, and X represents a substituted or unsubstituted acyloxy group having 2 to 3 carbon atoms, a substituted or unsubstituted alkylsulfonyloxy group, a substituted or unsubstituted An arylsulfonyloxy group or a halogen atom, The method according to claim 1,
Wherein the phthalocyanine pigment (B) is Pigment Blue 15: 6. A colored curable composition characterized by containing the coloring composition according to any one of claims 1 to 5, (E) a polymerizable compound, and (F) a polymerization initiator. The method according to claim 6,
Wherein the (E) polymerizable compound is a (meth) acrylate-based polyfunctional monomer. The method according to claim 6,
Wherein the polymerization initiator (F) is a oxime-based compound. A color filter comprising a colored layer formed by using the coloring composition according to any one of claims 1, 4 and 5. A colored layer forming step of forming a colored layer by applying the colored curable composition according to claim 6 on a substrate;
An exposure step of forming a latent image by exposing the colored layer in a pattern shape;
And developing the colored layer on which the latent image is formed to form a pattern. A color filter produced by the method for manufacturing a color filter according to claim 10. A solid-state imaging device comprising the color filter according to claim 11. A liquid crystal display device comprising the color filter according to claim 11.