TWI505028B - Red color hardening composition, color filter manufacturing method, color filter, and liquid crystal display element - Google Patents

Description

Red color hardening composition, color filter manufacturing method, color filter, and liquid crystal display element

The present invention relates to a red coloring composition, a method of producing a color filter, a color filter, and a liquid crystal display element including the color filter.

A "pigment dispersion method" is well known for a method of producing a color filter for a liquid crystal display element (LCD) and a solid-state image sensor (CCD, COMS, etc.). This pigment dispersion method is a method of producing a color filter by a photolithography method using a colored photosensitive composition in which a pigment is dispersed on various photosensitive compositions. This method is an appropriate method for producing a color filter having high positional accuracy, large screen, and high definition in order to be patterned by photolithography. When a color filter is produced by a pigment dispersion method, a photosensitive film is applied onto a glass substrate by a spin coater or a roll coater to form a coating film, and the coating film pattern is exposed and developed to form a colored pattern. This operation is repeated on various colors to obtain a color filter.

For example, a blue coloring composition for a color filter in which a quinophthalone pigment and an anthraquinone pigment are mixed is described in Patent Document 1. Therefore, a high transmittance, high contrast color filter can be produced in the blue field.

However, when a color filter using a pigment is prepared to produce a display element such as a liquid crystal display element (LCD) or a solid-state image sensor, a pigment having a relatively small particle size is required from the viewpoint of enhancing contrast. This is a result of the rotation of the polarization axis by the pigment, such as scattering of light, birefringence, or the like. When the refinement of the pigment is incomplete, the light can be scattered and absorbed by the pigment light, the light transmittance is lowered, and the contrast is lowered, and the hardening sensitivity at the time of pattern exposure is further reduced.

A technique of using a dye in place of a pigment has been proposed so far as compared with the case of using a pigment as described above. However, dyes are known to have poor light resistance and heat resistance as compared with general pigments, and have been problematic from the viewpoint of the performance of color filters. Further, the solubility of the dye is low with respect to the photosensitive composition, and the stability of the liquid preparation or the coating film is low over time, and the dye has a problem of sucking out the dye. In response to such a problem, it has been proposed to use a color-curable composition containing a dipyrromethene-based compound and an anthraquinone dye to form a color filter excellent in storage stability and high light resistance. (For example, refer to Patent Document 2.)

Further, a color hardening composition in which a dye and a pigment are combined is known. For example, referring to Patent Document 3, it is possible to form a fine pixel excellent in color reproducibility and contrast by combining the two.

[Previous Technical Literature] (Invention patent document)

(Invention Patent Document 1) Japanese Patent Laid-Open Publication No. 2001-33619

(Invention Patent Document 2) Japanese Patent Laid-Open Publication No. 2008-292970

(Invention Patent Document 3) US Patent Publication No. 2008/0171271

As described above, a color filter having excellent storage stability and high light resistance is known from the selection of the dye to be used in the blue color-curable composition using a dye (see Patent Document 2). However, as described above, in order to correspond to higher refinement and lifting performance of the desired color filter, it is desirable to further improve the effect.

Therefore, the present invention has been made in view of the above, and it is an object of the invention to provide a red color-curable composition which is required to have excellent red optical characteristics, a storage stability, and a high-light-resistant color-curable film to be formed in color. Filter. Moreover, it is an object of the invention to provide a color filter excellent in light resistance, a method for producing the color filter, and a liquid crystal display device including the color filter using the red color-curable composition.

The above problems are solved by the following means.

(1) A red color-curable composition comprising a red color-curable composition containing a pigment, a dispersant, and a polymerizable compound in an organic solvent, and further comprising an organometallic complex; The organometallic complex has a metal atom or a metal compound and a residue of a compound represented by the following formula (I) which becomes a ligand.

(In the formula (I), R ¹ to R ⁶ each independently represent a hydrogen atom or a substituent, and R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group).

(2) The colored curable composition according to (1), wherein the organometallic complex is selected from the group consisting of a compound represented by the following formula (II-1) and a compound represented by the following formula (II-2) And at least one of the group consisting of the compounds represented by the following formula (III),

(In the formula (II-1), R ¹ to R ⁷ are synonymous with the above formula (I); Ma represents a metal atom or a metal compound; X ² represents a group necessary for neutralizing the charge of Ma; X ¹ represents a base that can be combined with Ma; X ¹ and X ² can be combined to form a ring of 5, 6 or 7 members), (In the general formula (II-2), R ¹ to R ⁷ are synonymous with the general formula (I); and R ⁸ to R ¹³ each independently represent a hydrogen atom or a substituent; and R ¹⁴ each independently represents a hydrogen atom or a halogen atom. , an alkyl group, an aryl group or a heterocyclic group; Ma represents a metal atom or a metal compound), (In the formula (III), R ² to R ⁵ and R ^{7 have the} same meanings as in the formula (I); Ma represents a metal atom or a metal compound; X ³ represents NR (R represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group) , a heterocyclic group, a fluorenyl group, an alkylsulfonyl group or an arylsulfonyl group), a nitrogen atom, an oxygen atom or a sulfur atom; X ⁴ represents NRa (Ra represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic ring) a group, a fluorenyl group, an alkylsulfonyl group or an arylsulfonyl group; an oxygen atom or a sulfur atom; Y ¹ represents NRc (Rc represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a fluorenyl group, an alkane group; Alkylsulfonyl or arylsulfonyl), a nitrogen atom or a carbon atom; Y ² represents a nitrogen atom or a carbon atom; and R ⁸ and R ⁹ each independently represent an alkyl group, an alkenyl group, an aryl group, a heterocyclic group or an alkyl group; An oxy group, an aryloxy group, an alkylamino group, an arylamino group or a heterocyclic amine group; R ⁸ and Y ¹ may be bonded to each other to form a ring of 5, 6 or 7 members; R ⁹ and Y ² may be bonded to each other; A ring of 5, 6 or 7 members is formed; X ⁵ represents a group which can bind to Ma; a represents 0, 1 or 2).

(3) The color hardening composition according to (1) or (2), wherein the metal atom or metal compound is an iron atom (Fe), a zinc atom (Zn), a cobalt atom (Co), or a vanadium oxide (VO). And any of the copper atoms (Cu).

(4) The color hardening composition according to any one of (1) to (3), wherein, in the formula (I), each of R ³ and R ⁴ is a phenyl group.

(5) The color hardening composition according to any one of (1) to (4), wherein the pigment is at least selected from the group consisting of a diketopyrrolopyrrole pigment, a condensed azo pigment, and an anthraquinone pigment. One.

(6) The colored curable composition according to any one of (1) to (5), which contains a yellow pigment.

(7) The colored curable composition according to any one of (1) to (6), wherein the colored curable composition further contains a photopolymerization initiator.

(8) A method of producing a color filter, comprising: applying a colored curable composition according to any one of (1) to (7) to a substrate to form a red curable composition layer; And the step of developing the red curable composition layer by a photomask to develop a colored pattern.

(9) A method of producing a color filter, comprising the steps of providing a partition wall on a substrate, and spraying the substrate toward the substrate using an ink jet ink jet device in a field surrounded by the partition wall (1) to ( 7) The step of forming a red curable composition layer by the colored curable composition according to any one of the items, and the step of solidifying the red curable composition layer by heat treatment.

(10) A color filter comprising a curable composition layer obtained by curing the colored curable composition according to any one of (1) to (7) on a substrate.

(11) A liquid crystal display device comprising the color filter according to (10).

In the present invention, the organometallic complex compound having a metal atom or a metal compound and a residue which is a ligand represented by the above formula (I) is represented by the above formula (II-1). The organometallic complex compound, the organometallic complex compound represented by the above formula (II-2), and the organometallic complex compound represented by the above formula (III) do not have an anthraquinone skeleton. An organometallic complex of a ligand.

The colored curable composition of the present invention achieves the function of the color-curing film which is excellent in optical characteristics such as red color purity required for forming a color filter, and has high storage stability and high light resistance. Moreover, the color filter of the present invention produced by using the coloring curable composition has particularly excellent red reproducibility and high light resistance, and therefore can suitably cope with a liquid crystal display element which is a high performance which is required recently. Optical components. Further, according to the method of producing a color filter of the present invention, a color filter having the above-described excellent performance can be produced.

[Formation for carrying out the invention]

The red color hardening composition of the present invention contains the organic metal complex (A-1), the pigment (A-2), the dispersing agent (B), and the polymerizable compound (C) in the organic solvent (D). In the organometallic complex, the residue of the compound represented by the above formula (I) is a ligand and has a metal atom or a metal compound. The above-mentioned organometallic complex (A-1) is conventionally known as a coloring agent (see Patent Document 2), but in the present invention, it is coexisted with a pigment as a performance improving agent. Achieving the effects that can not be obtained by any combination of the pigment and the dye: the good color purity of red and the further improvement of the excellent light resistance of the pigment, and the substantial improvement of the preservation stability when the photoresist is formed.

Although the reason for achieving the above-described effects has not been determined, the light resistance can be estimated to be a photochemical process that suppresses photodegradation of the pigment itself due to energy transfer or electron transfer from the pigment to the above metal complex. . With regard to the storage stability, it is presumed that the use of the above-mentioned organometallic complex and the pigment can reduce the amount of the pigment used, and the pigment particles having a large surface area can be stably dispersed.

[(A-1) specific organometallic complex]

The complex (A-1) is a complex of the coloring agent (A-1), and the colored curable composition of the present invention contains a compound represented by the following formula (I) as a ligand. A complex of a compound residue with a metal atom or a metal compound (hereinafter referred to as "specific organometallic complex".

○ dipyrromethene compound

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

In the above formula (I), R ¹ to R ⁶ are each independently represented by a hydrogen atom or a substituent. R ^{7 is} represented by a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group.

In the general formula (I), the substituent represented by R ¹ to R ⁶ may be a monovalent group (hereinafter referred to as "substituent T" as a group of monovalent groups listed below).

When the above monovalent group may be further substituted, it may be further substituted according to any one of the above groups. Further, in the case of having two or more substituents, the 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 each other to form a ring of 5 members, 6 members or 7 members. Further, in terms of the ring formed, there is a saturated ring or an unsaturated ring. Examples of the saturated or unsaturated ring of the 5-, 6- or 7-membered members include a pyrrole ring, a furan ring, a thiophene ring, a pyrazole ring, an imidazole ring, and a triazole ring. Oxazole ring, thiazole ring, pyrrolidine ring, piperidine ring, cyclopentene ring, cyclohexene ring, benzene ring, pyridine ring, pyridyl Ring, 嗒 The ring may preferably be a benzene ring or a pyridine ring.

Further, when the ring of the 5 members, 6 members, and 7 members formed is a group which can be further substituted, any one of the substituents T may be substituted, and when two or more substituents are substituted, the substituents may be The same can also be different.

The compound represented by the formula (I) or a residue thereof preferably does not have an anthraquinone skeleton, and the substituents R ¹ and R ⁶ do not form a ring.

○ metal atom or metal compound

Next, a description will be given of a metal atom or a metal compound constituting a specific complex.

That is, as the metal or metal compound to be used, it may be any one of a metal atom or a metal compound capable of forming a complex, including a divalent metal atom, a divalent metal oxide, a divalent metal hydroxide or 2 Valence metal chloride. For example, in addition to Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe, etc., also contains AlCl, InCl, FeCl, TiCl ₂ , SnCl ₂ , SiCl ₂ a metal chloride such as GeCl ₂ , a metal oxide such as TiO or VO, or a metal hydroxide such as Si(OH) ₂ .

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

Preferred aspects of the above specific organometallic complexes are shown below.

That is, in the formula (I), R ¹ and R ⁶ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a decyl group, a hydroxyl group, a cyano group, an alkoxy group, an aryloxy group, or the like. Heterocyclic oxy, fluorenyl, alkoxycarbonyl, amine carbyl, amine, anilino, heterocyclic amine, carboxy oxime, ureido, quinone, alkoxycarbonyl, aryl Oxycarbonylamino, sulfonylamino, azo, alkylthio, arylthio, heterocyclic thio, alkylsulfonyl, arylsulfonyl or phosphinoamine; R ² and R ^{5 is} independently represented by a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a hydroxyl group, a cyano group, a nitro group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, a decyl group or an alkoxy group. Carbonyl group, aryloxycarbonyl group, amine carbaryl group, oxime imido group, alkoxycarbonylamino group, sulfonylamino group, azo group, alkylthio group, arylthio group, heterocyclic thio group, alkyl sulfonate Anthracenyl, arylsulfonyl or sulfonyl; R ³ and R ⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a decyl group, a hydroxy group, a cyano group, an alkoxy group. Base, aryloxy, heterocyclic oxy, decyl, alkane Carbocarbonyl, amine mercapto, anilino, carboxy oxime, ureido, oximine, alkoxycarbonylamino, sulfonylamino, azo, alkylthio, arylthio, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, an amine sulfonyl group or a phosphino group; R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group; a metal atom or a metal compound A state indicating Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO or VO can be cited.

The preferred aspect of the above specific organometallic complex is shown below.

That is, in the formula (I), R ¹ and R ⁶ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a cyano group, a decyl group, an alkoxycarbonyl group, an aminomethyl group, an amine group. Base, heterocyclic amine group, carboxylamido group, ureido group, oxime imido group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonylamino group, azo group, alkyl sulfonyl group, aromatic Sulfosyl or phosphinoamino; R ² and R ⁵ each independently represent alkyl, alkenyl, aryl, heterocyclyl, cyano, nitro, decyl, alkoxycarbonyl, aryloxycarbonyl, An amidyl group, a fluorenylene group, an alkylsulfonyl group, an arylsulfonyl group or an amine sulfonyl group; and R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group; , cyano, decyl, alkoxycarbonyl, amine carbaryl, carboxy oxime, ureido, oxime imido, alkoxycarbonylamino, sulfonylamino, alkylthio, aryl sulphur Or a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group or an amine sulfonyl group; R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group; Zn, Mg, Si, Pt, Pd, Cu, Ni, Co or VO Aspects.

The preferred aspect of the above specific organometallic complex is shown below.

That is, in the formula (I), R ¹ and R ⁶ are each independently represented by a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an amine group, a heterocyclic amino group, a carboxy oxime group, a ureido group, and a sulfonium group. Amino, alkoxycarbonylamino, sulfonylamino, azo, alkylsulfonyl, arylsulfonyl or phosphonylamino; R ² and R ⁵ each independently represent alkyl, aryl a heterocyclic group, a cyano group, a decyl group, an alkoxycarbonyl group, an amine carbaryl group, an alkane sulfonyl group or an arylsulfonyl group; and R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group, an aryl group or a hetero atom; a ring group; R ⁷ represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group; and a metal atom or a metal compound may be in the form of Zn, Cu, Co or VO.

In particular, in the general formula (I), R ³ and R ⁴ are each preferably a phenyl group which may have a substituent from the viewpoint of excellent fastness. For this reason, (1) since each of R ³ and R ⁴ is a phenyl group, the wavelength of the compound is increased by a long wavelength, and the spectral overlap (about 550 nm) of the indigo pigment pigment to be used is increased, in order to Energy transfer becomes easy; (2) consideration is given to the fastness of the compound itself due to the presence of a sterically large substituent. Further, in the general formula (I), R ² and/or R ^{5 is} preferably a 2,6-di-tertiary-butyl-4-methylcyclohexyloxycarbonyl group from the viewpoint of excellent solvent solubility.

○ Compound represented by the formula (II-1)

The compound represented by the following formula (II-1) is a preferred example of the above specific organometallic complex.

In the above formula (II-1), R ¹ to R ⁷ and Ma in the formula (II-1) are synonymous with the formula (I), and preferred embodiments are also the same. X ² represents a group necessary for neutralizing the charge of Ma. Further, X ¹ and X ² may be combined with each other to form a ring of 5 members, 6 members or 7 members.

In the general formula (II-1), any group in which X ¹ may be bonded to Ma may, for example, be water, an alcohol (for example, methanol, ethanol or propanol), or a further "metal chelate compound" [1] 坂口武一‧ Ueno Jingping (1995 Nanjiangtang), the same as [2] (1996), the same [3] (1997) and other compounds derived from the compounds.

X ² in the formula (II-1) is 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.

In the formula (II-1), X ¹ and X ² may be bonded to each other to form a ring of 5 members, 6 members or 7 members. The formed ring of 5 members, 6 members, and 7 members may be a saturated ring or an unsaturated ring. Further, the 5-member, 6-member or 7-membered ring may be composed only of a carbon atom and a hydrogen atom, or may be a heterocyclic ring having at least one selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom.

The compound represented by the formula (II-1) is not an organometallic complex having an anthraquinone skeleton, and it is preferred that the substituents R ¹ and R ^{6 are} not bonded to form a ring.

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

With respect to the above specific organic complex, a compound represented by the following formula (II-2) is a preferred example.

In the above formula (II-2), R ¹ to R ⁶ and R ⁸ to R ^{13 are} synonymous with R ¹ to R ⁶ in the formula (I), and preferred embodiments are also the same.

When the substituent represented by R ⁸ to R ¹³ in the compound represented by the formula (II-2) is a further substitutable group, it may be substituted with any one of the substituents T described above, and substituted with two or more. When substituted, the replacement machines may be the same or different.

Formula (II-2) R ⁷ in the general formula (I), the same meaning as R ^7, the same preferred aspect of Formula (II-2) in the R ¹⁴ represents a hydrogen, a halogen atom, an alkyl group, The preferred range of R ¹⁴ for the aryl or heterocyclic group is the same as the preferred range of the above R ⁷ . When R ¹⁴ is a further substitutable group, it may be substituted with any one of the above substituents T, and when substituted with two or more substituents, the substituents may be the same or different.

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

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

The compound represented by the formula (II-2) is not an organometallic complex having an anthraquinone skeleton, and it is preferred that the substituents R ¹ and R ¹³ , R ⁶ and R ^{8 are} not bonded to form a ring.

○ a compound represented by the formula (III)

The compound represented by the following formula (III) is a preferred example of the above specific organometallic complex.

In the above formula (III):

‧R ² ~ R ⁵ and R ⁷ in the general formula (I), the R ² ~ R ⁵ and R ⁷ are synonymous, preferred aspects are also the same.

‧Ma denotes a metal or a metal compound, which is synonymous with a metal atom or a metal compound constituting the aforementioned specific complex, and the preferred range is also the same.

‧ X ³ represents NR (R represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a fluorenyl group, an alkylsulfonyl group, an arylsulfonyl group), a nitrogen atom, an oxygen atom and a sulfur atom.

‧X ⁴ represents NRa (Ra represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a fluorenyl group, an alkylsulfonyl group or an arylsulfonyl group), an oxygen atom or a sulfur atom.

‧Y ¹ represents NRc (Rc represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a fluorenyl group, an alkylsulfonyl group, 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 amine group. R ⁸ and R ¹ may be combined to form a ring of 5 members, 6 members or 7 members, and R ⁹ and R ² may be combined with each other to form a ring of 5 members, 6 members or 7 members. When the group may be further substituted, it may be substituted with any one of the substituents T, and when substituted with two or more substituents, the substituents may be the same or different.

‧ X ⁵ indicates the base that can be combined with Ma. Examples of the above formula (II-1) include the same groups as those of X ¹ .

‧ a means 0.1 or 2.

In the formula (III), R ⁸ and R ⁹ each independently represent an alkyl group (preferably having a carbon number of from 1 to 36, more preferably a linear, branched or cyclic alkyl group of from 1 to 12, for example, Methyl, ethyl, propyl, isopropyl, butyl, isobutylbutyl, tert-butyl, hexyl, 2-ethylhexyl, dodecyl, cyclopropyl, cyclopentyl, cyclohexyl , 1-adamantyl), alkenyl (preferably having a carbon number of 2 to 24, more preferably an alkenyl group of 2 to 12, such as a vinyl group, an allyl group, a 3-buten-1-yl group) or a aryl group a base (preferably having a carbon number of 6 to 36, preferably an aryl group of 6 to 18, such as a phenyl group or a naphthyl group), or a heterocyclic group (preferably having a carbon number of 1 to 24 and a heterocyclic ring of 1 to 12). More preferably, for example, 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyridyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, benzene And triazol-1-yl), alkoxy (preferably having a carbon number of from 1 to 36, more preferably an alkoxy group of from 1 to 18, such as methoxy, ethoxy, propoxy or butoxy) , hexyloxy, 2-ethylhexyloxy, dodecyloxy, cyclohexyloxy), aryloxy (preferably having a carbon number of 6 to 24, more preferably an aryloxy group of 1 to 18, For example, phenoxy, naphthyloxy), alkylamino ( Preferably, the carbon number is from 1 to 36, more preferably from 1 to 18 alkylamine groups, such as methylamino, ethylamino, propylamino, butylamino, hexylamino, 2-ethyl Hexylamino, isopropylamino, tert-butylamino, trioctylamino, cyclohexylamino, N,N-diethylamino, N,N-dipropylamino, N , N-dibutylamino, N-methyl-N-ethylamino), arylamine (preferably having a carbon number of 6 to 36, more preferably an arylamine group of 6 to 18, for example Phenylamino, naphthylamino, N,N-diphenylamino, N-ethyl-N-phenylamino), or heterocyclic amine (preferably from 1 to 24, to 1) More preferably, the heterocyclic amino group of ~12 is, for example, 2-aminopyrrolyl, 3-aminopyrazolyl, 2-aminopyridyl, 3-aminopyridyl).

In the above X ³ and X ⁴ , R and Ra each independently represent a hydrogen atom or an alkyl group (preferably having a carbon number of 1 to 36, and more preferably a linear, branched or cyclic alkyl group of 1 to 12). , for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, hexyl, 2-ethylhexyl, dodecyl, cyclopropyl, cyclopentyl, cyclohexyl, 1-adamantyl), alkenyl (preferably having a carbon number of 2 to 24, more preferably an alkenyl group of 2 to 12, such as a vinyl group, an allyl group, a 3-buten-1-yl group) or an aryl group. (preferably having a carbon number of 6 to 36, preferably an aryl group of 6 to 18, such as a phenyl group or a naphthyl group) or a heterocyclic group (preferably having a carbon number of 1 to 24 and a heterocyclic group of 1 to 12). More preferably, for example, 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyridyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, benzo Triazol-1-yl, fluorenyl (preferably having a carbon number of 1 to 24, more preferably a fluorenyl group of 2 to 18, such as an ethyl fluorenyl group, a trimethyl ethane group, a 2-ethylhexyl group, or a benzoyl group) Anthracenyl, cyclohexyl), alkylsulfonyl (preferably having a carbon number of 1 to 24, more preferably an alkylsulfonyl group of 1 to 18, such as methylsulfonyl or ethylsulfonyl) Isopropyl sulfonyl, ring More preferably, the hexylsulfonyl group, the arylsulfonyl group (preferably having a carbon number of 6 to 24, and a 6 to 18 arylsulfonyl group), for example, a phenylsulfonyl group or a naphthylsulfonyl group.

The alkyl group, the alkenyl group, the aryl group, the heterocyclic group, the fluorenyl group, the alkylsulfonyl group or the arylsulfonyl group of R and Ra may be further substituted with any one of the substituents T described above, and a plurality of substituents may be used. When substituted, the substituents may be the same or different.

In the formula (III), when R ³ and Y ¹ are bonded to each other to form a ring, R ⁸ , Y ¹ and a carbon atom may together form a 5-membered ring (for example, cyclopentane, pyrrolidine, tetrahydrofuran, dioxolane, Tetrahydrothiophene, pyrrole, furan, thiophene, anthracene, benzofuran, benzothiophene), 6-membered ring (eg cyclohexane, piperidine, piperidine) , morpholine, tetrahydropyran, two Alkane, pentamethylene sulfide, dithiane, benzene, piperidine, piperazine ,despair , quinoline, quinazoline), or a 7-membered ring (eg, cycloheptane, hexamethyleneimine).

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

In the formula (III), when R ⁸ and Y ¹ and R ⁹ and Y ^{2 are} bonded to form a ring of 5 members, 6 members and 7 members, which may be further substituted, any of the substituents T may be used. The substituents described above may be substituted or substituted with two or more substituents, and the substituents may be the same or different.

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

That is, R ² to R ⁵ , R ⁷ and Ma each contain a preferred embodiment of a compound represented by the 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 (Ra is a hydrogen atom, an alkyl group, a heterocyclic group) or an oxygen atom, Y ¹ is NRc (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 bonded via an oxygen atom, and R ⁸ and R ⁹ each independently represent an alkyl group, an aryl group, a heterocyclic group, an alkoxy group or an alkylamino group, and R ⁸ And Y ^{1 is} combined with each other to form a 5-member or 6-membered ring, and R ⁹ and Y ² are combined with each other to form a 5-member or 6-membered ring, and a is a state represented by 0 or 1.

A more preferred aspect of the compound represented by the formula (III) is shown below.

That is, R ² to R ⁵ , R ⁷ and Ma each contain a preferred embodiment of a compound represented by the 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 bonded via an oxygen atom, and R ⁸ and R ⁹ each independently represent an alkyl group, an aryl group, a heterocyclic group, an alkoxy group or an alkylamino group, R ⁸ and Y ^{1 is} combined with each other to form a 5- or 6-membered ring, and R ⁹ and Y ² are combined to form a 5- or 6-membered ring, and a represents a 0 or 1 aspect.

The compound represented by the formula (III) is not an organometallic complex having an anthraquinone skeleton, and the substituents R ⁸ and X ³ and R ⁹ and X ^{4 are} not linked to form a ring, and the two are not further It is preferred that the joint forms a ring.

Hereinafter, specific examples of specific complexes in the present invention are shown, but the present invention is not limited to these examples.

From the viewpoint of film thickness, the molar absorption coefficient of the specific organometallic complex in the present invention is preferably as high as possible. Further, from the viewpoint of color purity upward, the maximum absorption wavelength λ max is preferably 520 nm to 580 nm, more preferably 530 nm to 570 nm. Further, the maximum absorption wavelength and the molar absorption coefficient were measured by a spectrophotometer UV-2400PC (manufactured by Shimadzu Corp.). From the viewpoint of solubility, the melting point of the specific organometallic complex of the present invention is not too high.

The specific organometallic complex of the present invention can be used in the U.S. Patent No. 4,774,339, U.S. Patent No. 5,343,896, JP-A-2001-240761, JP-A-2002-155052, No. 3,614,586, Aust. Synthesis by Chem, 1965, 11, 1835-1845, JH Boger et al., Heteroatom Chemistry, Vol. 1, No. 5, 389 (1990). The method for synthesizing a specific complex in the present invention is specifically applicable to the method described in paragraphs [0131] to [0157] of JP-A-2008-292970.

In the photosensitive colored curable composition of the present invention, one type of specific organometallic complex may be used alone or two or more kinds may be used in combination. The content of the colored curable composition of the specific organometallic complex in the present invention varies depending on the molecular weight and the molar absorptivity, and is preferably from 1% by mass to 70% by mass based on the total solid content of the colored curable composition. More preferably, it is 3 mass% to 50 mass%, and most preferably 6 mass% to 30 mass%. It is preferably 3 to 150 parts by mass, and more preferably 10 to 100 parts by mass, per 100 parts by mass of the pigment. In the above-mentioned lower limit or more, the pigment fine particles having a finer surface and increased surface area can be stably dispersed, and below the above upper limit, the color value displayed by the pigment can be prevented from being lowered.

[Substituent T]

A halogen atom (for example, a fluorine atom, a chlorine atom or a bromine atom) or an alkyl group (preferably having a carbon number of 1 to 48, preferably a linear, branched or cyclic alkyl group having 1 to 24 carbon atoms, For example, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, dodecyl, hexadecyl, cyclopropane Base, cyclopentyl, cyclohexyl, 1-norbornyl, 1-adamantyl), alkenyl (preferably having a carbon number of 2 to 48, more preferably an alkenyl group having 2 to 18 carbon atoms, such as a vinyl group) , allyl, 3-buten-1-yl), aryl (preferably having a carbon number of 6 to 48, more preferably an aryl group having 6 to 24 carbon atoms, such as a phenyl group or a naphthyl group) or a heterocyclic ring. a base (preferably having a carbon number of 1 to 32, more preferably a heterocyclic group having 1 to 18 carbon atoms, such as 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyridyl , 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, benzotriazol-1-yl), decylalkyl (preferably having a carbon number of 3 to 38 and having a carbon number of 3 to 18 alkyl) More preferably, for example, trimethyldecyl, triethyldecyl, tributyldecyl, tert-butyldimethylalkyl, tert-hexyldimethyldecyl, hydroxy, A cyano group, a nitro group, an alkoxy group (preferably having a carbon number of 1 to 48, more preferably an alkoxy group having 1 to 24 carbon atoms, such as a methoxy group, an ethoxy group, a 1-butoxy group, or a 2- Butoxy, isopropoxy, tert-butoxy, dodecyloxy, further, if cycloalkyloxy, for example cyclopentyloxy, cyclohexyloxy), aryloxy (preferably The carbon number is 6 to 48, and more preferably an aryloxy group having 6 to 24 carbon atoms, such as a phenoxy group, a 1-naphthyloxy group or a heterocyclic oxy group (preferably having a carbon number of 1 to 32 and a carbon number of 1 to 2). More preferably, the heterocyclic oxy group of 18 is, for example, 1-phenyltetrazole-5-oxy, 2-tetrahydropyranyloxy, decyloxy (preferably having a carbon number of 1 to 32, and having a carbon number of 1~) More preferably, the 18-decyloxy group is, for example, trimethyldecaneoxy, tert-butyldimethyloxaneoxy, diphenylmethylnonyloxy), decyloxy (preferably having a carbon number of 2 to 48). More preferably, the alkoxy group having 2 to 24 carbon atoms is, for example, an ethoxycarbonyl group, a trimethylethoxycarbonyl group, a benzamethyleneoxy group, a dodecyloxy group, or an alkoxycarbonyloxy group. It is preferably a carbon number of 2 to 48, and more preferably an alkoxycarbonyloxy group having 2 to 24 carbon atoms, such as an ethoxycarbonyloxy group, a third butoxycarbonyloxy group, and, if it is a cycloalkoxycarbonyl group. Oxyl group, such as a ring a hexyloxycarbonyloxy group, an aryloxycarbonyloxy group (preferably having a carbon number of 7 to 32, more preferably an aryloxycarbonyloxy group having 7 to 24 carbon atoms, for example, a phenoxycarbonyloxy group), Aminomethyl methoxy group (preferably having a carbon number of 1 to 48, more preferably an amine methyl oxy group having 1 to 24 carbon atoms, such as N,N-dimethylamine methyl methoxy group, N-butylamine) Methoxy group, N-phenylamine methyl methoxy group, N-ethyl-N-phenylamine methoxy group), sulfonyloxy group (preferably carbon number 1 to 32, carbon number 1~) More preferably, the sulfonyloxy group of 24 is, for example, N,N-diethylaminesulfonyloxy, N-propylsulfonyloxy, or alkylsulfonyloxy (preferably having a carbon number of from 1 to 38). More preferably, the alkylsulfonyloxy group having 1 to 24 carbon atoms, such as methylsulfonyloxy, hexylsulfonyloxy, cyclohexylsulfonyloxy, or arylsulfonyloxy (preferably) The carbon number is 6 to 32, and the arylsulfonyloxy group having 6 to 24 carbon atoms is more preferable, for example, phenylsulfonyloxy group, fluorenyl group (preferably having a carbon number of 1 to 48, and having a carbon number of 1~) More preferably, the sulfhydryl group of 24 is, for example, a fluorenyl group, an ethyl fluorenyl group, a trimethyl ethane group, a benzhydryl group, a tetradecyl fluorenyl group, a cyclohexyl fluorenyl group, an alkoxycarbonyl group (preferably a carbon). The number is 2 to 48, and the alkoxycarbonyl group having 2 to 24 carbon atoms is more preferably For example, methoxycarbonyl, ethoxycarbonyl, octadecyloxycarbonyl, cyclohexyloxycarbonyl, 2,6-di-t-butyl-4-methylcyclohexyloxycarbonyl), aryloxycarbonyl (preferably) It is preferably a carbon number of 7 to 32, preferably an aryloxycarbonyl group having 7 to 24 carbon atoms, for example, a phenoxycarbonyl group, an amine formazan group (preferably a carbon number of 1 to 48, and an amine having 1 to 24 carbon atoms). More preferably, the methyl group is, for example, an aminomethyl group, N,N-diethylamine, a N-ethyl-N-octylamine, a N,N-dibutylamine, a fluorenyl group. , N-propylamine methyl sulfhydryl, N-phenylamine methyl sulfhydryl, N-methyl-N-phenylamine methyl sulfhydryl, N,N-dicyclohexylamine carbhydryl), amine Preferably, the carbon number is 32 or less, and the amine group having a carbon number of 24 or less is more preferable, for example, an amine group, a methylamino group, an N,N-dibutylamino group, a tetradecylamino group, or a 2-ethylhexylamine. a group, a cyclohexylamino group, an anilino group (preferably having a carbon number of 6 to 32, more preferably an anilino group of 6 to 24, such as an anilino group or an N-methylanilino group) or a heterocyclic amino group (preferably, It is preferably a carbon number of 1 to 32, preferably a heterocyclic amino group of 1 to 18, such as a 4-pyridyl group, or a carboguanamine group (preferably a carbon number of 2 to 48, and a 2 to 24 carboxamide group). More preferably, such as acetaminophen, benzene Amidino, tetradecylguanamine, trimethylacetamidoguanamine, cyclohexaneguanidino, ureido (preferably having a carbon number of 1 to 32, and a ureido group having a carbon number of 1 to 24) More preferably, for example, a ureido group, an N,N-dimethylureido group, an N-phenylureido group, or a quinone imine group (preferably having a carbon number of 36 or less, and a ruthenium imine group having a carbon number of 24 or less is more Preferably, for example, N-succinimide group, N-phthalimido group, alkoxycarbonylamino group (preferably carbon number 2 to 48, alkoxycarbonyl group having 2 to 24 carbon atoms) More preferably, the amine group is, for example, a methoxycarbonylamino group, an ethoxycarbonylamino group, a third butoxycarbonylamino group, an octadecyloxycarbonylamino group, a cyclohexyloxycarbonylamino group, or an aryl group. An oxycarbonylamino group (preferably having a carbon number of 7 to 32, more preferably an aryloxycarbonylamino group having 7 to 24 carbon atoms, such as a phenoxyoxycarbonylamino group) or a sulfonylamino group (more preferably Preferably, the carbon number is from 1 to 48, and more preferably a sulfonamide group having from 1 to 24 carbon atoms, such as methanesulfonamide, butanesulfonylamino, benzenesulfonylamino, hexadecanesulfonylamino , cyclohexanesulfonylamino), sulfonamide group (preferably having a carbon number of 1 to 48, more preferably an amine sulfonamide having a carbon number of 1 to 24, such as N, N) -dipropylamine sulfonamide, N-ethyl-N-dodecyl), azo (preferably having a carbon number of from 1 to 32, more preferably an azo group having from 1 to 24 carbon atoms, For example, phenylazo group, 3-pyrazolylazo group, alkylthio group (preferably having a carbon number of 1 to 48, more preferably an alkylthio group having 1 to 24 carbon atoms, such as methylthio group) , ethylthio, octylthio, cyclohexylthio), arylthio (preferably having a carbon number of 6 to 48, more preferably an arylthio group having 6 to 24 carbon atoms, such as phenyl sulfide a heterocyclic thio group (preferably having a carbon number of 1 to 32, more preferably a heterocyclic thio group having 1 to 18 carbon atoms, such as a 2-benzothiazolylthio group, a 2-pyridylthio group, 1 -Phenyltetrazolylthio), alkylsulfinyl (preferably having a carbon number of 1 to 32, more preferably an alkylsulfinyl group having 1 to 24 carbon atoms, for example, a sulfinyl group; , an arylsulfinyl group (preferably having a carbon number of 6 to 32, more preferably an arylsulfinyl group having a carbon number of 6 to 24, such as a phenylsulfinyl group) or an alkylsulfonyl group ( Preferably, the carbon number is from 1 to 48, and more preferably an alkylsulfonyl group having from 1 to 24 carbon atoms, such as methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, Isopropylsulfonyl, 2-ethylhexylsulfonyl More preferably, hexylsulfonyl, octylsulfonyl, cyclohexylsulfonyl) or arylsulfonyl (preferably having a carbon number of 6 to 48, preferably an arylsulfonyl group having 6 to 24 carbon atoms) For example, a phenylsulfonyl group, a 1-naphthylsulfonyl group, an aminesulfonyl group (preferably having a carbon number of 32 or less, more preferably an sulfonamide group having a carbon number of 24 or less, such as an aminesulfonyl group, N,N-dipropylamine sulfonyl, N-ethyl-N-dodecylamine sulfonyl, N-ethyl-N-phenylamine sulfonyl, N-cyclohexylamine sulfonyl a sulfo group or a phosphinium group (preferably having a carbon number of 1 to 32, more preferably a phosphino group having 1 to 24 carbon atoms, such as a phenoxyphosphonium group, an octyloxyphosphonium group, or a phenyl group; Phosphonium), phosphiniumamine group (preferably having a carbon number of 1 to 32, more preferably a phosphonium amino group having 1 to 24 carbon atoms, such as diethoxyphosphonium amide, dioctyloxyphosphine Amidoxime).

[(A-2) pigment]

The pigment used in the present invention is preferably any one selected from the group consisting of a diketopyrrolopyrrole pigment, a condensed azo pigment, and an anthraquinone pigment. Specifically, C.I. Pigment Red 254, Pigment Red 209, and Pigment Red 177 are listed.

The content of the color hardening composition of the pigment in the present invention is preferably from 10% by mass to 70% by mass, more preferably from 20% by mass to 60% by mass, based on the total solid component of the colored curable composition. Good is 35% by mass to 50% by mass.

[(B) Dispersant]

The colored curable composition of the present invention contains a dispersing agent. As the (B) dispersant, a known pigment dispersant or surfactant can be used. As the dispersing agent, various kinds of compounds can be used, for example, an anthraquinone derivative (commercial product EFKA-745 (manufactured by Efka)), SOLSPERSE 5000 (Japan Lubrizol Co., Ltd.), and an organic polyoxyalkylene polymer KP341. (Shin-Etsu Chemical Co., Ltd.), (meth)acrylic (co)polymer POLYFLOW No. 75, No. 90, No. 95 (above, Kyoei Oil & Fat Chemical Industry Co., Ltd.), W001 (Yu Shang Cationic surfactants, etc.; polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene decyl benzene Nonionic surfactants such as ethyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester; W004, W005, W017 (above, Yushang Co., Ltd.) Anionic surfactants such as EFKA-46, EFKA-47, EFKA-47EA, EFKA Polymer 100, EFKA Polymer 400, EFKA Polymer 401, EFKA Polymer 450 (above, Morishita Sangyo Co., Ltd.), Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 (above a polymer dispersant such as San Nopco Co., Ltd.; various SOLSPERSE dispersants (made by Japan Lubrizol Co., Ltd.) of SOLSPERSE 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000; Adekapluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (above, manufactured by Asahi Denki Kogyo Co., Ltd.), And IONET S-20 (manufactured by Sanyo Chemical Industry Co., Ltd.).

In the present invention, the content of the (B) dispersant in the colored curable composition is preferably from 1% by mass to 80% by mass, more preferably from 5% by mass to 70% by mass, most preferably 10% by mass. ~60% by mass.

[(C) Polymerizable Compound]

The color hardening composition of the present invention has a polymerizable compound. The polymerizable compound may, for example, be an addition polymerizable compound containing at least one ethylenically unsaturated double bond. Specifically, it is selected from compounds containing at least one, preferably two or more terminal ethylenically unsaturated bonds. Such a compound group is well known in the art, and the present invention is not limited to such a compound group. Thus, for example, a monomer, a prepolymer, that is, may be any of a dimer, a trimer, and an oligomer, or a chemical type of the mixture and the (co)polymer.

Examples of the monomer and its (co)polymer include an unsaturated carboxylic acid (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or an ester thereof. Classes, guanamines and their (co)polymers, preferably unsaturated carboxylic acids and aliphatic polyol compounds and esters thereof, and unsaturated carboxylic acids and aliphatic polyamine compounds and their guanamines and copolymerization thereof Things. Further, an addition reaction product of an unsaturated carboxylic acid ester having a nucleophilic substituent such as a hydroxyl group, an amine group or a thiol group, or a guanamine, a monofunctional or polyfunctional isocyanate or an epoxy is preferably used. A dehydration condensation reaction product of a monofunctional or polyfunctional carboxylic acid or the like. Further, it is preferably an unsaturated carboxylic acid ester having an electrophilic substituent such as an isocyanate group or an epoxy group or a guanamine thereof, a monofunctional or polyfunctional alcohol, an amine or a mercaptan substituted reactant. Further, as another example, in place of the above unsaturated carboxylic acid, a compound group substituted with an unsaturated phosphonic acid, styrene, vinyl ether or the like may be used.

Specific examples of the aliphatic polyol compound and the ester monomer of the unsaturated carboxylic acid include, for example, ethylene glycol diacrylate, triethylene glycol diacrylate, and 1,3-butylene glycol diacrylate. , tetramethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tris(propylene oxypropyl) ether, three Trimethylolethane acrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, dipentaerythritol diacrylate, neopentyl glycol triacrylate Ester, neopentyl glycol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentoxide, sorbitol hexaacrylate Ester, tris(propylene decyloxyethyl) cyanurate, polyester acrylate oligomer, triacrylate modified by isomeric cyanurate EO, and the like.

Further, examples of the methacrylate include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, and trishydroxytrimethacrylate. Methylpropane ester, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, hexanediol dimethacrylate, dimethyl Neopentyl glycol acrylate, neopentyl glycol methacrylate, neopentyl glycol tetramethacrylate, di pentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, Sorbyl methacrylate, sorbitan tetramethacrylate, bis[p-(3-methylpropenyloxy-2-hydroxypropoxy)phenyl]dimethylmethane, bis-[pair- (Methethyloxyethoxy)phenyl]dimethylmethane.

Further, as the isonic acid ester, for example, ethylene glycol diisoacetate, propylene glycol diconiate, 1,3-butylene glycol di-conconate, and 1,4-diconic acid are exemplified. Butylene glycol ester, dicamethylene glycol di-i-conconate, neopentyl glycol di-iconate, sorbitan tetraconate, etc. Further, as the crotonate, for example, dicropped beans Acidic acid glycol ester, tetracromethylene glycol dicrotonate, neopentyl glycol dicrotonate, sorbitan tetrabromate, etc., in the case of isocrotonate, for example, diisocrotonate B a glycol ester, a neopentyl glycol diisocrotonate, a sorbitan tetraisocrotonate, etc. Further, as the maleic acid ester, for example, ethylene glycol maleate, and Triethylene glycol maleate, neopentyl glycol maleate, sorbitan tetramaleate, and the like.

For example, the aliphatic alcohol-based esters described in JP-A-59-196231, JP-A-59-196231, and JP-A-59-5240, JP-A-59-59 Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Further, the aforementioned ester monomer can be used as a mixture.

Further, as a specific example of the monomer of the aliphatic polyamine compound and the decylamine of the unsaturated carboxylic acid, there are methylene bis-acrylamide, methylene bis-methyl acrylamide, 1,6-hexa Methylene bis-acrylamide, 1,6-hexamethylene bis-methyl acrylamide, di-ethyltriamine propylene amide, xylene bis acrylamide, xylene dimethyl methacrylate Amines, etc.

As an example of another preferable amide-based monomer, a structure having a stretched cyclohexyl group described in Japanese Patent Publication No. 54-21726 can be exemplified.

In addition, it is also suitable to use an addition reaction of an isocyanate and a hydroxyl group to produce a urethane-based addition polymerizable compound, and a specific example thereof is described in JP-A-48-41708, for example, The addition of a vinyl monomer having a hydroxyl group represented by the formula (A) to a vinylamine group having two or more polymerizable vinyl groups in one molecule of a polyisocyanate compound having two or more isocyanate groups in one molecule Formate compound.

CH ₂ =C(R)COOCH ₂ CH(R')OH ... (A)

[In the formula (A), R and R' each independently represent H or CH ₃ ].

With respect to these polymerizable compounds, the final performance setting of the coloring curable composition can be arbitrarily set by using the structure alone or in combination, and the method of using the detailed addition amount. For example, from the viewpoint of sensitivity, a structure having a large content per one molecule of unsaturated groups is preferable, and in many cases, a bifunctional group or more is preferable. Further, from the viewpoint of the strength of the highly colored cured film, a trifunctional group or more is preferable, and a heterofunctional number or a heteropolymerizable group (for example, an acrylate, a methacrylate, a styrene compound, or a vinyl ether) is used in combination. For the compound, the method of adjusting both sensitivity and intensity is also effective. Further, the compatibility and dispersibility of other components (for example, a photopolymerization initiator, a colorant (pigment), a binder polymer, etc.) contained in the coloring curable composition, and the selection of a polymerizable compound are used. The method is an important factor, for example, by the use of a low-purity compound or a combination of two or more for improving compatibility. Moreover, it is obtained by selecting a specific structure from the viewpoint of improving the hard surface and the adhesion of a support etc.

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

[(D) Photopolymerization Initiator]

The colored curable composition of the present invention preferably contains a photopolymerization initiator. The ink jet ink-use type color resist is not essential, and a color resist containing a polymerization initiator in a coating method to be described later is preferable.

The photopolymerization initiator is not particularly limited as long as it can be polymerized with the above-mentioned (C) polymerizable compound, and is preferably selected from the viewpoints of starting efficiency, absorption wavelength, availability, cost, and the like.

In the case of a photoinitiator, for example, a halogenated methyl group is exemplified. Diazole and halomethyl-s-triazole At least one active halogen compound, 3-aryl substituted coumarin compound, oxophene dimer, benzophenone compound, acetophenone compound and derivative thereof, cyclopentadiene-benzene-iron And its salts, lanthanide compounds and the like. Specific examples of the photopolymerization initiator include the descriptions of paragraphs [0070] to [0077] of JP-A-2004-295116. Among them, from the viewpoint of rapid polymerization, a lanthanide compound is preferred.

The ruthenium-based compound (hereinafter referred to as "anthracene-based photopolymerization initiator" is not particularly limited, and examples thereof include those described in JP-A-2000-80068, WO02/100903A1, and JP-A-2001-233842. a compound.

As a specific example, 2-(O-benzylidene fluorenyl)-1-[4-(phenylthio)phenyl]-1,2-butanedione, 2-(O-benzylidene fluorenyl) )-1-[4-(phenylthio)phenyl]-1,2-pentanedione, 2-(O-benzylidene fluorenyl)-1-[4-(phenylthio)phenyl]- 1,2-hexanedione, 2-(O-benzylidene fluorenyl)-1-[4-(phenylthio)phenyl]-1,2-heptanedione, 2-(O-benzamide (肟)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 2-(O-benzylidene fluorenyl)-1-[4-(methylphenylthio) Phenyl]-1,2-butanedione, 2-(O-benzylidene fluorenyl)-1-[4-(ethylphenylthio)phenyl]-1,2-butanedione, 2-(O-benzylidene fluorenyl)-1-[4-(butylphenylthio)phenyl]-1,2-butanedione, 1-(O-ethylindenyl)-1- [9-Ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]ethanone, 1-(O-ethylindenyl)-1-[9-methyl -6-(2-methylbenzhydryl)-9H-indazol-3-yl]ethanone, 1-(O-ethylindenyl)-1-[9-propyl-6-(2 -Methylbenzylidene)-9H-indazol-3-yl]ethanone, 1-(O-ethylindenyl)-1-[9-ethyl-6-(2-ethylbenzene) Mercapto)-9H-carbazol-3-yl]ethane ketone, 1-(O-ethylhydrazinyl)-1-[9-ethyl-6-(2-butylbenzylidene)-9H - oxazol-3-yl]ethane ketone and the like.

Among these, 2-(O-benzylidene fluorenyl)-1-[4-(benzene) is obtained from a pattern having a good shape (especially rectangular in the case of a solid-state imaging element) with a small amount of exposure. Thio)phenyl]-1,2-octanedione, 1-(O-ethylindenyl)-1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indole The fluorene-fluorenyl compound such as oxazol-3-yl]ethane ketone is particularly preferable, and specific examples thereof include CGI-124 and CGI-242 (manufactured by Kabate Chemicals Co., Ltd.).

In the present invention, the oxime compound is preferably a compound represented by the following formula (1) from the viewpoints of sensitivity, stability over time, and coloring upon post-heating.

In the above formula (1), R and X each independently represent a monovalent substituent, A represents a divalent substituent, and Ar represents an aryl group. n is an integer from 1 to 5.

In the case of R, from the viewpoint of high sensitivity, a mercapto group is preferred, and specifically, an ethylidene group, a propyl group, a benzamidine group or a tolylmethyl group is preferable.

In the case of A, from the viewpoint of suppressing coloration by high sensitivity and heating duration, an unsubstituted alkyl group is substituted with an alkyl group (for example, methyl group, ethyl group, tert-butyl group, dodecyl group). An alkyl group, an alkyl group substituted with an alkenyl group (e.g., a vinyl group, an allyl group), an aryl group (e.g., phenyl, p-tolyl, methylbenzyl, cumyl, naphthyl, anthryl, phenanthryl) A styryl group substituted with a styryl group is preferred.

In the case of Ar, a phenyl group which is substituted or unsubstituted is preferred from the viewpoint of suppressing coloration by high sensitivity and heating. When the phenyl group is substituted, the substituent is preferably a halogen group such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

In the case of the solvent, the alkyl group which may have a substituent, the aryl group which may have a substituent, the alkenyl group which may have a substituent, and the substituent may also have a substituent from the viewpoint of the solvent solubility and the absorption efficiency in the long-wavelength region. An alkynyl group, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group, a thioaryl group, or an amine group which may have a substituent good.

Hereinafter, specific examples of the compound represented by the general formula (1) are shown below, but are not intended to limit the present invention.

Further, in addition to the photopolymerization initiator described above, other known photopolymerization initiators described in paragraph [0079] of JP-A-2004-295116 can be used as the color-curable composition of the present invention.

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

The content of the photopolymerization initiator (the content of two or more kinds) in the total solid content of the colored curable composition is preferably from 3% by mass to 20% by mass, more preferably from the viewpoint of obtaining the effect of the present invention. It is 4% by mass to 19% by mass, particularly preferably 5% by mass to 18% by mass.

[(E) organic solvent]

The color hardening composition of the present invention uses an organic solvent (E) as a medium. The organic solvent is not particularly limited as long as it satisfies the solubility of each component and the continuous phase of the coating property in the coloring-curable composition, and in particular, it is preferable to consider the solubility and coating property of the binder. Choice, security.

Examples of the organic solvent include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl acetate, isoamyl acetate, isobutyl acetate, butyl propionate, and isopropyl butyrate. Ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, alkyl oxyacetate (such as methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (specifically, methoxy) Methyl acetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), alkyl 3-oxopropionate (for example, 3 Methyloxypropionate, ethyl 3-oxypropionate (specifically, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate , 3-ethoxypropionate ethyl ester, etc.), 2-oxypropionic acid alkyl ester (for example, methyl 2-oxypropionate, ethyl 2-oxypropionate, 2-oxypropane) Acid propyl ester, etc. (specifically, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2 -ethyl ethoxypropionate, etc.)), methyl 2-oxy-2-methylpropanoate, ethyl 2-oxy-2-methylpropionate (with Body, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate Ethylacetate methyl acetate, ethyl acetoxyacetate, methyl 2-oxobutanoate, ethyl 2-oxobutyrate, and the like.

Further, examples of the ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl sulphate acetate, and ethyl acetate. Sulfester, 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, acetic acid Propylene glycol monopropyl ether ester and the like.

The ketone may, for example, be methyl ethyl ketone, cyclohexanone, 2-heptanone or 3-heptanone.

Examples of the aromatic hydrocarbons include toluene and xylene.

When the organic solvent contains the solubility of each of the above components and the alkali-soluble binder, it is preferred to mix two or more kinds thereof from the viewpoints of solubility and improvement of the coating surface. In this case, it is particularly selected from the group consisting of methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl celecoxib acetate, ethyl lactate, diethylene glycol dimethyl ether, and butyl acetate. Ester, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether and propylene glycol methyl ether acetate 2 A mixed solution composed of the above.

The content of the total solid content in the composition in the color hardening composition of the organic solvent is preferably from 10% by mass to 80% by mass, more preferably from 15% by mass to 60% by mass.

[(F) yellow pigment]

In the present invention, the colored curable composition may contain a yellow pigment. In the case where the yellow pigment is used in the present invention, the total content of the yellow pigment in the total content of the pigment and the dye is preferably from 1% by mass to 50% by mass, more preferably from 5% by mass to 30% by mass. Further, the term "yellow pigment" as used in the specification of the present invention means a yellow pigment and a yellow dye.

The yellow pigment which can be used in the present invention is not particularly limited and may be selected from known solvent-soluble dyes and the like. For example, JP-A-64-90403, JP-A-64-91102, JP-A-1-94301, JP-A-6-11614, JP-A No. 2592207, and US Patent No. 4808501, The invention is described in the specification of the U.S. Patent No. 5,676,920, the U.S. Patent No. 5,059,500, the U.S. Patent No. 5,059,500, the Japanese Patent Application Publication No. Hei. No. Hei. No. Hei. Yellow pigment. As the chemical structure, an azo group such as an anilino azo group, an aryl azo group, a pyrazole triazole azo, a pyridone azo or a pyrazole azo, a triphenylmethane system or a lanthanoid system can be used. , pyridinone, benzylidene, oxysterol, cyanine, thiophene , pyrazole triazole methine, pyrrolopyrazole azomethine, A dye such as a cord, an anthracycline, a benzopyran, or an indigo.

[(G) Other ingredients]

The color hardening composition of the present invention may further contain other components such as an alkali-soluble binder and a crosslinking agent in addition to the above components, without detracting from the effects of the present invention.

○ Alkali soluble binder

The alkali-soluble binder is not particularly limited as long as it has alkali solubility, and is preferably selected from the viewpoints of heat resistance, developability, and availability. In the case of the alkali-soluble binder, it is preferred to have a linear organic high molecular polymer and be soluble in an organic solvent, and it can be developed in a weakly alkaline aqueous solution. In the case of such a linear organic polymer, a polymer having a carboxylic acid in a side chain is exemplified by, for example, JP-A-59-44615, JP-A-54-34327, and JP-A-58-12577. Methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, as described in each of the publications of JP-A-59-53836, JP-A-59-71048 A maleic acid copolymer, a partially esterified maleic acid copolymer or the like is similarly useful as an acidic cellulose derivative having a carboxylic acid in a side chain.

In addition to the above, in the case of the alkali-soluble binder of the present invention, an acid anhydride or the like is added to a polymer having a hydroxyl group, or a polyhydroxystyrene resin, a polyoxyalkylene resin, or a poly(2-hydroxyethyl group). (Meth) acrylate), polyvinylpyrrolidone or polyethylene oxide, polyvinyl alcohol and the like are also useful. Further, the linear organic high molecular polymer can copolymerize a monomer having hydrophilicity. Examples of the examples include alkoxyalkyl (meth)acrylate, hydroxyalkyl (meth)acrylate, glycerol (meth)acrylate, (meth)acrylamide, and N- Methylol methacrylate, 2 or 3 alkyl decylamine, dialkylaminoalkyl (meth) acrylate, morpholinyl (meth) acrylate, N-vinyl pyrrolidone, N -vinyl caprolactam, vinyl imidazole, vinyl triazole, methyl (meth)acrylate, ethyl (meth)acrylate, branched or linear propyl (meth)acrylate, branched or linear Butyl (meth)acrylate or phenoxyhydroxypropyl (meth)acrylate. In the case of other hydrophilic monomers, do they contain a tetrahydrofuranyl group, a phosphoric acid group, a phosphate group, a quaternary ammonium salt group, an extended ethoxy chain, a propoxy chain, a sulfonic acid group, and a salt thereof? Monomers such as morphyl ethyl ester are also useful.

Further, the alkali-soluble binder may have a polymerizable group in the side chain in order to improve the crosslinking efficiency, and may be, for example, a polymer containing an allyl group, a (meth)acryl group or an allyloxyalkyl group in a side chain. As an example of the polymer containing the above polymerizable group, commercially available KS photoresist - 106 (manufactured by Osaka Organic Chemical Industry Ltd.), CYCLOMER P (DAICEL Chemical Industry Co., Ltd.) Company (manufactured by Daicel Chemical Industries, Ltd.). Further, in order to increase the strength of the hardened film, alkali-soluble nylon or a polyether of 2,2-bis-(4-hydroxyphenyl)-propane and epichlorohydrin is also useful.

From the viewpoint of heat resistance, among these various alkali-soluble binders, polyhydroxystyrene resin, polyoxyalkylene resin, acryl resin, acrylamide resin, and propylene/acrylamide resin are preferable. The copolymer resin is preferably a propylene-based resin, an acrylamide-based resin, or a propylene/acrylamide-based resin copolymer resin from the viewpoint of developability inhibition.

The propylene-based resin is preferably a single benzyl (meth)acrylate, (meth)acrylic acid, (meth)acrylic acid-hydroxyethyl ester or (meth)acrylamide. A copolymer composed of a body, or a commercially available KS photoresist - 106 (manufactured by Osaka Organic Chemical Industry Ltd.), CYCLOMER P (Daicel Chemical Industries, Ltd.) , Ltd.) Manufacturing).

The weight average molecular weight of the alkali-soluble binder (in terms of polystyrene measured by the GPC method) is preferably from 1000 to 2 × 10 ⁵ , more preferably from 2000 to 1 × 10 ⁵ , from the viewpoints of developability, liquid viscosity, and the like. The polymer is particularly preferably a polymer of 5000 to 5 x 10 ⁴ .

○ Crosslinker

When a sufficient crosslinking agent is used in the colored curable composition of the present invention, the hardness of the colored cured film of the cured colored curable composition can be further improved. The crosslinking agent is not particularly limited as long as it can be cured by a crosslinking reaction, and examples thereof include (a) an epoxy resin and (b) selected from a methylol group, an alkoxymethyl group, and a decyloxy group. Substituting at least one substituent in the methyl group, a melamine compound, a guanamine compound, a glycoluril compound, and a urea-based compound, (c) substituted with at least one selected from the group consisting of a methylol group, an alkoxymethyl group, and a decyloxymethyl group A phenol compound, a naphthol compound or a hydroxy hydrazine compound substituted by a base. Among them, a polyfunctional epoxy resin is preferred. For specific examples of the specific crosslinking agent, etc., the descriptions of paragraphs [0134] to [0147] of JP-A-2004-295116 can be referred to.

○Other additives

The colored curable composition may be mixed with various additives such as a filler, a polymer compound other than the above, a nonionic surfactant, a cationic surfactant, an anionic surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber, and an anti-aggregation. Agents, etc. As for these additives, those described in paragraphs [0155] to [0156] of JP-A-2004-295116 can be cited. The coloring-curable composition of the present invention may contain the sensitizer or the photosensitizer described in paragraph [0078] of JP-A-2004-295116, and the thermal polymerization inhibitor described in paragraph [0081] of the same publication.

Further, when the alkali solubility in the non-light-emitting region is promoted and the developability of the colored curable composition is attempted, the organic carboxylic acid in the composition is preferably added to a low molecular weight organic carboxylic acid having a preferred molecular weight of 1,000 or less.

Specific examples thereof include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trimethylacetic acid, caproic acid, diethyl acetic acid, heptanoic acid, and octanoic acid; oxalic acid, malonic acid, and the like. Succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, malic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, An aliphatic dicarboxylic acid such as methyl succinic acid, tetramethyl succinic acid or citraconic acid; an aliphatic tricarboxylic acid such as 1,2,3-propanetricarboxylic acid, aconitic acid or oxalic acid; benzoic acid; An aromatic monocarboxylic acid such as toluic acid, cumanoic acid, 2,3-xylenecarboxylic acid or 3,5-dimethylbenzoic acid; citric acid, isophthalic acid, terephthalic acid, trimellitic acid, An aromatic polycarboxylic acid such as trimesic acid, pyromellitic acid or pyroic acid; phenylacetic acid, hydroxyatoleic acid, hydroxycinnamic acid, phenylglycolic acid, phenylsuccinic acid, atopic acid, cinnamic acid Other carboxylic acids such as methyl cinnamate, benzyl cinnamate, cinnamic acid acetic acid, coumaric acid, and umbrella acid.

[Modulation and characteristics of hardenable composition]

The color hardening composition of the present invention is prepared by mixing the above-mentioned essential components and optional components as needed. Further, in order to enhance the dispersibility of the pigment, a pigment dispersion liquid of the dispersed pigment is prepared in advance, and the colored thermosetting composition of the present invention can be adjusted by using the pigment dispersion liquid.

The color hardening composition of the present invention has excellent storage stability, and further improves light resistance due to the advantage of using a pigment, and particularly forms a color material having an excellent color hardening film as an industrial color filter. Preferably. For example, it is useful for forming a color pixel such as a color filter of a liquid crystal display element (LCD) or a solid-state image sensor (for example, CCD or CMOS). In particular, it can be suitably used for the formation of colored pixels for liquid crystal display elements such as CCDs and CMOSs.

[Color filter and method of manufacturing the same]

The color filter of the present invention and a method of manufacturing the same are described in detail below. The coloring curable composition of the present invention as described above can be used in the method for producing a color filter of the present invention. The method for producing a color filter of the present invention comprises the step of applying a colored curable composition of the present invention as described above to a substrate (support or temporary support) to form a colored curable composition (hereinafter referred to as coating). Step), after exposing the colored curable composition layer through a photomask, and developing to form a colored pattern (hereinafter referred to as exposure/development step). The following describes the coating step and the exposure ‧ development step.

○ coating method ‧ coating step

In the coating step, a colored curable composition is applied onto a support by a coating method such as spin coating, cast coating, or roll coating. The coated film is prebaked to form a colored curable composition layer. The thickness of the color-curable composition layer to be formed is preferably in the range of 1.0 μm to 5.0 μm, and particularly preferably from the viewpoint of thinning or color reproducibility of the color filter for liquid crystal display elements. From 1.0 μm to 4.0 μm, more preferably from 1.0 μm to 3.0 μm.

Examples of the support include a soda lime glass, a Pyrex (registered trademark) glass, a quartz glass, and a transparent conductive film used for a liquid crystal display element, or a photoelectric conversion element substrate for an image pickup element or the like. For example, a germanium substrate or a complementary metal oxide semiconductor (CMOS) substrate can be cited. The substrates form black stripes that separate the pixels. Further, an undercoat layer may be provided on the support as needed in order to improve adhesion to the upper layer, prevent diffusion of the substance, or flatten the surface.

Exposure ‧ development step

The color-curable composition formed on the support is exposed through a photomask. As the light or radiation obtained is suitable for the exposure, ultraviolet rays such as g-line, h-line, and i-line are preferable. The exposure can be performed in any of a proximity mode, a mirror projection mode, and a stepper mode, but in particular, in a stepper mode (reduced projection exposure mode using a reduced projection exposure machine) Preferably. The stepper method is a method in which a pattern is formed by gradually changing the exposure amount while forming a pattern, and a rectangular pattern having a good pattern can be obtained when performing stepwise exposure. Further, as the exposure apparatus for stepwise exposure, for example, an i-line stepping machine (trade name: FPA-3000i5+, manufactured by CANON, INC.) can be used. Further, the amount of exposure at the time of exposure is not particularly limited, but is preferably 50 mJ/cm ² to 1000 mJ/cm ² .

development

The developer develops the color hardening composition after exposure. Development can be carried out using a developer. In the developer, one of the unhardened (unexposed portions) of the colored curable composition layer is dissolved, and any of the components having no dissolution and hardening portion (exposure portion) can be used. Specifically, a composition of various organic solvents or an aqueous alkaline solution can be used. The organic solvent is exemplified as the organic solvent used in the preparation of the coloring curable composition. The alkaline aqueous solution is, for example, an alkaline aqueous solution which is dissolved in a concentration of 0.001% by mass to 10% by mass, preferably 0.01% by mass to 1% by mass. Examples of the basic compound include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, and tetramethylammonium hydroxide. Alkyl ammonium, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo-[5.4.0]-7-undecene, and the like. Further, when alkaline water-soluble is used as the developer, it is usually washed with water after development.

Other (heat treatment, etc.)

The colored pattern can be formed through the coating step, the exposure ‧ development step as described above. The obtained color pattern can be further subjected to heat treatment. The colored pattern formed by heating (so-called post-baking) can be further hardened.

For example, heat treatment is performed by a pattern heating method such as a hot plate, various heaters, or an oven.

The temperature of the heat treatment is preferably from 160 ° C to 260 ° C, more preferably from 180 ° C to 220 ° C, in terms of increasing the hardening efficiency. The heat treatment time varies depending on the heating temperature, and is usually preferably carried out between 3 minutes and 10 minutes.

In the method for producing a color filter of the present invention, the coloring pattern (pixel) having a desired number of hue can be obtained by repeating the coating step, the exposure, the development step, and the heating step as needed in accordance with the desired color number. Color filter.

○Inkjet method

A color filter can be produced by the ink jet method of the present invention. In the ink jet ink, the embodiment of the present invention is not particularly limited, and the method described in, for example, JP-A-2002-201387 is preferably used. The ink jet ink uses the above colored curable composition, and it is preferred that no photopolymerization initiator or photopolymerization initiator is used.

As for the inkjet ink, it is preferable to suppress the ink temperature within a range of ±5% or less of the viscosity variation. It is preferable that the viscosity at the time of injection is 5 to 25 mPa ‧ , more preferably 8 to 22 mPa ‧ , and particularly preferably 10 to 20 mPa ‧ (the viscosity of the present invention is not particularly limited to 25 ° C). In addition to the aforementioned setting of the injection temperature, the viscosity can be adjusted by adjusting the type and amount of the component containing the ink. For example, the viscosity can be measured by a general device such as a conical flat type rotary viscometer or an E type viscometer.

Further, from the viewpoint of improving the flatness of the pixels, it is preferable that the surface tension of the ink at the time of injection is 15 to 40 mN/m (the surface tension in the present invention is not particularly limited to 23 °C). More preferably, it is 20 to 35 mN/m, and most preferably 25 to 30 mN/m. The surface tension can be adjusted by the addition of a surfactant or the kind of solvent. The aforementioned surface tension can be, for example, a platinum plate method using a surface tension measuring device (manufactured by Kyowa Interface Science Co., Ltd., CBVP-Z) or a fully automatic balanced electronic surface tension meter (manufactured by Kyowa Scientific Co., Ltd.) To determine.

As for the inkjet ink for spraying a color filter, various methods can be employed for the method of suppressing the ink by continuously jetting the ink, and spraying the intermittent ink using the piezoelectric element to heat the ink by using the foaming method. The method of intermittent spraying, and the like.

Further, regarding the ink jet method for forming various pixels, the method of thermally curing the ink, and the photo-curing method, since a transparent image receiving layer is formed on the substrate, a general method such as a drip method can be used.

In the present invention, before the pixels are formed by the ink jet ink using the color filter, the partition walls are prepared in advance, and it is preferable that the ink is sprayed on the portion surrounded by the partition walls. When the color filter is produced, the partition wall may be any one, and it is preferably a functional light-shielding partition wall (hereinafter simply referred to as "partition wall") having a black matrix. The partition wall can be produced by the same material and method as the general color filter using a black matrix.

Thereafter, the heat treatment is carried out by the above-mentioned "heat treatment or the like", and it is preferable to solidify the layer of the above-described sprayed inkjet ink.

○Color filter performance

A color filter (color filter of the present invention) obtained by the method for producing a color filter of the present invention has excellent light resistance because the coloring hardening composition of the present invention is used. Therefore, the color filter of the present invention can be used for a solid-state imaging element such as a liquid crystal display element or a CCD.

[Liquid Crystal Display Element]

When the color filter of the present invention is used for television, the chromaticity of all the monochromatic colors of the red (R), green (G), and blue (B) by the F10 light source and the values described in the following table (hereinafter referred to as the present) The difference (ΔE) of the "target chromaticity" of the invention is preferably within a range of 5, more preferably within 3, and particularly preferably within 2.

The chromaticity of the present invention was measured by a microspectrophotometer (manufactured by OLYMPUS Optical Industries Co., Ltd.; OSP 100 or 200), and the result of the field of view of the F10 light source was calculated to be 2 degrees, and xyz represents the xyY value of the color system. Further, the difference from the target color value is represented by the color difference of the La*b color system.

The liquid crystal display device having the color filter of the present invention is preferably high contrast, excellent black drawing power, in particular VA mode. It can be suitably used for a large-screen liquid crystal display device such as a notebook computer display or a television monitor. Further, the color filter of the present invention can use a CCD device to exhibit excellent performance.

[Examples]

The embodiments of the present invention are further described in detail below, and the following embodiments are not limited thereto. Furthermore, it is not particularly limited, and "parts" and "%" are quality standards.

(Example I) (Example I-1) [1. Modulation of red hardening composition]

Each of the components described below was mixed and dissolved to obtain a colored curable composition.

<Binder 1>

‧ polymer (benzyl methacrylate / methacrylic acid = 78/22 molar ratio of random copolymer, molecular weight 40,000) 27 parts by mass

‧ Propylene glycol monomethyl ether acetate 73 parts by mass

<DPHA liquid>

‧ Dipentaerythritol hexaacrylate (polymerization inhibitor MEHQ) containing 500 ppm, manufactured by Nippon Kayaku Co., Ltd., trade name: KAYARAD DPHA) 76 parts by mass

‧ propylene glycol monomethyl ether 24 parts by mass

<Polymerization initiator A>

(2,4-bis(trichloromethyl)-6-[4'-(N,N-diethoxycarbonylmethyl)amino-3'-bromophenyl]-s-triazole )

<Polymerization initiator B>

2-trichloromethyl-(p-styrylstyryl) 1,3,4- Diazole

<Interacting Agent 1>

MEGAFACE F-780-F (manufactured by Dainippon Ink Chemical Industry Co., Ltd.): The composition is as follows

‧C ₆ F ₁₃ CH ₂ CH ₂ OCOCH=CH ₂ 40 parts by mass, and H(OCH(CH ₃ )CH ₂ ) ₇ OCOCH=CH ₂ 55 parts by mass, and H(OCH ₂ CH ₂ ) ₇ OCOCH=CH ₂ 5 parts by mass of a copolymer (molecular weight 30,000) 30 parts by mass,

‧ methyl ethyl ketone 70 parts by mass

[2. Assessment of preservation stability]

The colored hardening composition obtained above was visually evaluated for the degree of precipitation based on the following criteria based on the visual observation of the foreign matter stored at room temperature for one month. Table 1 shows the results.

○: It is determined that there is no precipitation.

△: Only a few precipitates were identified.

×: The determination is made.

[3. Production of color filters and evaluation of light resistance]

The color-curable composition obtained above was applied onto a glass substrate by a spin coater to have a film thickness of 0.6 μm, and prebaked at 100 ° C for 120 seconds to obtain a monochromatic color filter for evaluation of light resistance. The monochromatic color filter for light resistance evaluation obtained was irradiated with a 100,000 lux, 20 hour xenon lamp (equivalent to 200 lux.h). The color difference (ΔE*ab) of the monochromatic color filter was measured before the xenon lamp irradiation, and it was used as an indicator of light resistance. Furthermore, the smaller the ΔE*ab, the better the light resistance is by the following criterion. Table 1 shows the results.

~Judgement criteria~

◎: ΔE*ab value <1

○: 1 ≦ ΔE*ab value <3

△: 3≦ΔE*ab value ≦10

×: 10<ΔE*ab value

(Examples I-2 to I-30, Comparative Examples Ic1 to Ic4)

Table 1 below shows each compound of the "specific complex (exemplary compound Ia-5)" in the colored curable composition of Example I-1. In addition, the yellow dye 1 which is equivalent to the pigment of "CIPY150" is replaced by "yellow dye 1", and the binder 1 is added in accordance with this, and the solid content concentration is the same as the color hardening property of the example I-1. The same thing is prepared. In addition, as for the pigment, the coloring curable composition was prepared in the same manner as in Example I-1 except that "CIPR254" and "CIPY150" were not added. With respect to the obtained color-curable composition, a monochromatic color filter was produced by a coating method in the same manner as in Example I-1, and the monochromatic color filter was subjected to light resistance in the same manner as in Example I-1. Evaluation. Table 1 shows the results.

Further, for example, the solid content concentration of the pigment and/or the dye is used as follows. The colored curable composition of the colored curable composition of Preparation Example I-1 is used.

Comparative Example Ic1 was prepared by substituting the dispersion of CIPR254 and CIPY150 used in Example I-1 with the binder 1 to adjust the solid content concentration of the dye (IIIb-1).

Comparative Example 2 was substituted with a specific complex (exemplified compound Ia-5) used in Example I-1 to form C.I. Acid Violet-17.

Comparative Example 3 The amount of the specific complex (exemplified compound Ia-5) used in Example I-1 was the same as the amount of the pigment, and the CIPV23 dispersion (solid content concentration 18.70%, pigment concentration 13.10%) was added, corresponding to This reduces the solid content concentration of the binder 1 adjusting pigment (CIPV23).

Comparative Example 4 is the same as the total amount of the specific complex (exemplified compound Ia-5) used in Example I-1 and the pigment, and does not change the ratio of CIPR254 to CIPY150 dispersion used in Example I-1, and increases CIPR254. The amount of the CIPY 150 dispersion corresponds to the reduction of the binder 1 to adjust the concentration of the solid component.

(Examples II, III)

In place of the pigment type described in Table 1, a colored curable composition was obtained in the same manner except that the blending amount was replaced with the following table. Regarding the obtained color hardening composition (the same as in Example I), the evaluation of the storage stability was performed. Further, a monochromatic color filter was produced using the obtained color-curable composition (the same as in Example I), and the monochromatic color filter (the same as in Example 1) was used to evaluate the light resistance.

The amount of pigment blended in Example II

The amount of pigment blended in Example III

As is clear from Table 1, the colored hardenable composition of the specific organometallic complex and the pigment has excellent storage stability, and the monochromatic color filter formed using the colored curable composition has excellent light resistance. Further, it was judged that the color filter of the present invention has higher contrast and luminance than Comparative Examples c2 and c3, and is a color filter suitable for a liquid crystal display device. Further, it was found that when only the pigment of Comparative Example c4 was used, the light resistance and the storage stability were further improved, and the performance of the specific metal complex compound was enhanced. Further, it is understood that the above-described excellent effects of the present invention can be exhibited in the same manner even if the type of the pigment is changed.

Claims (15)

A red color-curable composition which is a red color-curable composition containing a pigment, a dispersant, and a polymerizable compound in an organic solvent, and is characterized in that the organic metal is further contained in an amount of 100 parts by mass based on the pigment. 3 to 150 parts by mass of the organometallic complex having a metal atom or a metal compound and a residue of a compound represented by the following formula (I) which becomes a ligand; (In the formula (I), R ¹ to R ⁶ each independently represent a hydrogen atom or a substituent, and R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group). The colored hardening composition of the first aspect of the invention, wherein the organometallic complex is selected from the group consisting of a compound represented by the following formula (II-1) and a compound represented by the following formula (II-2); At least one of the group consisting of the compounds represented by the following formula (III), (In the formula (II-1), R ¹ to R ⁷ are synonymous with the above formula (I); Ma represents a metal atom or a metal compound; X ² represents a group necessary for neutralizing the charge of Ma; X ¹ represents a base that can be combined with Ma; X ¹ and X ² can be combined to form a ring of 5, 6 or 7 members), (In the general formula (II-2), R ¹ to R ⁷ are synonymous with the general formula (I); and R ⁸ to R ¹³ each independently represent a hydrogen atom or a substituent; and R ¹⁴ each independently represents a hydrogen atom or a halogen atom. , an alkyl group, an aryl group or a heterocyclic group; Ma represents a metal atom or a metal compound), (In the formula (III), R ² to R ⁵ and R ^{7 have the} same meanings as in the formula (I); Ma represents a metal atom or a metal compound; X ³ represents NR (R represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group) , heterocyclic group, mercapto group, alkylsulfonyl or arylsulfonyl), nitrogen atom, oxygen atom or sulfur atom; X ⁴ represents NRa (Ra represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a hetero atom a cyclic group, a fluorenyl group, an alkylsulfonyl group or an arylsulfonyl group), an oxygen atom or a sulfur atom; Y ¹ represents NRc (Rc represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a fluorenyl group) , alkylsulfonyl or arylsulfonyl), a nitrogen atom or a carbon atom; Y ² represents a nitrogen atom or a carbon atom; and R ⁸ and R ⁹ each independently represent an alkyl group, an alkenyl group, an aryl group or a heterocyclic group; , alkoxy, aryloxy, alkylamino, arylamino or heterocyclic amine; R ⁸ and Y ¹ may be combined to form a ring of 5, 6 or 7 members; R ⁹ and Y ² may Combines with each other to form a ring of 5, 6 or 7 members; X ⁵ represents a group which can bind to Ma; a is represented by 0, 1 or 2). The colored hardening composition of claim 1 or 2, wherein the metal atom or metal compound is an iron atom (Fe), a zinc atom (Zn), a cobalt atom (Co), a vanadium oxide (VO), and a copper atom. Any of (Cu). The colored hardening composition according to claim 1 or 2, wherein in the above formula (1), each of R ³ and R ⁴ is a phenyl group. The color hardening composition according to claim 1 or 2, wherein the pigment is at least one selected from the group consisting of a diketopyrrolopyrrole pigment, a condensed azo pigment, and an anthraquinone pigment. A colored hardening composition according to claim 1 or 2, which contains a yellow pigment. The colored curable composition according to claim 1 or 2, wherein the colored curable composition further contains a photopolymerization initiator. The colored hardening composition of claim 1 or 2, wherein the pigment is selected from the group consisting of C.I. Pigment Red 254, C.I. Pigment Red 209, C.I. At least one of red 177 and C.I. pigment red 242. The colored hardening composition of claim 1 or 2, wherein the pigment is contained in an amount of 10 to 70% by mass. The color hardening composition according to claim 1 or 2, wherein the content of the dispersant is from 1 to 80% by mass. The color hardening composition according to claim 1 or 2, wherein the content of the polymerizable compound is from 10 to 80% by mass. A method for producing a color filter, comprising the steps of applying a colored curable composition according to any one of claims 1 to 11 to form a red curable composition layer on a substrate, and passing the step After the photomask exposes the red curable composition layer, it develops to form a colored pattern. A method of manufacturing a color filter, comprising the steps of disposing a partition wall on a substrate, and spraying the substrate toward the substrate in an area surrounded by the partition wall, as claimed in claims 1 to 11 A step of forming a red curable composition layer by forming a colored curable composition according to any one of the items, and a step of solidifying the red curable composition layer by heat treatment. A color filter comprising a curable composition layer obtained by curing a colored curable composition according to any one of claims 1 to 11 on a substrate. A liquid crystal display element comprising a color filter as in claim 14 of the patent application.