KR101821236B1 - Colored curable composition, method of producing color filter, color filter, solid-state imaging device, and liquid crystal display - Google Patents

Abstract

[일반식(I) 중, R¹∼R⁶은 각각 독립적으로 수소원자 또는 치환기를 나타낸다. R⁷은 수소원자, 할로겐원자, 알킬기, 아릴기 또는 헤테로환기를 나타낸다. 단, R¹과 R⁶이 서로 결합해서 환을 형성하는 경우는 없다]Disclosed is a colored curable composition which is capable of forming a colored cured film having a small dependency of development time in pattern formation and having high light resistance.
(A-2) a phthalocyanine-based pigment; (B) a dispersing agent; (C) a pigment having a specific structure represented by the following formula (D) a photopolymerization initiator, and (E) an organic solvent.

[In the general formula (I), R ¹ to R ⁶ each independently represent a hydrogen atom or a substituent. R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group. Provided that R < ¹ > and R < ⁶ > are not bonded to each other to form a ring]

Description

TECHNICAL FIELD [0001] The present invention relates to a color curable composition, a color filter manufacturing method, a color filter, a solid-state image pickup device, and a liquid crystal display (LCD)

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

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.).

The pigment dispersion method is a method of producing a color filter by photolithography using a colored photosensitive composition in which a pigment is dispersed in various photosensitive compositions. This is because it is patterned by a photolithography method, and therefore, it is highly suitable for manufacturing a large-sized, high-definition color filter having a high positional accuracy. When a color filter is produced by a pigment dispersion method, a photosensitive composition is applied on a glass substrate by a spin coater, a roll coater or the like to form a coated film, and the colored film is formed by pattern exposure and development to form colored pixels. By repeating color by color, a color filter is obtained.

As a coloring photosensitive composition using a pigment, for example, a blue coloring composition for a color filter containing the phthalocyanine-based pigment described in Patent Document 1 is known.

When a color filter using a pigment is provided to manufacture a display device such as a liquid crystal display device or a solid-state image pickup device, a pigment with a smaller particle size is required from the viewpoint of improving the contrast. This is due to the fact that the polarization axis is rotated by light scattering and birefringence due to the pigment. If the fineness of the pigment is insufficient, light is scattered and absorbed by the pigment to lower the light transmittance, lowering the contrast, and lowering the curing sensitivity at the time of pattern exposure.

Particularly, in the color filter for a solid-state image pickup device, a higher fineness is desired in recent years, and thus it is difficult to further improve the resolution in a pigment dispersion system which has been conventionally performed. That is, there is a problem that color unevenness occurs due to the influence of coarse particles of the pigment. Therefore, the pigment dispersion system is not suitable for use in which a fine pattern having a pixel size of 1.5 占 퐉 占 1.5 占 퐉 to 3.0 占 占 占 퐉 like the solid-state image pickup element is required.

In response to such a situation, there has been proposed a technique of using a dye instead of a pigment. However, it has been known that the dye generally has deteriorated light resistance and heat resistance as compared with the pigment, which is a problem in terms of color filter performance. In addition, the dye has a low solubility in the photosensitive composition and has a problem that stability in time is low in the state of the liquid preparation or the coating film, and the dye is precipitated.

For these problems, there has been proposed a colored curable composition capable of forming a color filter having excellent storage stability and high light resistance by using a dye containing a dipyramethylene group compound and a phthalocyanine dye in combination (see, for example, Patent Document 2 ).

Further, a colored curable composition in which a dye and a pigment are combined is also known (see, for example, 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

As described above, it is known that an effect of forming a color filter having high light resistance according to the selection of a dye to be used can be obtained for a colored curable composition using a dye. However, in order to further improve the fineness and performance of the color filter, It is a present situation that further improvement of the effect is desired.

SUMMARY OF THE INVENTION It is therefore an object of the present invention to provide a colored curable composition capable of forming a colored cured film having a small dependency of development time in pattern formation and having high light resistance, We assume one task.

A second object of the present invention is to provide a color filter excellent in 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.

Specific means for achieving the above object are as follows.

(A-2) a phthalocyanine-based pigment, (B) a dispersant, (C) a compound represented by the following general formula (A-1) (D) a photopolymerization initiator, and (E) an organic solvent, wherein the at least one compound is at least one compound selected from the group consisting of MO-1 to MO-5.

[In the general formula (I), R ¹ to R ⁶ each independently represent a hydrogen atom or a substituent. R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group. Provided that R < ¹ > and R < ⁶ > are not bonded to each other to form a ring]

In the general formulas (MO-1) to (MO-5), n is an integer of 0 to 14, and m1 to m4 are integers of 1 to 8. A plurality of R and T present in the same molecule may be the same or different.

At least one of the plurality of R present in each of the polymerizable compounds represented by the general formulas (MO-1) to (MO-5) is -OC (═O) CH═CH ₂ or -OC (═O) C It represents a (CH ₃₎ = CH _2. In the formula (MO-2), when Z is -O-, n is 1 or more, or R is a group other than -OC (= O) CH = CH ₂ .

&Lt; 2 > The polymerizable composition according to < 1 >, wherein the polymerizable compound (C) is a compound represented by the formula (MO-2) Any one of the following triblock color-curable compositions.

In the above groups, m1 and m2 are each an integer of 1 to 8.

<3> The colored curable composition according to <1> or <2>, wherein the photopolymerization initiator (D) is a oxime-based compound.

(4) The complex represented by any one of (1) to (3), wherein the complex represented by the general formula (I) Lt; RTI ID = 0.0 &gt; 1, &lt; / RTI &gt;

[In the formula (II-1), R ¹ to R ⁶ each independently represent a hydrogen atom or a substituent. R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group. Ma represents a metal atom or a metal compound, X ² represents a group necessary for neutralizing the charge of Ma, and X ¹ represents a group capable of binding to Ma. X ¹ and X ² may be bonded to each other to form a 5-membered, 6-membered or 7-membered ring. Provided that R &lt; ¹ &gt; and R &lt; ⁶ &gt; are not bonded to each other to form a ring]

&Lt; 5 > A complex containing a compound represented by the general formula (I) and a metal atom or a metal compound represented by the general formula (II-2) Lt; RTI ID = 0.0 &gt; 1, &lt; / RTI &gt;

[In the formula (II-2), R ¹ to R ⁶ and R ⁸ to R ¹³ each independently represent a hydrogen atom or a substituent. R ⁷ and R ¹⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group. And Ma represents a metal atom or a metal compound. Provided that R ¹ and R ⁸ or R ¹³ and R ⁶ and R ⁸ or R ¹³ do not bond to each other to form a ring]

<6> A complex according to any one of <1> to <3>, wherein the compound represented by formula (A-1) &Lt; / RTI &gt;

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

<7> The colored curable composition according to any one of <1> to <3>, wherein the metal atom or the metal compound is any one of Fe, Zn, Co, V = O and Cu.

<8> The colored curable composition according to any one of <1> to <3>, wherein R ³ and R ⁴ in the general formula (I) are each a phenyl group.

(A) forming a colored curable composition layer by applying the colored curable composition according to any one of (1) to (8) on a support,

And (B) a step of exposing the layer of the colored curable composition formed in the step (A) through a mask and developing the layer to form a colored pattern.

<10> The method of producing a color filter according to <9>, which comprises a step (C) of irradiating a colored pattern formed in the step (B) with ultraviolet light, a step of performing a heat treatment on a colored pattern irradiated with ultraviolet rays in the step (C) ). &Lt; / RTI &gt;

<11> A color filter produced by the method of manufacturing a color filter according to <9> or <10>.

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

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

According to the present invention, it is possible to provide a colored curable composition capable of forming a colored cured film having a small dependency of development time in pattern formation and having high light resistance.

According to the present invention, it is possible to provide a color filter excellent in 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.

&Quot; Coloring curable composition &

First, the colored curable composition of the present invention will be described.

(A-2) a phthalocyanine-based pigment, (B) a dispersing agent, (C) a dispersing agent, (C) a colorant, At least one compound selected from the polymerizable compounds represented by the following general formulas (MO-1) to (MO-5), (D) a photopolymerization initiator, and (E) an organic solvent.

The respective components of (A-1), (A-2), (B), (C), (D) and (E) will be described below.

[(A-1) Complex containing a compound represented by the general formula (I) and a metal atom or a metal compound]

The colored curable composition of the present invention contains, as one of the coloring agents, (A-1) a complex represented by the following general formula (I) and a metal atom or a metal compound (hereinafter referred to as "specific complex" . Certain complexes typically comprise the compound of formula (I) in a deprotonated state.

- dipyrromethene compound -

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

In the general formula (I), R ¹ to R ⁶ each independently represent a hydrogen atom or a substituent. R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group. Provided that R ¹ and R ⁶ are not bonded to each other to form a ring.

The substituents represented by R ¹ to R ⁶ in the general formula (I) include monovalent groups as shown below (hereinafter, the group of the open monovalent groups may be collectively referred to as "substituent R") have.

A halogen atom (e.g., fluorine atom, chlorine atom, bromine atom), an alkyl group (preferably a linear, branched or cyclic alkyl group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, And examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a 2-ethylhexyl group, a dodecyl group, a hexadecyl group, An alkenyl group (preferably having 2 to 48 carbon atoms, more preferably an alkenyl group having 2 to 18 carbon atoms, such as a vinyl group (e.g., a methyl group, an ethyl group, an n-propyl group, (Preferably an aryl group having 6 to 48 carbon atoms, more preferably a 6 to 24 carbon atoms, such as a phenyl group or a naphthyl group), a heterocyclic group (e.g., Preferably 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, and includes, for example, 2- Pyridyl group, 2-benzothiazolyl group, 1-imidazolyl group, 1-pyrazolyl group, benzotriazol-1-yl group, A silyl group (preferably a silyl group having 3 to 38 carbon atoms, more preferably 3 to 18 carbon atoms, such as a trimethylsilyl group, a triethylsilyl group, a tributylsilyl group, t-butyldimethylsilyl An alkoxy group (preferably an alkoxy group having 1 to 48 carbon atoms, more preferably a carbon number of 1 to 24, for example, a methoxy group (for example, a methoxy group or an ethoxy group) , A cyclohexyloxy group, a cyclohexyloxy group), an aryloxy group (for example, a methoxy group, an ethoxy group, a 1-butoxy group, a 2-butoxy group, an isopropoxy group, (Preferably an aryloxy group having from 6 to 48 carbon atoms, more preferably from 6 to 24 carbon atoms, such as a phenoxy group, a 1- (Preferably 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms) such as a 1-phenyltetrazole-5-oxy group, a 2-tetra (Preferably a silyloxy group having 1 to 32 carbon atoms, more preferably a silyloxy group having 1 to 18 carbon atoms, such as a trimethylsilyloxy group, a t-butyldimethylsilyloxy group, a di Phenylmethylsilyloxy), an acyloxy group (preferably an acyloxy group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, such as an acetoxy group, a pivaloyloxy group, a benzoyloxy group, An alkoxycarbonyloxy group (preferably having 2 to 48 carbon atoms, more preferably an alkoxycarbonyloxy group having 2 to 24 carbon atoms, such as an ethoxycarbonyloxy group, a t-butoxycarbonyloxy group, A t-butoxycarbonyloxy group, a cycloalkyloxycarbonyloxy group (For example, a cyclohexyloxycarbonyloxy group), an aryloxycarbonyloxy group (preferably an aryloxycarbonyloxy group having from 7 to 32 carbon atoms, more preferably from 7 to 24 carbon atoms, for example, A carbamoyloxy group (preferably a carbamoyloxy group having 1 to 48 carbon atoms, more preferably a carbamoyloxy group having 1 to 24 carbon atoms, such as N, N-dimethylcarbamoyloxy group, N N-phenylcarbamoyloxy group), a sulfamoyloxy group (preferably having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, (For example, N, N-diethylsulfamoyloxy, N-propylsulfamoyloxy), an alkylsulfonyloxy group (preferably having 1 to 38 carbon atoms, more preferably 1 to 24 carbon atoms Sulfonyloxy group, such as methylsulfonyloxy group, Sardis room sulfonyloxy group, cyclohexyl sulfonyloxy 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, More 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-4-methylcyclohexyl Oxycarbonyl group), 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 Is a carbamoyl group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, and examples thereof include a carbamoyl group, an N, N-diethylcarbamoyl group, an N-ethyl- N-dibutylcarbamoyl group, N-propylcarbamoyl group, N-phenylcarbamoyl group, N-methyl-N-phenylcarbamoyl group and N, N-dicyclohexylcarbamoyl group) Is an amino group having not more than 32 carbon atoms, more preferably not more than 24 carbon atoms, such as an amino group, a methylamino group, an N, N-dibutylamino group, a tetradecylamino group, a 2-ethylhexylamino group, a cyclohexylamino group, An anilino group (preferably an anilino group having 6 to 32 carbon atoms, and more preferably 6 to 24 carbon atoms, such as an anilino group and an N-methylanilino group), a heterocyclic amino group To 32, more preferably 1 to 18, heterocyclic amino groups, A pyridylamino 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, Pivaloylamide group, cyclohexanamide group), an ureido group (preferably an 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 , An N-phenylureido group), an imide group (preferably an imide 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 an alkoxycarbonylamino group having from 2 to 48 carbon atoms, more preferably from 2 to 24 carbon atoms, such as methoxycarbonylamino group, ethoxycarbonylamino group, t-butoxycarbonyl Amino group, octadecylox Carbonylamino group, cyclohexyloxycarbonylamino group), an aryloxycarbonylamino group (preferably an aryloxycarbonylamino group having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms, such as phenoxycarbo Sulfonamido group (preferably having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as a methanesulfonamide group, a butanesulfonamide group, a benzenesulfonamide group, hexa Decane sulfonamide group, cyclohexane sulfonamide group), a sulfamoylamino group (preferably having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as N, N-dipropylsulfamoyl An amino group, an N-ethyl-N-dodecylsulfamoylamino group), an azo group (preferably having 1 to 32 carbon atoms, more preferably an azo group having 1 to 24 carbon atoms such as a phenyl azo group, Lil azo)

(Preferably an alkylthio group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as methylthio group, ethylthio group, octylthio group, cyclohexylthio group), arylthio group (Preferably an arylthio group having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms, such as a phenylthio group), a heterocyclic thio group (preferably having 1 to 32 carbon atoms, Is a heterocyclic thio group having 1 to 18 carbon atoms, such as 2-benzothiazolylthio group, 2-pyridylthio group or 1-phenyltetazolylthio group), an alkylsulfinyl group (preferably having 1 to 32 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 Is an alkylsulfonyl group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, and examples thereof include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, a butylsulfonyl group, an isopropylsulfonyl group, An arylsulfonyl group (preferably an arylsulfonyl group having 6 to 48 carbon atoms, more preferably a carbon number of 6 to 24, such as a phenylsulfonyl group (for example, a phenylsulfonyl group, an isobutylsulfonyl group, an octylsulfonyl 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-dipropyl sulfamoyl group Ethyl-N-dodecylsulfamoyl group, N-ethyl-N-phenylsulfamoyl group, N-cyclohexylsulfamoyl group), sulfo group, phosphonyl group (preferably having 1 to 32 carbon atoms, Preferably a phosphonyl group having 1 to 24 carbon atoms, such as phenoxyphosphine (Preferably having 1 to 32 carbon atoms, more preferably a phosphinoylamino group having 1 to 24 carbon atoms, such as diethoxyphosphino (methoxy) phosphine, An amino group, a dioctyloxyphosphinoylamino group).

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

In the formula (I), R ¹ and R ² , R ² and R ³ , R ⁴ and R ⁵ , and R ⁵ and R ⁶ are each independently bonded to form a 5-membered, 6-membered or 7-membered ring Or may be formed. 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 pyrrole 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 more substitutable groups, they may be substituted with any one of the substituents R. When the substituents are substituted with two or more substituents, these substituents may be the same or different.

- metal atoms or metal compounds -

Next, the metal atom or metal compound constituting the specific complex will be described.

The metal or metal compound used herein 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, Zn, Mg, Si, Sn , Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe , etc. In addition, AlCl, InCl, FeCl, TiCl 2, SnCl 2, SiCl 2, GeCl _2, and the like, metal oxides such as TiO ₂ and VO ₂ , and metal hydroxides such as Si (OH) ₂ .

Among them, Fe, Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO or VO are preferable from the standpoints of stability of the complex, spectral characteristics, heat resistance, light resistance, Fe, Zn, Mg, Si, Pt, Pd, Cu, Ni, Co or VO is more preferable and Fe, Zn, Cu, Co or VO (V = O) is most preferable.

Preferable forms of the complex represented by the general formula (I) and the metal atom or the metal compound are shown below.

That is, in the general formula (I), each of R ¹ and R ⁶ independently represents a hydrogen 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 amino group, an anilino group, a heterocyclic amino group, a carbonamido group, an ureido group, an imide group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonamido group, an azo group, an alkyl group R ² and R ⁵ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, an aryl group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group or a phosphinoylamino group, , A heterocyclic group, a hydroxyl group, a cyano group, a nitro group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, Group, a sulfonamide group, an azo group, alkylthio group, arylthio group, heterocyclic thio group, alkylsulfonyl group, arylsulfonyl group or sulfamoyl group is represented by group, R ³ and R ⁴ are each independently a hydrogen atom, 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 aryloxy group, a heterocycleoxy group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, An alkyl group, an aryl group, an aryl group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group or a phosphinoylamino group, R ⁷ is a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group, and the metal atom or the metal compound is Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, The form represented by VO Can.

More preferred forms of the compound represented by the general formula (I) and the complex containing the metal atom or the metal compound are shown below.

That is, in the general formula (I), R ¹ and R ⁶ 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, An alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonamido group, an azo group, an alkylsulfonyl group, an arylsulfonyl group or a phosphinoylamino group, and R ² and R ⁵ are each independently a hydrogen atom, An aryl group, an aryl group, a heterocyclic group, a cyano group, a nitro group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an imide group, an alkylsulfonyl group, an arylsulfonyl group, or a sulfamoyl group, each independently represent an alkyl group, an alkenyl group, is, R ³ and R ⁴ are each independently 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 carbon amide group, w Ido group, an imide group, alkoxycarbonylamino group, sulfonamide group, alkylthio group, arylthio group, heterocyclic thio group, alkylsulfonyl group, arylsulfonyl group or sulfamoyl group is represented as a group, R ⁷ is a hydrogen atom, a halogen A form in which the metal atom or the metal compound is represented by Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, or VO is exemplified by an atom, an alkyl group, an aryl group or a heterocyclic group.

Particularly preferred forms of the complex represented by the general formula (I) and the metal atom or the metal compound are shown below.

That is, in the general formula (I), R ¹ and R ⁶ each independently represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an amino group, a heterocyclic amino group, a carbonamido group, an ureido group, an imide group, an alkoxycarbonylamino group, R ² and R ⁵ are each independently selected from the group consisting of an alkyl group, an aryl group, a heterocyclic group, a cyano group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, an acyl group, an acyl group, an alkylsulfonyl group, an arylsulfonyl group, or a phosphinoylamino group; R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, R ⁷ is a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, And the metal atom or metal compound is represented by Zn, Cu, Co or VO.

Particularly, it is preferable that R ³ and R ⁴ in the general formula (I) are each a phenyl group because they are excellent in fastness. This is because (1) R ³ and R ⁴ are each a phenyl group, the spectroscopy of the compound is long-wavelength and the energy transfer is facilitated by overlapping with the spectroscopy (around 550 nm) with the phthalocyanine pigment used in combination 2) It is considered that the fastness of this compound itself is enhanced by the presence of a sterically bulky substituent.

In the general formula (I), it is preferable that R ² and / or R ⁵ is a 2,6-di-tert-butyl-4-methylcyclohexyloxycarbonyl group in view of excellent solvent solubility.

- a compound represented by the general formula (II-1)

The specific complex in the present invention is one of preferred examples of the compound represented by the following general formula (II-1).

In the general formula (II-1), R ¹ to R ⁶ each independently represent a hydrogen atom or a substituent. R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group. Ma represents a metal atom or a metal compound, X ² represents a group necessary for neutralizing the charge of Ma, and X ¹ represents a group capable of binding to Ma. X ¹ and X ² may be bonded to each other to form a 5-membered, 6-membered or 7-membered ring. Provided that R ¹ and R ⁶ are not bonded to each other to form a ring.

R ¹ ~R ⁶ in the general formula (II-1) is the same meaning as that of R ¹ ~R ⁶ in the general formula (I), as a preferred form.

Ma in the general formula (II-1) represents a metal atom or a metal compound and has the same meaning as the metal atom or the metal compound constituting the above-mentioned specific complex, and the preferable range thereof is also the same.

R ⁷ in the general formula (II-1) is the same meaning as that of R ⁷ in the general formula (I), as a preferred form.

X ¹ in the general formula (II-1) may be any group capable of binding to Ma, and may be a metal chelate such as water, alcohols (e.g., methanol, ethanol, propanol) A group derived from a compound described in Ueno Kagelera (1995 Nankodo), 2 (1996), 3 (1997) and the like.

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

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

- a compound represented by the general formula (II-2)

The specific complex in the present invention is one of preferred examples of the compound represented by the following general formula (II-2).

In the general formula (II-2), R ¹ to R ⁶ and R ⁸ to R ¹³ each independently represent a hydrogen atom or a substituent. R ⁷ and R ¹⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group. And Ma represents a metal atom or a metal compound. Provided that R ¹ and R ⁸ or R ¹³ and R ⁶ and R ⁸ or R ¹³ do not bond to each other to form a ring.

R ¹ ~R ⁶ in the general formula (II-2) is the same meaning as that of R ¹ ~R ⁶ in the general formula (I), as a preferred form.

The substituents represented by R ⁸ to R ¹³ in the general formula (II-2) are the same as the substituents represented by R ¹ to R ⁶ of the compound represented by the general formula (I), and their preferred forms are also the same. When the substituent represented by R ⁸ to R ¹³ in the compound represented by the general formula (II-2) is a substitutable group, it may be substituted with any one of the above-mentioned substituents R. When the substituent is substituted with two or more substituents These substituents may be the same or different.

R ⁷ in the general formula (II-2) is the same meaning as that of R ⁷ in the general formula (I), as a preferred form.

R ¹⁴ in the general formula (II-2) represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group, and the preferable range of R ¹⁴ is the same as the preferable range of R ⁷ . When R ¹⁴ is a more substitutable group, it may be substituted with any one of the above substituents R. When the substituent is substituted with two or more substituents, these substituents may be the same or different.

Ma in the general formula (II-2) represents a metal or a metal compound and has the same meaning as the metal atom or the metal compound constituting the above-mentioned specific complex, and the preferable range thereof is also the same.

R ⁸ and R ⁹ , R ⁹ and R ¹⁰ , R ¹¹ and R ¹² , and R ¹² and R ¹³ in the general formula (II-2) are independently bonded to form a 5-membered, 6-membered or 7-membered ring or Or an unsaturated ring may be formed. The formed ring or unsaturated ring is the same as the ring or unsaturated ring formed by R ¹ and R ² , R ² and R ³ , R ⁴ and R ⁵ , and R ⁵ and R ⁶ in formula (I) The preferred example is also the same.

- a compound represented by the general formula (III)

The specific complex in the present invention is one of preferred examples of the compound represented by the following general formula (III).

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

R ² and R ³ in formula (III) and R ⁴ and R ⁵ may be independently bonded to each other to form a 5-membered, 6-membered or 7-membered ring or unsaturated ring. As the forming ring or unsaturated ring to be formed, the same meaning as the forming ring or unsaturated ring formed by R ² and R ³ and R ⁴ and R ⁵ in the general formula (I) is also preferable.

R ² to R ⁵ and R ⁷ in the general formula (III) have the same meanings as R ¹ to R ⁶ and R ⁷ in the general formula (I), and their preferred forms are also the same.

Ma in the general formula (III) represents a metal or a metal compound and has the same meaning as the metal atom or the metal compound constituting the above-mentioned specific complex, and the preferable range thereof is also the same.

In the general formula (III), R ⁸ and R ⁹ each independently represent an alkyl group (preferably a straight chain, branched chain or cyclic alkyl group having 1 to 36 carbon atoms, more preferably 1 to 12 carbon atoms, Ethyl, propyl, isopropyl, isopropyl, butyl, isobutyl, t-butyl, hexyl, , An alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 12 alkenyl groups such as a vinyl group, an allyl group and a 3-butene-1-yl group), an aryl group Preferably 6 to 36, more preferably 6 to 18, aryl groups such as phenyl and naphthyl groups), a heterocyclic group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 hetero ring groups, For example, 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 alkoxy group (preferably having 1 to 36 carbon atoms, more preferably 1 to 18 carbon atoms, such as methoxy group, ethoxy group (preferably methoxy group), ethoxy group , A propyloxy group, a butoxy group, a hexyloxy group, a 2-ethylhexyloxy group, a dodecyloxy group and a cyclohexyloxy group), an aryloxy group (preferably having 6 to 24 carbon atoms, more preferably 1 to 18 An alkylamino group (preferably an alkylamino group having from 1 to 36 carbon atoms, more preferably from 1 to 18 carbon atoms, such as a methylamino group, an ethylamino group, a propylamino group, a propylamino group, N, N-diethylamino group, N, N-dipropylamino group, N, N-dipropylamino group, N, N-diethylamino group, N-dibutylamino group, N-methyl-N-ethylamino group), aryl (Preferably having 6 to 36 carbon atoms and more preferably 6 to 18 amino groups, and examples thereof include a phenylamino group, a naphthylamino group, an N, N-diphenylamino group, an N-ethyl- Or a heterocyclic amino group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 hetero ring amino groups, for example, a 2-aminopyrrole group, a 3-aminopyrazole group, - 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 (III) The substituent R may be the same or different when it is substituted with two or more substituents.

In formula (III), X ³ represents NR, a nitrogen atom, an oxygen atom or a sulfur atom, X ⁴ represents NRa, an oxygen atom or a sulfur atom, and R and Ra each independently represent a hydrogen atom, an alkyl group Branched or cyclic alkyl group having 1 to 36, more preferably 1 to 12, straight, branched or cyclic alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, Cyclohexyl group, 1-adamantyl group), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, (Preferably a vinyl group, an allyl group, a 3-buten-1-yl group), an aryl group (preferably an aryl group having 6 to 36 carbon atoms, more preferably 6 to 18 carbon atoms, Naphthyl group), a heterocyclic group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 heteroatoms For example, 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 acyl group (preferably an acyl group having 1 to 24 carbon atoms, and more preferably 2 to 18 carbon atoms, such as an acetyl group, a pivaloyl group, a 2-ethylhexyl 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 isopropylsulfonyl group, an isopropylsulfonyl group, an isopropylsulfonyl group, A cyclohexylsulfonyl group), an arylsulfonyl group (preferably an arylsulfonyl group having 6 to 24 carbon atoms, and more preferably 6 to 18 carbon atoms, such as phenylsulfonyl group and naphthylsulfonyl group).

The alkyl group, alkenyl group, aryl group, heterocyclic group, acyl group, alkylsulfonyl group and arylsulfonyl group of R and Ra may be further substituted with any one of the substituents R. When the substituents are substituted with a plurality of substituents, May be the same or different.

In the general formula (III), Y ¹ represents NRc, a nitrogen atom or a carbon atom, Y ² represents a nitrogen atom or a carbon atom, and Rc has the same meaning as R in the above X ³ .

In the formula (III), 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 (III), R ⁹ and Y ² may combine with each other to form a 5-membered, 6-membered or 7-membered ring together with R ⁸ , Y ¹ , 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.

In the formula (III), when the 5-membered, 6-membered or 7-membered ring formed by combining R ⁸ and Y ¹ and R ⁹ and Y ² is a substitutable ring, the group described in any one of the substituents R These substituents may be the same or different when they are substituted with two or more substituents.

In the general formula (III), X ⁵ represents a group capable of binding to Ma, and the same group as X ¹ in the general formula (II-1) can be mentioned.

a represents 0, 1 or 2;

Preferred forms of the compound represented by the general formula (III) are shown below.

In other words, 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 (I) and a metal atom or a metal compound, and X ³ is NR (R is a hydrogen atom, an alkyl group) , a nitrogen atom or an oxygen atom, X ⁴ is NRa and (Ra is a hydrogen atom, an alkyl group, a heterocyclic group) or an oxygen atom, Y ¹ is NRc a (Rc is a hydrogen atom or an alkyl group), a nitrogen atom or a carbon atom, Y ² is a nitrogen atom or a carbon atom, X ⁵ is a group that binds via an oxygen atom, R ⁸ and R ⁹ are each alkyl group independently, an aryl group, a heterocyclic group, or represent an alkoxy group or alkylamino group, R ⁸ and Y ¹ are bonded to each other to form a 5-membered or 6-membered ring, R ⁹ and Y ² are bonded to each other to form a 5-membered or 6-membered ring, and a is 0 or 1.

More preferred forms of the compound represented by the general formula (III) are shown below.

In other words, 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 (I) and a metal atom or a metal compound, X ³ and X ⁴ are oxygen atoms, Y ¹ is NH, Y ² is a nitrogen atom, X ⁵ is a group that binds via an oxygen atom, R ⁸ and R ⁹ are each alkyl group independently, an aryl group, a heterocyclic group, or represent an alkoxy group or alkylamino group, R ⁸ and Y ¹ are bonded to each other to form a 5-membered or 6-membered ring, R ⁹ and Y ² are bonded to each other to form a 5-membered or 6-membered ring, and a is 0 or 1.

Specific examples of specific complexes in the present invention are shown below, but the present invention is not limited thereto.

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

The melting point of the specific complex in the present invention is preferably not too high in view of solubility.

Specific complexes in the present invention are described in U.S. Patent Nos. 4,774,339, 5,433,896, JP-A-2001-240761, 2002-155052, JP-A-3614586, Aust. J. Chem., 1965, 11, 1835-1845, J.H. Boger et al., Heteroatom Chemistry, Vol. 1, No. 5, 389 (1990), and the like.

As a concrete method of synthesizing the specific complex in the present invention, the method described in paragraphs [0131] to [0157] of Japanese Patent Application Laid-Open No. 2008-292970 can be applied.

The photosensitive colored curable composition of the present invention may be used singly or in combination of two or more of the specific complexes.

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

[(A-2) Phthalocyanine Pigment]

The phthalocyanine-based pigment used in 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. In view of light resistance and tinting strength, C.I. Pigment Blue 15, C.I. Pigment Blue 15: 6, Pigment Blue 15: 1, C.I. Pigment Blue 15: 2 is preferable, and C.I. Pigment Blue 15: 6 is preferred.

The content of the phthalocyanine pigment in the coloring and curing composition of the present invention is preferably 10% by mass to 70% by mass, more preferably 20% by mass to 60% by mass, and most preferably 35% by mass, And most preferably from about 50% by mass to about 50% by mass.

The content ratio of the specific complex to the phthalocyanine-based pigment is preferably 100: 15 to 100: 75, more preferably 100: 25 to 100: 50, Is more preferable.

[(B) Dispersant]

The colored curable composition of the present invention contains (B) a dispersant.

As the dispersant (B), a known pigment dispersant or a surfactant is used.

As the dispersing agent, many kinds of compounds are used, for example, phthalocyanine derivatives (commercial product EFKA-745 EFKA CHEMICALS B. V.), SOLSPERSE 5000 (manufactured by The Lubrizol Corp.); Organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.), (meth) acrylic acid-based (co) polymer Polyflow No. 75, No. 90, No. 95 (manufactured by Kyoeisha Chemical Industry Co., Ltd.) and W001 (manufactured by Yusho Co., Ltd.); 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, W017 (manufactured by Yusho Co., Ltd.); Polymer dispersants such as EFKA-46, EFKA-47, EFKA-47EA, EFKA POLYMER 100, EFKA POLYMER 400, EFKA POLYMER 401 and EFKA POLYMER 450 (manufactured by Morishita Sangyo K.K.); SOLSPERSE dispersants (manufactured by The Lubrizol Corp.) such as SOLSPERSE 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000; ADEKA PLURONIC L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P- S-20 (manufactured by Sanyo Chemical Industries).

The content of the dispersant (B) in the colored curable composition in the present invention is preferably 1% by mass to 80% by mass, more preferably 5% by mass to 70% by mass, more preferably 10% % Is most preferable.

[(C) Polymerizable compound]

The colored curable composition of the present invention (C) contains at least one compound selected from the polymerizable compounds represented by the following general formulas (MO-1) to (MO-5).

In the general formulas (MO-1) to (MO-5), n is an integer of 0 to 14, and m1 to m4 are integers of 1 to 8. A plurality of R and T present in the same molecule may be the same or different.

In addition, at least one of the plurality of R present in each of the polymerizable compounds represented by the general formulas (MO-1) to (MO-5) is -OC (═O) CH═CH ₂ or -OC (═O ) represents a _{C (CH 3) = CH 2} . In the formula (MO-2), when Z is -O-, n is 1 or more, or R is a group other than -OC (= O) CH = CH ₂ .

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.

In the general formulas (MO-1) to (MO-5), n is an integer of 0 to 14, and more preferably an integer of 0 to 2. M1 to m4 are preferably an integer of 1 to 8, more preferably 1 to 2.

In the formulas (MO-1) to (MO-5), at least one of Rs present in the same molecule is -OC (═O) CH═CH ₂ or -OC (═O) C ₃ ) = CH ₂ . The other R may be any of the above, but it is preferable that R is the following group.

In the above groups, m1 and m2 are integers of 1 to 8. m1 and m2 are preferably an integer of 1 to 2.

In the formulas (MO-1) to (MO-5), T is preferably - (CH ₂ ) m- or -OCH ₂ -, and particularly preferably - (CH ₂ ) m-.

Z is preferably -O-.

A plurality of R and T present in the same molecule may be the same or different, but the same is preferable from the viewpoint of ease of synthesis.

Among the polymerizable compounds represented by the general formulas (MO-1) to (MO-5), compounds represented by the general formulas (MO-2) and (MO- -2).

Among them, it is particularly preferable that the compound represented by the formula (MO-2) and at least one R present in the formula (MO-2) is any one of the groups shown below.

In the above group, m1 and m2 are each an integer of 1 to 8.

Specific examples of the polymerizable compounds represented by formulas (MO-1) to (MO-5) are shown below. The present invention is not limited thereto.

(2-acryloxyethyl) isocyanate, ethoxylated glycerin triacrylate, pentaerythritol triacrylate, trimethylolpropane acrylate, ditrimethylolpropane tetraacrylate,? -Caprolactone modified tris Acrylate, dipentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, hexa (acryloyloxyethyl ethoxy) dipentaerythritol, dipentaerythritol pentaacrylate, Succinic acid monoester of triethanolamine, trimethylolpropane trimethacrylate,

The colored curable composition of the present invention contains (C) one or more polymerizable compounds represented by the general formulas (MO-1) to (MO-5), but may also comprise two or more kinds. In the case of two or more types, two or more polymerizable compounds represented by the same general formula or two or more polymerizable compounds represented by other general formulas may be used.

The colored curable composition of the present invention may contain a polymerizable compound having a structure other than the polymerizable compound represented by any one of formulas (MO-1) to (MO-5).

Examples of the polymerizable compound having a structure other than the polymerizable compound represented by any one of formulas (MO-1) to (MO-5) (hereinafter appropriately referred to as "other polymerizable compound") include unsaturated carboxylic acids (for example, Acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, and maleic acid), esters and amides thereof, preferably an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, an unsaturated carboxyl Amides of an 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 such as a hydroxyl group, an amino group or a mercapto group with a monofunctional or polyfunctional isocyanate or an epoxy, and a monofunctional or polyfunctional carboxylic acid Dehydration-condensation reaction product with a carboxylic acid and the like are also used as other preferable polymerizable compounds.

Examples of other polymerizable compounds include unsaturated carboxylic acid esters or amides having an isocyanate group or an electrophilic substituent group such as an epoxy group and addition reactants of monofunctional or polyfunctional alcohols, amines and thiols, as well as halogen groups such as a tosyloxy group Substituted carboxylic acid esters or amides having a leaving group substituent and mono- or polyfunctional alcohols, amines and thiol substitution reaction products are also suitable. As another example, it is also possible to use a compound group substituted by an unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid.

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, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate, tetraethylene Glycerol diacrylate, tetrapentaerythritol polyacrylate (number of acrylate groups: 1 to 10), pentapentaerythritol polyacrylate (number of acrylate groups: 1 to 12), sorbitol triacrylate, sorbitol tetra Acrylate, sorbitol pentaacrylate, sorbitol Tolylacetate, polyester acrylate oligomer, and the like.

Examples of the methacrylic ester include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylol ethane trimethacrylate, ethylene glycol dimethacrylate Butanediol dimethacrylate, hexanediol dimethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacryloxy-2-hydroxypropoxy) phenyl ] Dimethylmethane, bis- [p- (methacryloxyethoxy) 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- 59-5241, those having an aromatic skeleton described in JP-A No. 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.

As other polymerizable compounds, 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, Hexamethylene bis-methacrylamide, diethylenetriamine trisacrylamide, 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.

As other polymerizable compounds, urethane-based addition polymerizable compounds prepared by the addition reaction of isocyanate and hydroxyl group are also suitable. As specific examples thereof, there may be mentioned, for example, a single molecule described in Japanese Patent Publication No. 48-41708 Vinyl urethane compounds containing two or more polymerizable vinyl groups in a molecule in which a vinyl monomer containing a hydroxyl group represented by the following general formula (V) is added to a polyisocyanate compound having two or more isocyanate groups.

???????? CH ₂ = C (R ⁴ ) COOCH ₂ CH (R ⁵ ) OH ????? (V)

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

In addition, polymerizable compounds having structures other than the polymerizable compounds represented by the general formulas (MO-1) to (MO-5) in the compounds described in the following literatures can also be used in combination with the polymerizable compounds in the present invention, .

Urethane acrylates such as those described in JP-A-51-37193, JP-A-2-32293, JP-A-2-16765, JP-A-58-49860, Japanese Patent Publication No. 56-17654, Japanese Patent Publication No. 62-39417, Japanese Patent Publication No. 62-39418, urethane compounds having an ethylene oxide skeleton,

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 ,

Polyester acrylates, epoxy resins and (meth) acrylic acid, which are described in the respective publications of JP-B-48-64183, JP-A-49-43191 and JP-A-52-30490, Polyfunctional acrylates and methacrylates such as epoxy acrylates reacted, and specific unsaturated compounds described in JP-A-46-43946, JP-A-1-40337 and JP-A-1-40336 , A vinylphosphonic acid-based compound described in JP-A No. 2-25493, a structure containing a perfluoroalkyl group disclosed in JP-A-61-22048, 20, No. 7, pp. 300-308 (1984), which is incorporated herein by reference in its entirety.

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

[(D) Photopolymerization initiator]

The colored curable composition of the present invention contains (D) a photopolymerization initiator.

The photopolymerization initiator is not particularly limited as long as it can polymerize at least one compound selected from the above-mentioned (C) polymerizable compounds represented by formulas (MO-1) to (MO-5) , Absorption wavelength, availability, cost, and the like.

Examples of the photopolymerization 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 photopolymerization initiator include those described in paragraphs [0070] to [0077] of Japanese Patent Application Laid-Open No. 2004-295116. Of these, oxime compounds are preferable from the point that the 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-based compounds described in Japanese Patent Application Laid-Open Nos. 2000-80068, WO02 / 100903A1, and 2001-233842 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.

Among these, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] - (4- (phenylthio) phenyl) Oxacillin such as 1,2-octanedione and 1- (O-acetyloxime) -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol- Based compounds are particularly preferable. Specific examples thereof include OXE-01 and OXE-02 (manufactured by BASF).

(D-1) to (d-4) shown below as the oxime compounds from the viewpoints of sensitivity, stability with time, and prevention of discoloration at the time of post- Is more preferable.

In the general formulas (d-1) to (d-4), R ²² and X ²² each independently represent a monovalent substituent, A ²² represents a divalent organic group, and Ar represents an aryl group. n is an integer of 1 to 5; The plurality of R ²² , X ²² , A ²² and Ar may be the same or different.

As R ²² , an acyl group is preferable in view of high sensitivity, and specifically, an acetyl group, a propionyl group, a benzoyl group, and a toluyl group are preferable.

Examples of A ²² include an alkylene group substituted with an unsubstituted alkylene group, an alkyl group (for example, methyl group, ethyl group, tert-butyl group or dodecyl group), an alkenyl 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, a styryl group) substituted with an alkyl group Is preferably an alkylene group substituted by an alkylene group.

As the Ar, a substituted or unsubstituted phenyl group is preferable in that the sensitivity is increased and the coloring due to heating over time is suppressed. In the case of the 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.

X ²² is preferably 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 general formulas (d-1) to (d-4), n is preferably an integer of 1 to 2.

Specific examples of the compounds represented by the general formulas (d-1) to (d-4) are shown below, but the present invention is not limited thereto.

In addition to the photopolymerization initiator, other known photopolymerization initiators described in paragraph [0079] of JP 2004-295116 A may be used in the colored curable composition of the present invention.

The photopolymerization initiator may be contained singly or in combination of two or more.

From the viewpoint of obtaining the effect of the present invention more effectively, the content of the photopolymerization initiator (total content in the case of two or more) in the total solid content of the tinting curable composition is preferably 3% by mass to 20% by mass, more preferably 4% %, And particularly preferably from 5% by mass to 18% by mass.

- Increase dye -

The color-curable composition of the present invention may contain a sensitizing dye if necessary. The sensitizing dye can accelerate the radical generation reaction of the photopolymerization initiator and the polymerization reaction of the photopolymerizable compound thereby by the exposure of the wavelength capable of being absorbed by the sensitizing dye.

Examples of such sensitizing dyes include dyes or pigments which absorb known spectral sensitizing dyes or dyes or lights and interact with photopolymerization initiators.

(Spectral sensitizing dyes or dyes)

Preferred spectral sensitizing dyes or dyes for use as the sensitizing dyes used in the present invention include polynuclear aromatic compounds (e.g., pyrene, perylene, triphenylene), xanthines (such as fluorescein, eosine, erythrosine, (For example, benzoic acid, benzoic acid, benzoic acid, benzoic acid, benzoic acid, benzoic acid, benzoic acid and the like), cyanines (for example, thiacarbocyanine, oxacarbocyanine), merocyanines (E.g., thionine, methylene blue, toluidine blue), acridines (e.g., acridine orange, chloroflavin, acriflavine), phthalocyanines (e.g., phthalocyanine, metal phthalocyanine), porphyrins (E.g., tetraphenylporphyrin, a central metal substituted porphyrin), chlorophylls (e.g., chlorophyll, chlorophyllin, central metal substituted chlorophyll), metal complexes (for example, the following compounds), anthraquinones , Anthraquinone), squalium ( For example, squalium), and the like.

Examples of a more preferable spectral sensitizing dye or dye are shown below.

The styryl-based coloring matters described in JP-A-37-13034; Cationic dyes described in JP-A-62-143044; Quinoxalinium salts described in Japanese Patent Publication No. 59-24147; Shinmethylene blue compounds described in JP-A-64-33104; The anthraquinones described in JP-A-64-56767; Benzo xanthene dyes described in JP-A-2-1714; The acridines described in JP-A-2-226148 and JP-A-2-226149; Pyrylium salts described in JP-A-40-28499; Cyanines described in Japanese Patent Publication No. 46-42363; A benzofuran dye described in JP-A No. 2-63053; Conjugated ketone dyes disclosed in JP-A-2-85858 and JP-A-2-216154; The dye described in JP-A-57-10605; Azo-cinnamylidene derivatives described in Japanese Patent Publication (Kokai) No. Hei 2-30321; A cyanine dye described in JP-A-1-287105; The xanthan-based coloring matters described in JP-A-62-31844, JP-A-62-31848 and JP-A-62-143043; Aminostyril ketones described in Japanese Patent Publication No. 59-28325; The dye described in JP-A-2-179643; A merocyanine coloring matter described in JP-A-2-244050; A merocyanine coloring matter described in Japanese Patent Publication No. 59-28326; A merocyanine coloring matter described in Japanese Patent Application Laid-Open No. 59-89303; A merocyanine coloring matter described in JP-A-8-129257; And a benzopyran dye described in JP-A-8-334897.

(A pigment having a maximum absorption wavelength at 350 to 450 nm)

Another preferred form of the sensitizing dye is a dye belonging to the following group of compounds and having a maximum absorption wavelength at 350 to 450 nm.

Examples thereof include polynuclear aromatics (e.g., pyrene, perylene, triphenylene), xanthines (e.g., fluorescein, eosine, erythrosine, rhodamine B, rose bengal), cyanines For example thiocarbocyanine, oxacarbocyanine), merocyanines (for example, merocyanine, carbomerocyanine), thiazines (for example, thionine, methylene blue, toluidine blue) There may be mentioned acridines (for example, acridine orange, chloroflavin, acriflavine), anthraquinones (for example, anthraquinone), and squaluminium (for example, squalum).

With respect to the above sensitizing dye, various chemical formulas as described below can be carried out for the purpose of improving the properties of the colored curable composition of the present invention. For example, by attaching a sensitizing dye and an addition polymerizable compound structure (for example, an acryloyl group or a methacryloyl group) by a method such as covalent bonding, ionic bonding, or hydrogen bonding, high strength of the cured crosslinked film, It is possible to obtain an effect of suppressing unnecessary precipitation of the coloring matter from the coloring material.

The content of the sensitizing dye is preferably from 0.01 to 20% by mass, more preferably from 0.01 to 10% by mass, and still more preferably from 0.1 to 5% by mass, based on the total solid content of the colored curable composition.

Since the content of the sensitizing dye is within this range, it is highly sensitive to the exposure wavelength of the ultrahigh pressure mercury lamp, and it is preferable from the viewpoint of the developing margin and the pattern forming property that the curing property of the center portion is obtained.

- Hydrogen Compounds -

The colored curable composition of the present invention preferably contains a hydrogen cyanide compound. In the present invention, the hydrogen donor compound has an action of further enhancing the sensitivity of the sensitizing dye or photopolymerization initiator to the active radiation, or inhibiting polymerization inhibition of the polymerizable compound by oxygen.

Examples of such hydrogen donor compounds include amines such as MRSander et al., Journal of Polymer Society, vol. 10, p. 3173 (1972), JP-A-44-20189, JP-A-51-82102 , Japanese Patent Application Laid-Open Nos. 52-134692, 59-138205, 60-84305, 62-18537, 64-33104 , And Research Disclosure 33825, and specific examples thereof include triethanolamine, p-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, and p-methylthiodymethyl aniline.

Other examples of the hydrogen donor compound include thiols and sulfides such as thiol compounds described in JP 53-702 A, JP 55-500806 A and JP 5-142772 A, And disulfide compounds disclosed in Japanese Patent Application Laid-Open No. 56-75643. Specific examples thereof include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, 2- (3H) -quinazoline,? -Mercaptonaphthalene, and the like.

Further, examples of the hydrogen donor compound include amino acid compounds (e.g., N-phenylglycine), organometallic compounds (e.g., tributyltin acetate) disclosed in Japanese Patent Publication No. 48-42965, The hydrogen donor described in JP-A-55-34414, and the sulfur compound described in JP-A-6-308727 (e.g., trithian).

The content of these hydrogenated compounds is preferably in the range of 0.1 to 30% by mass, more preferably 1 to 25% by mass with respect to the mass of the total solid content of the colored curable composition from the viewpoints of improvement in the curing rate due to balance of polymerization growth rate and chain transfer , More preferably in the range of 0.5 to 20 mass%.

[(E) Organic solvent]

The colored curable composition of the present invention contains (E) an organic solvent.

The organic solvent is not particularly limited so far as it can satisfy the solubility of the coexisting components and the coating property when it is formed into the colored curable composition, and is preferably selected in consideration of the solubility, coating ability, and safety of the binder.

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, ethyl butyrate, butyl lactate, Ethyl, oxyacetic acid alkyl esters such as methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (specifically, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate Oxypropionic acid alkyl esters such as methyl 3-oxypropionate and ethyl 3-oxypropionate (specifically, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3- Ethoxypropionate, 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 monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate and the like.

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

Examples of the aromatic hydrocarbons include toluene, xylene, and the like.

When these organic solvents include the solubility of the respective components and the alkali-soluble binder, it is also preferable to mix two or more kinds of these organic solvents from the viewpoints of their solubility and the shape of the coated surface. 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, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate.

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

[(F) Other ingredients]

The colored curable composition of the present invention may further contain other components such as an alkali-soluble binder and a cross-linking agent in addition to the above-mentioned respective components as long as the effect of the present invention is not impaired.

- Alkali soluble binder -

The alkali-soluble binder is not particularly limited as long as 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 include polymers having a carboxylic acid in the side chain, such as those disclosed in Japanese Patent Application Laid-open No. 59-44615, Japanese Patent Publication No. 54-34327, Japanese Patent Publication No. 58-12577, Japanese Patent Publication 54 Methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers such as those described in the respective publications of JP-A-25957, JP-A 59-53836 and JP-A 59-71048, An acidic copolymer, a partially esterified maleic acid copolymer and the like, and an acidic cellulose derivative having a carboxylic acid in the side chain is also 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) Rate), 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, Monomers and the like are also useful.

Further, the alkali-soluble binder may have a polymerizable group in the side chain to improve the crosslinking efficiency, for example, a polymer containing an allyl group, a (meth) acrylic group, an aryloxyalkyl 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 Organic Chemical Industry, Ltd.) and CYCLOMER P series (manufactured by DAICEL CHEMICAL INDUSTRIES, LTD.). 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.

Of 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 standpoint of heat resistance, and from the viewpoint of development control, Acrylamide 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 and (meth) acrylamide, and commercially available products such as KS RESIST-106 Industry, Ltd.) and CYCLOMER P series (manufactured by DAICEL CHEMICAL INDUSTRIES, LTD.).

The alkali-soluble binder is a developing property, the weight-average molecular weight in terms of the liquid viscosity (in terms of polystyrene measured by GPC method level) is 1000~2 × 10 ^5, and the polymer is preferred, more preferably a polymer of 2000-1 × 10 ⁵ , And particularly preferably from 5000 to 5 x 10 &lt; ^{4 &} gt ;.

- Cross-linking 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 of the crosslinking agent include (a) an epoxy resin, (b) at least one substituent selected from methylol group, alkoxymethyl group, and 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 crosslinking agents and the like can be found in paragraphs [0134] to [0147] of Japanese Patent Application Laid-Open No. 2004-295116.

- Other additives -

Various additives such as fillers, polymer compounds other than the above, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation agents, and development accelerators can be added to the colored curable composition as necessary. Examples of these additives include those described in paragraphs [0155] to [0156] of Japanese Patent Application Laid-Open No. 2004-295116.

(Surfactants)

A surfactant which may be added to the above-mentioned colored curable composition of the present invention may be added with various surfactants from the viewpoint of further improving the applicability. As the surfactant, various surfactants such as a fluorine surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone surfactant can be used.

In particular, since the color-curable composition of the present invention contains a fluorine-based surfactant, the liquid properties (particularly, fluidity) when the composition is prepared as a coating liquid can be further improved, and uniformity of coating thickness and liquid-saving property can be further improved.

That is, in the case of forming a film using a coating solution to which a coloring curable composition containing a fluorine-containing surfactant is applied, wettability to the surface to be coated is improved by lowering the interfacial tension between the surface to be coated and the coating liquid, . Therefore, even when a thin film of about several microns in thickness is formed with a small amount of liquid, it is effective in forming a film having a uniform thickness with a small thickness variation more appropriately.

The fluorine content in the fluorine surfactant is preferably 3% by mass to 40% by mass, more preferably 5% by mass to 30% by mass, and particularly preferably 7% by mass to 25% by mass. The fluorine-containing surfactant having a fluorine content within this range is effective from the viewpoints of the uniformity of the thickness of the coating film and the liquid-saving property, and the solubility in the colored curing composition is also good.

Examples of the fluorochemical surfactant include MEGAFACE F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, Surflon S-382, SC-101, SC-103, SC-104, Dong F780, and F781 (manufactured by DIC Corporation), Fluorad FC430, FC431, FC171 (above, Sumitomo 3M product) SC-105, SC1068, SC-381, SC-383, S393 and KH-40 (manufactured by Asahi Glass).

Specific examples of the nonionic surfactant include glycerol, trimethylol propane, trimethylol ethane, and these ethoxylates and propoxylates (for example, glycerol propoxylate, glycerin ethoxylate and the like), polyoxyethylene lauryl ether , Polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1, SOLSPERSE 20000 (manufactured by The Lubrizol Corp.).

Specific examples of the cationic surfactant include a phthalocyanine derivative (trade name: EFKA-745, manufactured by Morishita Sangyo KK), an organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.) Polymer Polyflow No. 75, No. 90, No. 95 (manufactured by Kyoeisha Chemical Industry Co., Ltd.) and W001 (manufactured by Yusho Co., Ltd.).

Specific examples of the anionic surfactant include W004, W005, W017 (manufactured by Yusho Co., Ltd.) and the like.

As the silicone surfactant, for example, Dow Corning Toray Co., Ltd. TORAY SILICONE SH30PA "," TORAY SILICONE SH30PA "," TORAY SILICONE SH8PA "," TORAY SILICONE SH28PA "," TORAY SILICONE SH28PA "," TORAY SILICONE SH30PA " Momentive Performance Materials Inc. TSF-4440 "," TSF-4300 "," TSF-4445 "," TSF-4460 "," TSF-4452 ", Shin-Etsu Silicone Co., Ltd. KF341 "," KF6001 ", and" KF6002 "of BYK Chemie, and" BYK307 "," BYK323 ", and" BYK330 "of BYK Chemie.

Only one surfactant may be used, or two or more surfactants may be combined.

(Thermal polymerization inhibitor)

In addition, the color-curable composition of the present invention may contain a sensitizer or light stabilizer described in paragraph [0078] of Japanese Patent Application Laid-Open No. 2004-295116, or a thermal polymerization inhibitor described in paragraph [0081] of this publication.

That is, in the colored curable composition of the present invention, it is preferable to add a small amount of a thermal polymerization inhibitor in order to prevent unnecessary thermal polymerization of the polymerizable compound during or during storage of the colored curable composition.

Examples of the thermal polymerization inhibitor usable in the present invention include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis Methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol) and N-nitrosophenylhydroxyamine cerium salt.

The addition amount of the thermal polymerization inhibitor is preferably about 0.01% by mass to about 5% by mass with respect to the mass of the colored curable composition.

(Development accelerator)

In order to further improve the developability of the colored curable composition by promoting the alkali solubility of the non-exposed region, organic carboxylic acid having a molecular weight of 1000 or less, glycerol propoxylate having a molecular weight of 300 to 5,000 (for example, Glycerol propoxylate (Mw 1500), glycerol propoxylate (Mw 1000), glycerol propoxylate (Mw 750), glycerol propoxylate (Mw 4100), etc.) may be added.

Examples of the organic carboxylic acid having a molecular weight of 1000 or less 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; Other carboxylic acids such as phenylacetic acid, hydro atropic acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atrophic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylideneacetic acid, .

[Method of preparing colored thermosetting composition]

The colored thermosetting composition of the present invention is prepared by mixing the above-described 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 together, or each component may be dissolved and dispersed in a solvent and then blended continuously. In addition, the order of introduction and the working conditions at the time of compounding are not particularly limited. For example, all the components may be simultaneously dissolved and dispersed in a solvent to prepare a composition. If necessary, each component may be suitably used as two or more solutions and dispersions, and they may be mixed at the time of use (upon application) good.

The colored curable composition prepared as described above is preferably a filter made of a material such as PP (polypropylene), PE (polyethylene) or nylon having a diameter of about 0.01 to 3.0 탆, more preferably about 0.05 to 0.5 탆 And the like, and can be provided for use after filtration.

The colored curable composition of the present invention is excellent in storage stability and can form a colored cured film excellent in light resistance and can be used for a display device such as a liquid crystal display device or an organic EL display device or a solid state image pickup device For example, a color filter for use in a color filter, and also for the production of printing ink, ink-jet ink, and paint. Particularly, it can be suitably used for forming colored pixels for solid-state image pickup devices such as CCD and CMOS.

«Color filter and its manufacturing method»

Next, a method of manufacturing a color filter (a method of manufacturing a color filter of the present invention) using the colored curable composition of the present invention will be described.

The method for producing a color filter of the present invention comprises the steps of (A) forming a colored curable composition layer by applying the colored curable composition of the present invention on a support, (b) exposing the colored curable composition layer formed in the step (A) And a step (B) of forming a colored pattern by development.

In the method for producing a color filter according to the present invention, particularly, a step (C) of irradiating ultraviolet rays to a colored pattern formed in step (B), a step of performing a heat treatment on a colored pattern irradiated with ultraviolet rays in step D).

Hereinafter, the method of manufacturing the color filter of the present invention will be described in more detail.

- Process (A) -

In the method for producing a color filter of the present invention, the above-mentioned colored curable composition of the present invention is coated on a support by a coating method such as spin coating, soft coating or roll coating to form a colored curable composition layer, Therefore, preliminary curing (prebaking) is performed to dry the colored curable composition layer.

Examples of the support used in the method for producing a color filter of the present invention include soda glass, alkali-free glass, borosilicate glass (Pyrex (registered trademark) glass), quartz glass, and transparent conductive films And a photoelectric conversion element substrate used for a solid-state imaging element or the like, for example, a silicon substrate or a complementary metal oxide semiconductor (CMOS) substrate. These substrates may be formed with black stripes for isolating each pixel. In addition, a primer layer may be formed on these supports, if necessary, in order to improve adhesion with the upper layer, to prevent diffusion of the material, or to planarize the surface.

The colored curable composition of the present invention can be applied directly or through another layer to a substrate by a spin coating method, a slit coating method, a flexible coating method, a roll coating method, a roll coating method, a bar coating method or an ink jet method to form a coating film of a colored curable composition .

In addition, when the colored curable composition is spin-coated on the support, an appropriate organic solvent is dropped and rotated prior to the dropwise addition of the colored curable composition in order to reduce the drop amount of the solution, whereby the fusion of the colored curable composition to the support can be improved.

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

The thickness of the layer of the color-curable composition formed from the color-curable composition is appropriately selected in accordance with the purpose, but in general, it is preferably 0.2 to 5.0 m in a color filter for a solid-state image sensor, More preferably, 0.3 mu m to 1.5 mu m, and most preferably. In the case of a color filter for a liquid crystal display, etc., it is preferably 0.2 mu m to 5.0 mu m, more preferably 1.0 mu m to 4.0 mu m, and most preferably 1.5 mu m to 3.5 mu m.

The thickness of the layer of the color-curable composition referred to herein is the film thickness after pre-baking.

- Process (B) -

Then, in the method of manufacturing a color filter of the present invention, the layer of the colored curable composition formed on the support is exposed through a mask.

The light or radiation usable in this exposure is preferably g-line, h-line, i-line, KrF light, or ArF light, particularly i-line. When i-line is used for the irradiation light, it is preferable to perform irradiation with an exposure amount of 100 mJ / cm 2 to 10000 mJ / cm 2.

As other exposure light beams, various laser light sources such as visible light and ultraviolet light such as ultrahigh pressure, high pressure, medium pressure and low pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, fluorescent lamps, tungsten lamps and the like can be used .

(Exposure step using laser light source)

In the exposure method using the laser light source according to the present invention, an ultraviolet laser is used as the light source. The laser is the head character of English Light Amplification by Stimulated Emission of Radiation. An oscillator and an amplifier for generating monochromatic light having stronger coherence and directivity by amplification and oscillation of a light wave using the phenomenon of induced emission occurring in a material having an inverse distribution, and excitation media such as crystal, glass, liquid, coloring matter and gas , And a laser having an oscillation wavelength in a known ultraviolet light such as a solid laser, a liquid laser, a gas laser, or a semiconductor laser can be used from these media. Among them, a solid laser and a gas laser are preferable from the viewpoint of the output and the oscillation wavelength of the laser.

As the wavelength that can be used in the present invention, an ultraviolet laser in the wavelength range of 300 nm to 380 nm is preferable, and more preferable is an ultraviolet laser in which the wavelength is in the range of 300 nm to 360 nm coincides with the photosensitive wavelength of the resist Do.

Concretely, the third harmonic (355 nm) of the Nd: YAG laser of a relatively high-output, relatively inexpensive solid-state laser, XeCl (308 nm) and XeF (353 nm) of the excimer laser can be suitably used.

The exposed amount of the pinhole (pattern) is in the range of 1 mJ / cm 2 to 100 mJ / cm 2, more preferably in the range of 1 mJ / cm 2 to 50 mJ / cm 2. When the exposure dose is within this range, it is preferable from the viewpoint of productivity of pattern formation.

Examples of the exposure apparatus that can be used in the present invention include, but are not limited to, those available from Callisto (V Technology Co., Ltd.), EGIS (V Technology Co., Ltd.) and DF2200G (Dainippon Screen Mfg. Co., Ltd.) can be used. Apparatuses other than those described above are also suitably used.

It is also possible to use the light emitting diode (LED) and the laser diode (LD) as the active radiation source. In particular, when an ultraviolet ray source is required, ultraviolet LEDs and ultraviolet LDs can be used. For example, Nichia Corporation has marketed purple LEDs whose main emission spectrum has wavelengths between 365 nm and 420 nm. When shorter wavelengths are needed, U.S. Patent No. 6,084,250 discloses an LED capable of emitting centered active radiation between 300 and 370 nm. In addition, other ultraviolet LEDs are also available and can emit radiation in other ultraviolet band. A particularly preferred active radiation source in the present invention is a UV-LED, particularly preferably a UV-LED having a peak wavelength at 340 to 370 m.

Since the ultraviolet laser has a good parallelism, pattern exposure can be performed without using a mask at the time of exposure. However, when the pattern is exposed using a mask, the linearity of the pattern is further increased, which is more preferable.

The exposed colored curable composition layer can be heated at 70 ° C to 180 ° C for 0.5 minutes to 15 minutes using a hot plate or an oven before the next developing process.

In addition, the exposure can be performed while flowing nitrogen gas into the chamber so as to suppress oxidation and discoloration of the coloring material in the colored curable composition layer.

Subsequently, the colored curable composition layer after exposure is developed with a developer. As a result, a coloring pattern (resist pattern) of a negative type or a positive type can be formed.

The developing solution may be a combination of various organic solvents or an alkaline aqueous solution as long as it dissolves the uncured portion (unexposed portion) of the colored curable composition layer and does not dissolve the cured portion (exposed portion). When the developing solution is an alkaline aqueous solution, it is preferable to adjust the alkali concentration to preferably 11 to 13, more preferably 11.5 to 12.5.

Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium silicate, sodium metasilicate, ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, Alkaline aqueous solutions such as ammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo- [5,4,0] -7-undecene.

In particular, an alkaline aqueous solution in which tetraethylammonium hydroxide is adjusted to have a concentration of 0.001 mass% to 10 mass%, preferably 0.01 mass% to 5 mass%, can be used as a developer.

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 alkaline aqueous solution, it is preferable to rinse with water. The rinsing process can be appropriately selected depending on the purpose. Rinsing can be performed by supplying pure water from the spray nozzle to the showerhead from above the rotation center while rotating the support such as a silicon wafer substrate at a rotation number of 10 rpm to 500 rpm.

Thereafter, in the manufacturing method of the color filter of the present invention, post-heating and / or post-exposure may be performed on the coloring pattern formed by the development, if necessary, to promote curing of the coloring pattern.

- Process (C) -

Particularly, in the method of manufacturing a color filter of the present invention, the coloring pattern (pixel) formed by the color curable composition of the present invention is post-exposed by ultraviolet light irradiation to effectively suppress color shift to adjacent pixels or stacked upper and lower layers can do. This color shift is a unique problem that occurs when a dye such as a specific complex is used as a coloring material as in the tinting curable composition of the present invention. Such color shift can be reduced by post exposure by ultraviolet irradiation as described below .

(Post exposure by ultraviolet irradiation)

In the post-exposure by ultraviolet irradiation, ultraviolet light having an irradiation light amount [mJ / cm 2] or more of 10 times or more the exposure amount [mJ / cm 2] in the exposure processing before development is applied to the coloring pattern after the development processing as described above ). &Lt; / RTI &gt;

Between the developing treatment and the heat treatment in the step (D) to be described later, ultraviolet light (UV light) is irradiated to the colored pattern after development for a predetermined period of time to effectively prevent color shift when heated, thereby improving light resistance .

As the light source for irradiating ultraviolet light, for example, ultra high-pressure mercury lamp, high-pressure mercury lamp, low-pressure mercury lamp, DEEP UV lamp and the like can be used. Among them, the ultraviolet light to be irradiated can be irradiated with light having a wavelength of 275 nm or less and having an irradiation intensity [mW / cm 2] of wavelength light of 275 nm or less with respect to an integrated irradiation intensity of all wavelength light in ultraviolet light of 5% . By setting the irradiation intensity of the wavelength light of 275 nm or less in the ultraviolet light to 5% or more, it is possible to further improve the effect of suppressing the color shift to adjacent pixels or the upper and lower layers and the effect of improving the light resistance.

In this regard, the post-exposure by ultraviolet irradiation is performed by using a light source different from a light source such as an i line or the like used for exposure in the above-described step (B), specifically, a high-pressure mercury lamp or a low-pressure mercury lamp desirable. In particular, for the same reason as described above, the irradiation intensity [mW / cm 2] of the wavelength light of 275 nm or less is preferably 7% or more of the integrated irradiation intensity of the whole wavelength light in ultraviolet light. The upper limit of the irradiation intensity of the wavelength light of 275 nm or less is preferably 25% or less.

Also, the integrated illumination intensity refers to an illumination intensity when a curve is plotted along the horizontal axis of the light wavelength [nm] while the vertical axis is the illuminance per unit wavelength of the spectral wavelength (radiant energy passing through the unit area in unit time [mW / m ² ] (Area) of the illuminance of each wavelength light included in the light.

It is preferable that the irradiation of the ultraviolet light is performed with an irradiation light amount [mJ / cm &lt; 2 &gt;] at least 10 times the exposure amount at the time of exposure in the step (B) If the amount of irradiation light in this step (C) is less than 10 times the amount of exposure in exposure in the above-mentioned step (B), color shift between adjacent pixels or between upper and lower layers can not be prevented, .

Among them, the amount of ultraviolet light to be irradiated is preferably 12 times or more and 200 times or less, more preferably 15 times or more and 100 times or less the exposure amount in exposure in the above-mentioned step (B).

In this case, it is preferable that the integrated irradiation illuminance in the ultraviolet light to be irradiated is 200 mW / cm 2 or more. When the integral irradiation intensity is 200 mW / cm &lt; 2 &gt; or more, the effect of suppressing the color shift to adjacent pixels or the upper and lower layers and the effect of improving the light resistance can be improved more effectively. Among them, 250 mW / cm 2 to 2000 mW / cm 2 is preferable, and 300 mW / cm 2 to 1000 mW / cm 2 is more preferable.

- Process (D) -

It is preferable to perform the heat treatment for the colored pattern in which post exposure is performed by ultraviolet irradiation as described above. The coloring pattern can be further cured by heating the formed coloring pattern (so-called post baking).

This heat treatment can be performed by, for example, a hot plate, various heaters, an oven, or the like.

The temperature during 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 30 seconds to 30000 seconds, more preferably 60 seconds to 1000 seconds.

In the method of manufacturing a color filter according to the present invention, after the post-exposure by g-line, h-line, i-line, KrF, ArF, electron beam, X-ray or the like is performed instead of the post exposure by ultraviolet irradiation as in the above- good.

In the case of the post exposure by these means, the irradiation time is 10 seconds to 180 seconds, preferably 20 seconds to 120 seconds, and more preferably 30 seconds to 60 seconds.

In the method of manufacturing a color filter according to the present invention, post-exposure by ultraviolet irradiation as in the above-mentioned step (C) may not be performed, and only post-exposure as in the above-mentioned step (D) may be performed.

The post-exposure and the post-exposure may be performed first, but it is preferable to perform the post-exposure prior to the post-exposure. This facilitates curing by post exposure, thereby suppressing the deformation of the shape due to thermal deflection (sphering of a rectangular pattern) or edge hemming (reflowing of the lower layer of the pattern) of the coloring pattern seen in the post-heating process.

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 above-described steps (A), (B) and (C) and (D) may be repeated in accordance with the desired number of colors.

The above-described step (C) and / or step (D) may be carried out every time the formation of the monochromatic colored curable composition layer, the exposure and the development are completed (for each color), and all the coloring curability (C) and / or the step (D) may be performed collectively after the formation of the composition layer, the exposure, and the development are completed.

The color filter (color filter of the present invention) obtained by the method for producing a color filter of the present invention is excellent in light fastness because it uses the color curable composition of the present invention.

Therefore, the color filter of the present invention can be used for a solid-state image pickup device such as a liquid crystal display device, a CCD image sensor, a CMOS image sensor and the like, and a camera system using the solid-state image pickup device. Among them, the color filter is formed in a thin- And is suitable for use in a solid-state image pickup device requiring a rectangular cross-sectional profile, in particular, a high-resolution CCD element or CMOS exceeding one million pixels.

&Lt; Solid state imaging device &

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 a high light resistance, and a solid-state image pickup device having the 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 is possible.

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

In addition, the camera system having the color filter of the present invention is provided with a camera lens, a cover glass coated with a color-selective coating on the IR cut film, a microlens, etc. from the viewpoint of light color fading of the color material, It is preferable to absorb a part or all of the UV light. The structure of the camera system preferably has a structure in which the oxygen permeability to the color filter is reduced in order to suppress oxidation and discoloration of the coloring material. For example, it is preferable that a part or the whole of the camera system is sealed with nitrogen gas Do.

&Lt; Display device of liquid crystal display device, organic EL display device, etc. &

A display device such as a liquid crystal display device, an organic EL display device, etc. of the present invention is equipped with the color filter of the present invention.

Specific examples of the display device of the present invention include display devices for portable terminals such as a liquid crystal display (LCD), an organic EL display (organic EL display), a liquid crystal projector, a game device display device, A display device, a display device for a car navigation system and the like, particularly a color display device, are suitable.

The definition of the display device and the description of each display device are described in, for example, "Electronic display device (Sasaki Teruo, published by Kogyo Chosakai Publishing, Inc. 1990)", "Display device (Ibuki Sumi Architect, Sangyo-Tosho 1989 Quot; issued &quot; The liquid crystal display device is described in, for example, &quot; Next Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, published by Kogyo Chosakai Publishing, Inc. 1994) &quot;. 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 types of 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 (published by Kyoritsu Shuppan Co., Ltd. 1996) &quot;. The present invention can also be applied to a liquid crystal display device such as a transverse electric field driving system such as IPS, a pixel division system such as MVA or the like, or a STN, TN, VA, OCS, FFS and R-OCB.

Further, the color filter of the present invention can be provided in a bright and high-precision color-filter on array (COA) method. In the COA type liquid crystal display device, besides the above-mentioned usual required characteristics, required characteristics for the color filter layer are required for the interlayer insulating film, that is, low dielectric constant and peel liquid resistance. It is considered that the color filter of the present invention increases the transmittance of the ultraviolet laser as the exposure light by selecting the color or film thickness of the pixel specified by the present invention in addition to the exposure method using the ultraviolet laser. This makes it possible to improve the curability of the colored pixel and to form a pixel free from missing, peeling, or misdirection, so that the coloring layer, which is formed directly or indirectly on the TFT substrate, It is useful for a COA type liquid crystal display device. 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 make the dimension of the conduction path (i.e., the length of one side) particularly 5 m or smaller. However, by using the present invention, it is possible to form a conduction path of 5 m or smaller 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 of the market (Research Study Division, published by Toray Research Center, Inc. 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 assurance 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.

For example, "94 market of liquid crystal display materials and chemicals (published by CMC Publishing Co., Ltd., Shimada, 1994)" and "2003 LCD market" Published by Fuji Chimera Research Institute Inc., 2003).

The backlight is described in SID meeting Digest 1380 (2005) (A.Konno et al) or Monthly Display Dec. 2005, pp. 18-24 (Shimaya Yasuhiro) and 25-30 pages (Yagi Takaaki).

When the color filter of the present invention is used in a liquid crystal display device, high contrast can be realized when combined with a conventionally known three-wavelength tube of a cold-cathode tube. In addition, 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.

Further, when used in an organic EL display device, it is possible to provide an organic EL display device that realizes high contrast, high luminance, high color purity, and good color reproducibility.

Example

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the usual range. Further, unless otherwise specified, "parts" and "%" are all based on mass.

(Example 1)

-One. Preparation of colored curable composition -

The following components were mixed, dispersed, dissolved, and filtered to obtain colored curable composition 1.

(A-2) Pigment Blue 15: 6 dispersion 17.04 parts

          (Solid content concentration: 17.70%, pigment concentration: 11.80%)

(A-1) Specific complex (Example Compound Ia-5) 0.84 part

(D) Photopolymerization initiator (Initiator 1 of the following structure) 0.27 part

(C) Polymerizable compound (monomer A) 0.20 part

(C) Polymerizable compound (monomer F) 0.64 part

Alkali soluble binder: 20% cyclohexanone copolymer of benzyl methacrylate / methacrylic acid solution (molar ratio = 70: 30, weight average molecular weight 30000, hereinafter referred to as &quot; resin A &

0.10 part

(E) Solvent: 10.25 parts of propylene glycol monomethyl ether acetate (hereinafter referred to as "PGMEA")

In addition, the above-mentioned Pigment Blue 15: 6 dispersion was obtained by dispersing the composition of the following formulation in zirconia beads having a diameter of 0.5 mm in a dispersing machine (product name: DISPERMAT, GETZMANN) for 2 hours.

Colorant: Pigment Blue 15: 6 59.00 parts

19.65 parts of a resin solution (benzyl methacrylate / methacrylic acid copolymer, mole ratio: 80/20, Mw: 10000, resin solid concentration: 30%, solvent: PGMEA 70%

Solvent: PGMEA 342.7 parts

Dispersant: 30% solution of BYK-161 (manufactured by BYK) (solvent: PGMEA, butyl acetate)

78.65 parts

(Preparation of colored curable composition 2 to 10)

Except that the types and amounts of the pigment dispersion, the specific complex, the photopolymerization initiator, the polymerizable compound, the polymer and the solvent were changed as shown in Table 1, and the preparation of the colored curable composition of Example 1 To prepare colored curable compositions 2 to 10.

In Table 1, two types of polymerizable compounds are listed, and in the reference examples, two types are used in combination. The amount in parentheses is the amount used and is the mass conversion.

"Resin A" represents an alkali-soluble binder in Example 1, and "CyH" is cyclohexanone.

The preparation of the colored curable composition 1 and the initiators 1 to 3 of the polymerizable compound and the photopolymerization initiator used in Table 1 are as follows. The monomers A to D and F are polymerizable compounds in the present invention, but the monomer D is different from the polymerizable compounds in the present invention.

Polymerizable compound:

Monomer A: ethoxylated isocyanuric acid triacrylate

Monomer B: Pentaerythritol triacrylate

Monomer C: Pentaerythritol tetraacrylate

Monomer D: The following structure

Monomer E: dipentaerythritol hexaacrylate

Monomer F: The following structure

Further, &quot; PB15: 6 &quot; in the column of the pigment dispersion in Table 1 represents the above Pigment Blue 15: 6 dispersion. "PB15" and "PB15: 3" used a pigment Pigment Blue 15: 6 pigment Pigment Blue 15 and a pigment Pig15: 3, respectively, in the preparation of a Pigment Blue 15: 6 dispersion, 15: 6 dispersion liquid.

(Examples 2 to 9 and Reference Example 1)

Each of the colored curable compositions shown in Table 2 was used as Examples 2 to 9 and Reference Example 1.

Each of the color-curing compositions in Examples 1 to 9 and Reference Example 1 was evaluated for light resistance and development time dependency as described below, and the results are shown in Table 2

- Fabrication of single color filter and evaluation of light resistance -

Each colored curable composition obtained above was coated on a glass substrate using a spin coater so that the film thickness after drying was 0.6 占 퐉 and prebaked at 100 占 폚 for 120 seconds to obtain a monochromatic color filter for light resistance evaluation.

The resulting monochromatic color filter for evaluating light fastness was irradiated with a xenon lamp at 100,000 lux for 20 hours (equivalent to 2,000,000 lux · h). The color difference (? E * ab value) of the monochromatic color filter before and after the irradiation with the xenon lamp was measured and used as a light resistance index. The smaller the value of? E * ab is, the better the light resistance is, and the judgment standard is as follows. The results are shown in Table 2.

~ Judgment Criteria ~

?: ΔE * ab value <1

?: 1?? E * ab value <3

?: 3?? E * ab value? 10

×: 10 <ΔE * ab value

- Evaluation of development time dependency -

(1) Preparation of resist solution A (primer solution)

The following components were mixed and dissolved to prepare resist solution A.

· PGMEA 5.20 part

· CyH 52.60 parts

· Binder 30.50 parts

(Benzyl methacrylate / methacrylic acid / 2-hydroxyethyl methacrylate copolymer, molar ratio = 60: 20: 20, weight average molecular weight: 30200 (in terms of polystyrene), 41% cyclohexanone solution)

· Dipentaerythritol hexaacrylate 10.20 parts

Polymerization inhibitor (p-methoxyphenol) 0.006 part

· Fluorine-based surfactant (product of DIC Corporation, F-475) 0.80 part

Photopolymerization initiator: 0.58 parts of 4-benzoxazolane-2,6-bis (trichloromethyl) -s-triazine (TAZ-107 manufactured by Midori Kagaku Co., Ltd.)

(2) Preparation of a glass substrate having a primer layer

The glass substrate (1737, product of Corning Inc.) was ultrasonically washed with 0.5% NaOH water, followed by washing with water and dehydration baking (200 ° C / 20 minutes). Next, the resist solution A obtained in the above (1) was applied to a cleaned glass substrate using a spin coater so as to have a dry thickness of 2 탆, and dried by heating at 220 캜 for 1 hour to obtain a glass having a primer layer Substrate.

(3) Evaluation of development time dependency

A colored curable composition was applied on a primer layer of a silicon wafer substrate having a primer layer obtained in (2) so that the dried film thickness of each coated film was 0.7 m, thereby forming a photo-curable colored curable composition layer. Then, a heat treatment (pre-baking) was performed for 120 seconds using a hot plate at 100 占 폚. Subsequently, light having a wavelength of 365 nm was irradiated through an island pattern mask having a pattern of 1.2 占 퐉 占 1.2 占 퐉 in a range of 100 mJ / cm2 to 2500 mJ / cm2 using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.) The amount of exposure was changed by 100 mJ / cm &lt; 2 &gt; Thereafter, the silicon wafer substrate on which the coated film was formed was mounted on a horizontal rotary table of a spin shower developing machine (DW-30 type; manufactured by Chemitronics Co., Ltd.), and CD-2000 (manufactured by FUJIFILM Electronic Materials) Then, paddle development was performed at 23 DEG C for 30 seconds and 120 seconds to form a colored pattern on the silicon wafer substrate. The development time dependency was evaluated by the following formula.

Development time dependency (%) = D 120 -D 30 / D 120 x 100

D30: The amount of exposure to form a 1.2 mu m pattern when developing for 30 seconds

D120: When the development was carried out for 120 seconds, the exposure amount

~ Judgment Criteria ~

◎: Less than 5%

○: 5% or more and less than 10%

?: 10% or more and less than 15%

×: 15% or more

From the results shown in Tables 1 and 2, it can be seen that the use of the colored curable composition of the present invention resulted in a color filter having a small dependency on developing time and a good light resistance.

Claims (13)

(A-2) at least one compound selected from the group consisting of CI Pigment Blue 15, CI Pigment Blue 15: 3 and CI Pigment Blue 15 (A-1) (B) a dispersant, (C) at least one compound selected from polymerizable compounds represented by the following general formulas (MO-1) to (MO-5), (D) a photopolymerization initiator, And (E) an organic solvent.

[In the general formula (I), R ¹ to R ⁶ each independently represent a hydrogen atom or a substituent. R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group. Provided that R &lt; ¹ &gt; and R &lt; ⁶ &gt; are not bonded to each other to form a ring]

In the general formulas (MO-1) to (MO-5), n is an integer of 0 to 14, and m1 to m4 are integers of 1 to 8. A plurality of R and T present in the same molecule may be the same or different.
At least one of R present in plural of the polymerizable compounds represented by the general formulas (MO-1) to (MO-5) is -OC (═O) CH═CH ₂ or -OC (═O) C It represents a (CH ₃₎ = CH _2. In the formula (MO-2), when Z is -O-, the n is 1 or more, or R or the -OC (= O) a group other than CH = CH _2] The method according to claim 1,
Wherein the polymerizable compound (C) is a compound represented by the general formula (MO-2), and at least one R present in the general formula (MO-2) is any one of the following groups Curable composition.

[Wherein m1 and m2 are each an integer of 1 to 8] The method according to claim 1,
Wherein the photopolymerization initiator (D) is a oxime-based compound. The method according to claim 1,
The colored curable composition according to any one of (A-1) to (C-1), wherein the complex of the compound represented by the general formula (I) and the metal atom or the metal compound is a compound represented by the following general formula (II-1).

[In the formula (II-1), R ¹ to R ⁶ each independently represent a hydrogen atom or a substituent. R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group. Ma represents a metal atom or a metal compound, X ² represents a group capable of neutralizing the charge of Ma, and X ¹ represents a group capable of binding to Ma. X ¹ and X ² may be bonded to each other to form a 5-membered, 6-membered or 7-membered ring. Provided that R &lt; ¹ &gt; and R &lt; ⁶ &gt; are not bonded to each other to form a ring] The method according to claim 1,
Wherein the complex comprising the compound represented by the general formula (I) and the metal atom or the metal compound (A-1) is a compound represented by the following general formula (II-2).

[In the formula (II-2), R ¹ to R ⁶ and R ⁸ to R ¹³ each independently represent a hydrogen atom or a substituent. R ⁷ and R ¹⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group. And Ma represents a metal atom or a metal compound. Provided that R ¹ and R ⁸ or R ¹³ and R ⁶ and R ⁸ or R ¹³ do not bond to each other to form a ring] The method according to claim 1,
Wherein the complex comprising the compound represented by the general formula (I) and the metal atom or the metal compound (A-1) is a compound represented by the following general formula (III).

[In the formula (III), each of R ² to R ⁵ independently represents a hydrogen atom or a substituent. R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group. Ma represents a metal atom or a metal compound, X ³ is NR (R represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl or arylsulfonyl), a nitrogen atom, an oxygen atom X ⁴ represents 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 represents (Wherein Rc represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group or an arylsulfonyl group), a nitrogen atom or a carbon atom, Y ² represents a nitrogen atom or a carbon atom, R ⁸ and R ⁹ each independently represent an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylamino group, an arylamino group or a heterocyclic amino group. R ⁸ and Y ¹ may be bonded to each other to form a 5-membered, 6-membered or 7-membered ring, and R ⁹ and Y ² may be bonded to each other to form a 5-membered, 6-membered or 7-membered ring. X ⁵ represents a group capable of bonding to Ma, and a represents 0, 1 or 2; The method according to claim 1,
Wherein the metal atom or the metal compound is any one of Fe, Zn, Co, V = O, and Cu. The method according to claim 1,
Wherein each of R ³ and R ⁴ in the general formula (I) is a phenyl group. (A) forming a colored curable composition layer by applying the colored curable composition according to any one of claims 1 to 8 on a support;
And a step (B) of exposing the layer of the colored curable composition formed in the step (A) through a mask and then developing the colored layer to form a colored pattern. 10. The method of claim 9,
(C) irradiating the colored pattern formed in the step (B) with ultraviolet light,
Further comprising a step (D) of performing a heat treatment on a colored pattern irradiated with ultraviolet rays in the step (C). A color filter produced by the method of manufacturing a color filter according to claim 9. 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.