TW201337458A - Phthalocyanine compound, colored curable composition, color filter and manufacturing method thereof, liquid crystal display device, organic electroluminescence element and solid-state image element - Google Patents

Abstract

The invention provides a colored curable composition excellent in transmittance, heat resistance and light resistance. The colored curable composition contains a phthalocyanine compound represented by a general formula (1) shown as below. In the general formula (1), R1 to R4 respectively represent a substituent represented by a general formula (2) shown as below or a halogen atom. In the general formula (2), X1 represents -O-, -S-, -NR13- or -SO2-, and Ar1 represents an aromatic carbocyclic group which could have a substituent or an aromatic heterocyclic group which could have a substituent.

Description

Colored hardening composition and color filter

The present invention relates to a color hardening composition and a color filter using the colored curable composition. Further, it relates to a liquid crystal display device, an organic electroluminescence device, and a solid-state imaging device using the color filter. Further, it relates to a method of manufacturing a color filter.

Color filters have been manufactured by the prior art by dispersing a pigment dispersion composition containing an organic pigment or an inorganic pigment, a polyfunctional monomer, a polymerization initiator, an alkali soluble resin. A color-curable composition is prepared by using other components as needed, and a coloring pattern is formed by photolithography, inkjet method (Inkjet) or the like using the composition.

In recent years, color filters have been used not only for displays but also for televisions in liquid crystal display (LCD) applications, and require not only large screens but also high image quality. It also requires low power consumption. In response to such requirements, color filters are required to have high color characteristics such as chromaticity, contrast, and high transmittance. In addition, the same applies to color filters used for image sensors (solid-state imaging devices). Further, color characteristics such as reduction in color unevenness, color resolution, and improvement in transmittance are required.

However, in the conventional pigment dispersion system, problems such as generation of scattering due to coarse particles of the pigment and increase in viscosity due to poor dispersion stability are likely to occur, and it is difficult to further improve contrast and brightness.

Therefore, as a coloring agent to date, not only the coloring agent using a pigment but also a coloring agent using a dye has been studied (for example, refer to Japanese Laid-Open Patent Publication No. Hei 6-75375). When a dye is used as a coloring agent, the hue or brightness of the displayed image at the time of image display can be improved by the color purity of the dye itself or the definition of the hue, and the coarse particles disappear, so that the contrast can be improved. Considered useful.

As examples of dyes, Phthalocyanine dyes, dipyrromethene dyes, pyrimidineazo dyes, pyrazoleazo dyes, xanthene are known. A compound having a wide variety of dye precursors such as a dye (for example, see JP-A-2008-292970, JP-A-2007-039478, JP-A-H09-157536, and JP-A No. 6-157536 Japanese Laid-Open Patent Publication No. Hei 11-152415, No. WO2011/105603.

Here, it is required that the color hardening composition used in the color filter or the like has high color purity, and the portion which is unnecessary for the color filter does not have absorption (high transmission) rate). In addition, heat resistance and light resistance are also required to be high. In order to achieve the object of the present invention, it is an object of the present invention to provide a color-curable composition which is a non-essential portion of a color filter and which is capable of producing a color filter having high heat resistance and light resistance. In particular, the object is to provide a colorant that is useful as a green filter.

Based on this, the inventors of the present invention conducted an effort to find that a coloring curable composition having high transmittance and excellent light resistance can be obtained by using a halogen compound having a specific substituent instead of a phthalocyanine compound. In other words, by introducing an alkylene group at a specific position of the side chain of the indigo ring, the solubility is successfully improved, and aggregation of the compounds can be suppressed, and the heat resistance and light resistance can be maintained while the transmittance is improved. Further, it has been found that the pattern formability can also be improved, thereby completing the present invention. It has been found that particularly when it is formulated into a carboxylic acid-based binder, it exhibits a remarkable excellent effect.

Specifically, the above problem can be solved by the following method.

<1> A color hardening composition comprising a phthalocyanine compound represented by the following formula (1), wherein the formula (1)

(In the formula (1), R ¹ to R ⁴ are each a substituent represented by the following formula (2) or a halogen atom, and p, q, r, and s represent 0 to 4, respectively, in the formula (1) The number of substituents represented by the formula (2) is 1 to 12; R represents a hydrogen atom or a monovalent substituent, respectively; M represents Cu, Zn, V(=O), Mg, Ni, Ti(=O) , Mg, Sn or Si),

(In the formula (2), X ¹ represents -O-, -S-, -NR ¹³ - or -SO ₂ -, and Ar ¹ represents an aromatic carbocyclic group which may have a substituent or an aromatic group which may have a substituent a heterocyclic group; R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms; n1 represents an integer of 1 to 3; and in the case where n1 is 2 or 3, a plurality of R ¹¹ may be the same or different; Y ¹ represents -O-, -S-, -NR ¹³ -, -SO ₂ -, or -C(=O)-, and R ¹² represents a monovalent substituent; R ¹³ represents a hydrogen atom or a carbon number, respectively. 4 alkyl).

<2> The colored curable composition according to <1>, wherein a halogen atom represented by R ¹ to R ⁴ represents Br or Cl, and M represents Cu or Zn.

<3> The colored curable composition according to <1> or <2>, wherein X ¹ of the formula (2) is -O-, and Ar ¹ is a phenylene group which may have a substituent, Y ¹ is -O-, and R ¹² is an alkyl group which may have a substituent, an acyl which may have a substituent, or a sulfonyl which may have a substituent.

<4> The colored curable composition according to <1> or <2>, wherein X ¹ of the formula (2) is -O-, Ar ¹ is a phenyl group which may have a substituent, and Y ¹ is - C(=O)-, R ¹² is an alkoxyl group which may have a substituent, or an alkylamine group which may have a substituent.

The colored curable composition according to any one of <1> to <4> wherein the sum of p, q, r and s of the formula (1) is from 12 to 16.

The colored curable composition according to any one of <1> to <5>, further comprising a carboxylic acid-based binder.

The colored curable composition according to any one of <1> to <6>, further comprising a polymerizable compound and a photopolymerization initiator.

<8> The colored curable composition according to <7>, wherein the photopolymerization initiator is an oxime compound or a biimidazole compound.

The colored hardening composition according to any one of <1> to <8>, further comprising a yellow coloring agent.

<10> The colored curable composition according to <9>, wherein the yellow colorant is an azo dye or a monomethine dye.

<11> The colored curable composition according to <9>, wherein the yellow colorant is a monomethine dye represented by the following formula (5), and the formula (5)

(In the formula (5), R ¹¹ represents an alkyl group or a vinyl group, respectively, and R ¹² represents an aromatic ring group having a substituent, respectively).

The coloring curable composition according to any one of the above-mentioned <1>, wherein the compound represented by the formula (1) is a phthalocyanine compound represented by the following formula (1'). ,

(In the formula (1'), R ¹ to R ⁴ are each a substituent represented by the following formula (2'), a bromine atom or a chlorine atom, and p, q, r, and s represent 0 to 4, respectively. The sum of p, q, r and s is 12 to 16; the number of substituents represented by the formula (2') in the formula (1') is 4 to 12; R represents a hydrogen atom; M represents Cu or Zn) ,

(In the formula (2'), X ¹ represents -O-, Ar ¹ represents a phenyl group; R ¹¹ represents a hydrogen atom or a methly group, and n1 represents an integer of 1 to 3; and n1 is 2 or 3; In the case where a plurality of R ^{11 's} may be the same or different; in the case where Y ¹ represents -O-, R ¹² is an alkyl group or a fluorenyl group, and in the case where Y ¹ represents -C(=O)-, R ¹² It is an alkoxy group or an alkylamino group).

<13> A color filter comprising the coloring layer obtained by using the colored curable composition according to any one of <1> to <12>.

<14> A method of producing a color filter, comprising the steps of: forming a coloring layer by applying the color hardening composition according to any one of <1> to <13> on a substrate; The formed colored layer is exposed to a pattern and developed to form a colored region.

<15> A liquid crystal display device, an organic electroluminescence device, or a solid-state image sensor, comprising the color filter according to <13> or the method for producing a color filter according to <14> Color filter.

<16> A phthalocyanine compound represented by the following formula (1'),

(In the formula (1'), R ¹ to R ⁴ are each a substituent represented by the following formula (2'), a bromine atom or a chlorine atom, and p, q, r, and s represent 0 to 4, respectively. The sum of p, q, r and s is 12 to 16; the number of substituents represented by the formula (2') in the formula (1') is 4 to 12; R represents a hydrogen atom; M represents Cu or Zn) ,

(In the formula (2'), X ¹ represents -O-, Ar ¹ represents a phenyl group; R ¹¹ represents a hydrogen atom or a methyl group, and n1 represents an integer of 1 to 3; and in the case where n1 is 2 or 3, A plurality of R ^{11 's} may be the same or different; in the case where Y ¹ represents -O-, R ¹² is an alkyl group or a fluorenyl group, and in the case where Y ¹ represents -C(=O)-, R ¹² is an alkoxy group. Base or alkylamino group).

According to the present invention, it is possible to provide a color hardening composition which has high color purity, is not required to be a color filter, has no absorption (high transmittance), and is excellent in light resistance. Therefore, it can be preferably used as a color filter, and is particularly preferably used as a color filter for green. Further, according to the present invention, it is possible to provide a liquid crystal display device and a solid-state imaging element which display colors of a bright image and exhibit high contrast.

Hereinafter, the contents of the present invention will be described in detail. In addition, in the specification of the present application, "~" is used in the meaning of including the numerical values described before and after the lower limit and the upper limit. In the present specification, the "base" such as an alkyl group is not particularly specified unless otherwise specified. Then, it may have a substituent or may have no substituent. Further, in the case of a group defining a carbon number, the carbon number means the number including the number of carbon atoms of the substituent.

<Coloring hardenable composition>

The color hardening composition of the present invention is characterized by comprising a phthalocyanine compound represented by the formula (1). Usually, two or more phthalocyanine compounds represented by the general formula (1) are contained.

(In the formula (1), R ¹ to R ⁴ are each a substituent represented by the following formula (2) or a halogen atom, and p, q, r, and s represent 0 to 4, respectively, in the formula (1) The number of substituents represented by the formula (2) is 1 to 12. R represents a hydrogen atom or a monovalent substituent, respectively, and M represents Cu, Zn, V(=O), Mg, Ni, Ti(=O). , Mg, Sn or Si.)

(In the formula (2), X ¹ represents -O-, -S-, -NR ¹³ - or -SO ₂ -, and Ar ¹ represents an aromatic carbocyclic group which may have a substituent or an aromatic group which may have a substituent R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and n 1 represents an integer of 1 to 3. When n 1 is 2 or 3, a plurality of R ^{11 's} may be the same or different. Y ¹ represents -O-, -S-, -NR ¹³ -, -SO ₂ -, or -C(=O)-, and R ¹² represents a monovalent substituent.

Although most of the coloring matter using a phthalocyanine compound as a color filter has been studied (Japanese Patent No. 3476208, International Publication WO2011/105603), it is not possible to obtain a coloring composition which is particularly suitable for use as a green filter. A color-curable composition having color purity, transmittance, heat resistance, light resistance, hardening sensitivity, and resist storage stability. The present invention is of great significance in view of the fact that the colored curable composition of the present invention satisfies all of these aspects.

Further, the phthalocyanine compound used in the present invention is excellent in solubility, has high compatibility with a carboxylic acid-containing binder, and is excellent in heat resistance, so that high transmittance can be achieved.

Further, the phthalocyanine compound used in the present invention preferably has a ratio of the minimum value of the absorption intensity in the vicinity of 500 nm to the maximum value of the main absorption (the minimum value of the absorption intensity near 500 nm / the maximum value of the main absorption) In the range of 0 to 0.1, it is more preferably in the range of 0 to 0.02.

In the case where the phthalocyanine compound represented by the formula (1) used in the present invention is a mixture of two or more kinds, p, q, r, s and the formula (1) in the formula (1) The number of substituents represented means the average of the substituents in the mixture.

Hereinafter, the details of the phthalocyanine compound represented by the formula (1) will be described.

In the formula (1), R ¹ to R ⁴ are each a substituent represented by the formula (2) or a halogen atom.

The halogen atom is preferably a bromine atom or a chlorine atom, and particularly preferably a chlorine atom.

In the above formula (1), when the substitution position of the halogen atom is the α position of the phthalocyanine skeleton, the absorption wavelength can be made long, and it is suitably used as a green filter. α The number of substitutions of the bits is based on the total number of eight alpha positions on the phthalocyanine, preferably four to eight.

p, q, r, s represent 0~4, respectively, preferably any three of p, q, r, s represents 3~4, and particularly preferably any three of p, q, r, s represents 4 .

The number of the substituent represented by the formula (2) in the formula (1) is from 1 to 12, preferably from 2 to 10, and more preferably from 4 to 8.

R represents a hydrogen atom or a monovalent substituent, respectively. The substituent T may be the following substituent T, preferably an alkyl group or an alkoxy group, more preferably an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms. R is particularly preferably a hydrogen atom, a methyl group and a methoxy group, and more preferably a hydrogen atom.

M represents Cu, Zn, V(=O), Mg, Ni, Ti(=O), Mg, Sn or Si, preferably Cu, Zn or V(=O), and more preferably Cu or Zn.

In the formula (2), X ¹ represents -O-, -S-, -NR ¹³ - or -SO ₂ -, preferably -O- or -SO ₂ -, more preferably -O-. R ¹³ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.

Ar ¹ represents an aromatic carbocyclic group which may have a substituent or an aromatic heterocyclic group which may have a substituent, and is preferably an aromatic carbocyclic group.

The aromatic carbocyclic ring is preferably an aryl group having 6 to 24 carbon atoms, and examples thereof include a phenylene group and a naphthylene group, and may further have a substituent. The aromatic heterocyclic ring is preferably a heterocyclic group having 1 to 18 carbon atoms, and represents, for example, a 2-thienyl group, a 4-pyridyl group, a 2-furyl group, a 2-pyrimidinyl group ( Pyrimidinyl), 1-pyridyl, 2-benzothiazolyl, 1-imidazolyl, pyrazolyl, benzotriazol-1-yl, etc., and may also have a substitution base. As the substituent, the following substituent T can be exemplified. Ar ^{1 is} further preferably a stretched phenyl group which may have a substituent and a stretched naphthyl group which may have a substituent, and particularly preferably a stretched phenyl group which may have a substituent. Ar ¹ preferably has no substituent.

R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.

N1 represents an integer of 1 to 3, more preferably 1 or 2. In the case where n1 is 2 or 3, a plurality of R ¹¹ may be the same or different.

Y ¹ represents -O-, -S-, -NR ¹³ -, -SO ₂ -, or -C(=O)-, preferably -O-, -SO ₂ -, or -C(=O) -, more preferably -O- or -C(=O)-.

R ¹² represents a monovalent substituent, and as the substituent, the following substituent T can be exemplified, and the substituents may be further substituted by a substituent. R ^{12 is} preferably an alkyl group which may have a substituent, a mercapto group which may have a substituent, a sulfonyl group which may have a substituent, an alkoxy group which may have a substituent, or an alkylamine group which may have a substituent, and It is preferably an alkyl group having 1 to 12 carbon atoms which may have a substituent, an alkoxy group having 1 to 12 carbon atoms which may have a substituent, and an alkylamino group having 1 to 12 carbon atoms which may have a substituent.

The mass of the R ¹² moiety per molecule of the phthalocyanine compound represented by the formula (1) is preferably from 200 to 2,500, more preferably from 250 to 1,500.

An example of the substituent T is shown below.

The following group is represented by an alkyl group (preferably a linear, branched or cyclic alkyl group having 1 to 24 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group (isopropyl group). ), butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, dodecyl, Hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, norbornyl, adamantyl, alkenyl (preferably carbon number 2) Alkenyl groups of ~18, such as vinyl, allyl, 3-butene-1- An aryl group (preferably an aryl group having 6 to 24 carbon atoms, for example, a phenyl group or a naphthyl group) or a heterocyclic group (preferably a heterocyclic group having 1 to 18 carbon atoms). For example, 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyridyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, benzotriazole- 1-yl), silyl (preferably a decyl group having a carbon number of 3 to 18, such as trimethyl decyl, triethyl decyl, tributyl decyl, tert-butyl dimethyl decane a group, a third hexyl dimethyl decyl group, a hydroxyl group, a cyano group, a nitro group, an alkoxy group (preferably an alkoxy group having a carbon number of 1 to 24, for example, a methoxy group) a group, an ethoxy group, a 1-butoxy group, a 2-butoxy group, an isopropoxy group, a third butoxy group, a dodecyloxy group, and, if it is a cycloalkyloxy group, for example, a cyclopentyloxy group a group, a cyclohexyloxy group, an aryloxy group (preferably an aryloxy group having 6 to 24 carbon atoms, such as phenoxy, naphthoxy) or a heterocyclic oxy group (more Preferred are heterocyclic oxy groups having 1 to 18 carbon atoms, such as 1-phenyltetrazole-5-oxy, 2-tetrahydropyranyloxy, decyloxy (sil) Yyloxy) (preferably a decyloxy group having 1 to 18 carbon atoms, such as trimethyldecyloxy, tert-butyldimethylsilyloxy, diphenylmethylnonyloxy), decyloxy ( Acyloxy) (preferably a fluorenyloxy group having 2 to 24 carbon atoms, such as acetoxy, pivaloyloxy, benzoyloxy, dodecyloxy ( Dodecanoyloxy)), alkoxycarbonyloxy group (preferably an alkoxycarbonyloxy group having 2 to 24 carbon atoms, such as an ethoxycarbonyloxy group, a third butoxycarbonyloxy group, and, if The alkoxycarbonyloxy group is, for example, a cyclohexyloxycarbonyloxy group, an aryloxycarbonyloxy group (preferably an aryloxycarbonyloxy group having 7 to 24 carbon atoms, for example, a phenoxycarbonyloxy group). , an aminomethyl decyloxy group (preferably an aminomethyl decyloxy group having a carbon number of 1 to 24, such as N,N-dimethylamine, fluorenyloxy, N-butylamine, decyloxy) Base, N-phenylamine-mercaptooxy, N-ethyl-N-phenylamine-mercaptooxy), sulfamoyloxy (comparative) Preferred are sulfonyloxy groups having 1 to 24 carbon atoms, such as N,N-diethylaminesulfonyloxy, N-propylaminesulfonyloxy), alkylsulfonyloxy (preferably an alkylsulfonyloxy group having 1 to 24 carbon atoms, such as methylsulfonyloxy, hexadecylsulfonyloxy, cyclohexylsulfonyloxy), arylsulfonate a mercaptooxy group (preferably an arylsulfonyloxy group having 6 to 24 carbon atoms, for example, a phenylsulfonyloxy group) or a mercapto group (preferably a mercapto group having 1 to 24 carbon atoms, for example, a mercaptocarbonyl group, an ethyl fluorenyl group, a benzhydryl group, a fluorenyl group, a tetradecyl group, a cyclohexyl group, an alkoxycarbonyl group, preferably an alkoxycarbonyl group having a carbon number of 2 to 24, for example Methoxycarbonyl, ethoxycarbonyl, octadecyloxycarbonyl, cyclohexyloxycarbonyl, 2,6-di-t-butyl-4-methylcyclohexyloxycarbonyl, aryloxy a carbonyl group (preferably an aryloxycarbonyl group having 7 to 24 carbon atoms, for example, a phenoxycarbonyl group), an amine formazan group (preferably an amine carbenyl group having 1 to 24 carbon atoms, for example, an amine formazan group) , N,N-diethylamine, mercapto, N-ethyl-N-octylamine, mercapto, N,N-dibutylamine, N-propylamine, N-propyl, N- benzene An amine methyl sulfhydryl group, an N-methyl-N-phenylamine methyl fluorenyl group, an N,N-dicyclohexylamine methyl fluorenyl group, an amine group (preferably an amine group having a carbon number of 24 or less, for example, an amine group) , methylamino, N,N-dibutylamino, tetradecylamino, 2-ethylhexylamino, cyclohexylamino), anilino (preferably aniline having 6 to 24 carbon atoms) a group, for example, an anilino group, an N-methylanilino group, a heterocyclic amine group (preferably a heterocyclic amino group having 1 to 18 carbon atoms, for example, a 4-pyridylamino group), or a carboguanamine group (carbonamide) (preferably a carboguanamine group having a carbon number of 2 to 24, for example, acetamide, benzamide, tetradecylguanidino, pentamidine, cyclohexane Alkylamino), ureido (preferably a ureido group having a carbon number of 1 to 24, such as a urea group, an N,N-dimethylureido group, an N-phenylureido group), a quinone imine Imido (preferably a quinone imine group having a carbon number of 24 or less, such as N-butyl succinimido, N-phthalimido), alkoxy group carbonyl Alkylamino group (preferably alkoxycarbonylamino group having 2 to 24 carbon atoms, such as methoxycarbonylamino group, ethoxycarbonylamino group, tert-butoxycarbonylamino group, octadecyloxy group) a carbonylamino group, a cyclohexyloxycarbonylamino group, an aryloxycarbonylamino group (preferably an aryloxycarbonylamino group having 7 to 24 carbon atoms, for example, a phenoxycarbonylamino group), a sulfonylamino group (sulfonamido) (preferably a sulfonamide group having 1 to 24 carbon atoms, for example, methanesulfonamido, butanesulfonamido, benzenesulfonamido, hexadecane Hexadecanesulfonamido, cyclohexanesulfonamido, aminesulfonylamino group (preferably a sulfonylamino group having 1 to 24 carbon atoms, for example, N,N-dipropyl group Aminesulfonylamino, N-ethyl-N-dodecylaminesulfonylamino), azo (preferably an azo having 1 to 24 carbon atoms, such as phenylazo) , 3-pyrazolylazo), alkylthio (preferably alkylthio having 1 to 24 carbon atoms, such as methylthio, ethylthio, octylthio, cyclohexylthio) An arylthio group (preferably an arylthio group having a carbon number of 6 to 24, for example a phenylthio group, a heterocyclic thio group (preferably a heterocyclic thio group having 1 to 18 carbon atoms, such as a 2-benzothiazolylthio group, a 2-pyridylthio group, a 1-phenyltetrazolylsulfide group) An alkyl sulfinyl group (preferably an alkylsulfinylene group having 1 to 24 carbon atoms, for example, a dodecylsulfinyl group), an arylsulfinyl group (preferably a carbon number) 6 to 24, an arylsulfinyl group, for example, a phenylsulfinyl group, an alkylsulfonyl group (preferably an alkylsulfonyl group having 1 to 24 carbon atoms, for example, a methylsulfonyl group, Ethylsulfonyl, propylsulfonyl, butylsulfonyl, isopropylsulfonyl, 2-ethylhexylsulfonyl, hexadecylsulfonyl, octylsulfonyl, cyclohexyl Sulfosyl), arylsulfonyl (preferably arylsulfonyl having 6 to 24 carbon atoms, such as phenylsulfonyl, 1-naphthylsulfonyl), sulfamoyl (preferably an aminesulfonyl group having a carbon number of 24 or less, such as an aminesulfonyl group or an N,N-dipropylaminesulfonate Sulfhydryl, N-ethyl-N-dodecylamine sulfonyl, N-ethyl-N-phenylamine sulfonyl, N-cyclohexylamine sulfonyl), sulfo, phosphine Phosphonyl (preferably a phosphonium group having 1 to 24 carbon atoms, such as phenoxyphosphonium, octyloxyphosphonium, phenylphosphino), phosphinoylamino (preferably a phosphinylamino group having 1 to 24 carbon atoms, such as a diethoxyphosphinylamino group or a dioctyloxyphosphinylamino group).

In the case where the above monovalent group is a further substituted group, it may be further substituted by any of the above groups. Further, in the case of having two or more substituents, the substituents may be the same or different.

Further, in particular, in order to improve developability to an alkaline developing solution, an alkaline aqueous solution solubilizing portion such as a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a sulfonimide group, or a phenolic hydroxyl group (phenol) can be preferably used. a substituent such as a hydroxyl group, an acetamidine group or an acetamidine acetate group, and an alkyl group, an alkoxy group, an alkylthio group, an aryloxy group, an arylthio group or an alkylsulfonyl group substituted for the group. a substituent such as an arylsulfonyl group.

In the present invention, the following embodiments are particularly preferred.

(First embodiment)

In this embodiment, the halogen atom represented by R ¹ to R ⁴ represents Br or Cl, and M represents Cu or Zn.

(Second embodiment)

In this embodiment, X ¹ of the formula (2) is -O-, Ar ¹ is a phenyl group which may have a substituent, Y ¹ is -O-, and R ¹² is an alkyl group which may have a substituent, and may have a substitution. A mercapto group or a sulfonyl group which may have a substituent.

(Third embodiment)

In this embodiment, X ¹ of the formula (2) is -O-, Ar ¹ is a phenyl group which may have a substituent, Y ¹ is -C(=O)-, and R ¹² is an alkoxy group which may have a substituent. a group or an alkylamine group which may have a substituent.

(Fourth embodiment)

This embodiment is a combination of the first embodiment described above, the second embodiment, or the third embodiment.

The phthalocyanine compound represented by the formula (1) in the present invention is preferably a phthalocyanine compound represented by the following formula (1').

(In the formula (1'), R ¹ to R ⁴ are each a substituent represented by the following formula (2'), a bromine atom or a chlorine atom, and p, q, r, and s represent 0 to 4, respectively. The sum of p, q, r and s is 12 to 16. The number of substituents represented by the formula (2') in the formula (1') is 4 to 12. R represents a hydrogen atom, and M represents Cu or Zn. )

(In the formula (2'), X ¹ represents -O-, Ar ¹ represents a phenyl group, R ¹¹ represents a hydrogen atom or a methyl group, and n1 represents an integer of 1 to 3. In the case where n1 is 2 or 3, A plurality of R ^{11 's} may be the same or different. In the case where Y ¹ represents -O-, R ¹² is an alkyl group or a fluorenyl group, and in the case where Y ¹ represents -C(=O)-, R ¹² is an alkoxy group. Base or alkylamino group.)

The preferred range of each group of the above formula (1') is the same as that of the above formula (1).

Examples of the substituent represented by the formula (2) used in the present invention are listed below, but the present invention is not limited thereto.

The molecular weight of the phthalocyanine compound represented by the formula (1) is preferably from 900 to 4,000, more preferably from 1,000 to 2,500.

Next, the synthesis method of the phthalocyanine of the present invention will be described.

The phthalocyanine compound can be synthesized according to the method described in "Distribution of 功能Cyanine IPC Co., Ltd. as a functional dye", "After 酞花-Chemistry and Function-IPC Co., Ltd.", and the like.

In particular, since the compound of the present invention is a guanidinium cyanide halide, the halide intermediate can be cyclized to synthesize phthalocyanine or a phthalocyanine compound can be synthesized by halogenation.

In addition, the phthalocyanine of the present invention generally provides a complex mixture for the following reasons.

1) In the case where the synthetic intermediate A of the phthalocyanine of the present invention is a mixture

In general, phthalocyanine is synthesized by using phthalonitrile, phthalic anhydride, or phthalimide as an intermediate, and cyclizing these.

As an example, a case where a halogenated phthalonitrile is used as a starting material is shown, but a substituent may be introduced into any of the α-position and the β-position of the halogenated phthalonitrile, and in the case of introducing a substituent. The mixture is provided in the form of α1 or β1, and in the case of introducing two substituents, the mixture is provided in the form of α1-β1, α1-β2, α1-α2, β1-β2. In the present invention, it is preferred that the ratio of the mixture introduced into the β-position is high. Specifically, it is preferred that four or more of the eight β sites have a substituent represented by the formula (2).

2) Formation of an isomer mixture due to the asymmetry of the intermediate

Hereinafter, an example of formation of a phthalocyanine mixture in the case where a cyclization reaction is carried out using an asymmetric intermediate having different substituents at the β-position is shown as an example. At least four or more isomer mixtures are provided in the following manner. However, when benzophthalonitrile having a substituent R, phthalic anhydride, or phthalimide is halogenated to synthesize an intermediate, it is not limited thereto.

3) In the case of mixing two or more intermediates for the cyclization reaction

Hereinafter, as an example, a case where two kinds of intermediates having different substituents are used will be described. However, a mixture of the number of substitutions of each intermediate and a different substitution position is provided. Further, when the mixing ratio of the intermediates is changed or the reactivity of the intermediates is different, the number of substitution positions or the number of substitutions of the mixed product is also different.

As described above, the phthalocyanine compound is a mixture of substitution positions or substitution numbers, and thus it is difficult to describe it singly by means of a structural formula. Further, the number of substitutions shown in the following table is a value approximate to the average value of the number of substituents in the mixture, and may be a decimal.

Examples of the phthalocyanine compound used in the present invention are listed below, but the present invention is not limited thereto.

The content of the phthalocyanine compound represented by the formula (1) in the coloring curable composition varies depending on the molecular weight and the light absorption coefficient thereof, and is preferably 1 based on the total solid content of the colored curable composition. The mass % to 70% by mass, more preferably 10% by mass to 50% by mass. When the content of the dye is 10% by mass or more, a good color density (for example, a color density suitable for liquid crystal display) can be obtained, and if it is 50% by mass or less, it is advantageous in that patterning of pixels is good. .

[Coloring compound]

Further, the color hardening composition of the present invention may further contain other Structured dye compounds or pigment compounds and dispersions thereof. The dye compound may be any compound as long as it does not affect the hue of the colored image, and examples thereof include an azo system (for example, Solvent Yellow 162) and an anthraquinone system (for example). For example, an anthraquinone compound described in JP-A-2001-10881, a phthalocyanine system (for example, a phthalocyanine compound described in US Pat. No. 2008/0076044 A1), a dibenzopyranyl system (for example, CI (for example) Colour index, dye index) Acid Red 289 (CIAcid. Red 289)), Triarylmethane (eg CI Acid Blue 7), CI Acid Blue 83 (CIAcid Blue 83), CI Acid Blue 90 (CIAcid) Blue90), CI Solvent Blue 38, CI Acid Violet 17, CI Acid Violet 49, CI Acid Green 3, methine dye , a monomethyl dye (CIsolvent / yellow93) and the like.

Examples of the pigment compound include perylene, perinone, quinacridone, quinacridone oxime, anthraquinone, benzimidazolone, and benzimidazolone. , disazo condensation, disazo, azo, indanthrone, phthalocyanine, triarylcarbonium, dioxazine, aminoxime, diketone Diketopyrrolopyrrole, indigo, thioindigo, isoindoline, isoindolinone, pyranthrone or isoviolanthrone Wait. More specifically, for example, pigment pigments such as pigment red 190, pigment red 224, and pigment violet 29; picocyclic compound pigments such as Pigment Orange 43 or Pigment Red 194; Pigment Violet 19, Pigment Violet 42. Pigment red 122, pigment red 192, pigment red 202, pigment red 207, or pigment red 209 quinacridone compound pigment; pigment red 206, pigment orange 48, or pigment orange 49 quinacridone oxime compound pigment ; pigment yellow 147 and other hydrazine compound pigment; pigment red 168 and other flavonoid compound pigment; pigment brown 25, pigment purple 32, pigment orange 36, pigment yellow 120, pigment yellow 180, pigment yellow 181, pigment orange 62, or pigment Red 185 and other benzimidazolone compound pigments; Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Yellow 166, Pigment Orange 34, Pigment Orange 13, Pigment Orange 31, Pigment Red 144, Pigment Red 166, a bisazo condensation compound pigment such as Pigment Red 220, Pigment Red 221, Pigment Red 242, Pigment Red 248, Pigment Red 262, or Pigment Brown 23; a bisazo compound pigment such as Pigment Yellow 13, Pigment Yellow 83, or Pigment Yellow 188 ; pigment red 187, pigment red 170, pigment yellow 74, pigment yellow 150, pigment red 48, pigment red 53, pigment orange 64, or pigment red 247 and other azo compound pigment; pigment blue 60 and other indanthrene compound pigment; Pigment Green 7, Pigment Green 36, Pigment Green 37, Yan 58Cyanine compound pigment such as green 58, pigment blue 16, pigment blue 75, or pigment blue 15; triaryl carbon quinone compound pigment such as pigment blue 56 or pigment blue 61; dioxazine such as pigment violet 23 or pigment violet 37; a compound pigment; an amine hydrazine compound pigment such as Pigment Red 177; a diketopyrrolopyrrole compound pigment such as Pigment Red 254, Pigment Red 255, Pigment Red 264, Pigment Red 272, Pigment Orange 71, or Pigment Orange 73; Pigment Red 88 thioindigo compound pigment; pigment huang 139, pigment orange 66 and other isoporphyrin compound pigment; pigment yellow 109, or pigment orange 61 and other isoindolinone compound pigment; pigment orange 40, or pigment red 216 and other skin 蒽a ketone compound pigment; or an isopurin compound pigment such as Pigment Violet 31.

In the present invention, as the coloring agent, a yellow coloring agent is preferable, and as the pigment, pigment yellow 150 or pigment yellow 139 is more preferable, and as a preferable dye, it can be listed. Lift: CI solvent yellow 4, CI solvent yellow 88, CI solvent yellow 14, CI solvent yellow 15, CI solvent yellow 24, CI solvent yellow 94, CI solvent yellow 98, CI solvent yellow 162, CI solvent yellow 82, CI solvent yellow 93.

Further, in the present invention, the yellow coloring agent is preferably a monomethine dye, and more preferably the yellow coloring agent is a monomethine dye represented by the following formula (5).

(In the formula (5), R ¹¹ represents an alkyl group or a vinyl group, respectively, and R ¹² represents an aromatic ring group having a substituent, respectively.)

R ^{11 is} preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms. R ^{12 is} preferably a phenyl group or a naphthyl group, and as the substituent, an alkylsulfonylamino group, a vinylsulfonylamino group, an arylsulfonylamino group, an alkylcarbonylamino group, a vinyl group is preferred. A carbonylamino group, an arylcarbonylamino group, and more preferably an alkylsulfonylamino group. The alkyl group having 1 to 12 carbon atoms may have an unsaturated bond, and examples of such a substituent include an allylsulfonylamino group.

In the case where the above-mentioned dye or pigment is blended as a dispersion, it can be prepared as described in JP-A-H09-197118, JP-A-2000-239544.

The content of the above dye or pigment can be used within the range which does not impair the effects of the present invention, and is preferably from 0.5% by mass to 70% by mass based on the total solid content of the colored curable composition of the present invention. Further, it is preferably added to the color hardening in such a manner that the absorption intensity ratio (absorption at 450 nm / absorption at 650 nm) is in the range of 0.95 to 1.05. In the composition.

[Polymerizable compound]

The color hardening composition of the present invention preferably contains at least one polymerizable compound. The polymerizable compound may, for example, be an addition polymerizable compound having at least one ethylenically unsaturated double bond.

Specifically, it may be selected from compounds having at least one, preferably two or more terminal ethylenically unsaturated bonds. Such a compound group is widely known in the industrial field, and in the present invention, it can be used without particular limitation. These may also be, for example, monomers, prepolymers, i.e., dimers, trimers, and oligomers, or mixtures thereof, and such (co)polymers.

Examples of the monomer and its (co)polymer include unsaturated carboxylic acids (for example, polyacrylic acid, methacrylic acid, itaconic acid, and crotonic acid). ), methacrylic acid, maleic acid, etc. or esters thereof, guanamines, and such (co)polymers, preferably unsaturated carboxylic acids and aliphatic polyols An ester of a polyvalent alcohol compound, an amide of an unsaturated carboxylic acid and an aliphatic polyamine compound, and the (co)polymer. Further, an unsaturated carboxylic acid ester or a guanamine having a nucleophilic substituent such as a hydroxyl group or an amine group, a mercapto group or the like may be suitably used, and a monofunctional or polyfunctional isocyanate or epoxy group. An addition reactant such as a dehydration condensation reaction with a monofunctional or polyfunctional carboxylic acid. Further, it is also suitable for addition of an unsaturated carboxylic acid ester or a guanamine having an electrophilic substituent such as an isocyanate group or an epoxy group to a monofunctional or polyfunctional alcohol, an amine or a thiol. The reactant, and further preferably, has a halo or toluenesulfonyloxy group. A substituted reactant of an unsaturated carboxylic acid ester or a guanamine of a detachable substituent such as (tosyloxy) and a monofunctional or polyfunctional alcohol, an amine or a thiol. Further, as another example, a group of compounds substituted with an unsaturated phosphonic acid, styrene, vinyl ether or the like may be used instead of the above unsaturated carboxylic acid.

Specific examples of the monomer of the ester of the aliphatic polyol compound and the unsaturated carboxylic acid include, as the acrylate, ethylene glycol diacrylate, triethylene glycol diacrylate, and 1, Butanediol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane Acrylate, trimethylolpropane tris(propylene oxypropyl)ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate, tetraethyl Diol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate , sorbitol pentaacrylate, sorbitol hexaacrylate, tris(propylene methoxyethyl) isomeric cyanurate, polyester acrylate oligomer , Ethylene oxide (EO) modified triacrylate, and the like.

Further, examples of the methacrylate include butylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, and trimethylolpropane trimethyl. Acrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, hexanediol dimethacrylate, pentaerythritol dimethyl Acrylate, pentaerythritol trimethyl propyl Ethyl ester, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p--( 3-methylpropenyloxy-2-hydroxypropoxy)phenyl]dimethylmethane, bis[p-(methacryloxyethoxy)phenyl]dimethylmethane, and the like.

Further, examples of the itaconate ester include ethylene glycol benzoic acid ester, propylene glycol conjugated acid ester, 1,3-butylene glycol isaconate, and 1,4-butanediol. Tocoate, butanediol diitaconate, pentaerythritol diitaconate, sorbitol tetraconate, etc.; as a butenoate, for example, ethylene glycol bisenoic acid Ethyl ester, butanediol dibutenoate, pentaerythritol dibutenoate, sorbitol tetrakis (dibutacrylate), etc.; as the methacrylate, for example, ethylene glycol dimethacrylate or pentaerythritol Dimethacrylate, sorbitol tetramethacrylate, etc.; and, as the maleic acid ester, for example, ethylene glycol dimaleate or triethylene glycol dimaleate Pentaerythritol dimaleate, sorbitol tetramaleate, and the like.

For example, the aliphatic alcohol-based esters described in Japanese Patent Laid-Open Publication No. Sho 57-47231, and Japanese Patent Laid-Open Publication No. Sho 57-196231, or Japanese Patent Laid-Open No. 59-59 An ester having an aromatic skeleton described in Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. An ester having an amine group. Further, the above ester monomers can also be used in the form of a mixture.

Further, specific examples of the monomer of the aliphatic polyamine compound and the decylamine of the unsaturated carboxylic acid include methylene bis acrylamide, methylene bis methacrylamide, and 1,6-hexamethylene group. Bisacrylamide, 1,6-hexamethylene bismethyl decylamine, diexi B The base triamine tripropylene decylamine, xylylene bis propylene decylamine, xylylene bis methacrylamide and the like.

As an example of another preferable amide-based monomer, a monomer having a cyclohexylene structure described in Japanese Patent Publication No. Sho 54-21726 can be cited.

In addition, a urethane-based addition polymerizable compound produced by an addition reaction of an isocyanate and a hydroxyl group is also suitable, and as a specific example, for example, Japanese Patent Publication No. Sho 48-41708 The polyisocyanate compound having two or more isocyanate groups in one molecule and the hydroxyl group-containing vinyl monomer represented by the following formula (A) are contained in one molecule, and two or more polymerizations are contained in one molecule. A vinyl vinyl carbamate compound or the like.

CH ₂ =C(R)COOCH ₂ CH(R')OH (A)

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

The details of the use of the polymerizable compound, the structure, the use alone or in combination, or the amount of addition can be arbitrarily set depending on the final performance design of the colored curable composition. For example, from the viewpoint of sensitivity, it is preferred that the structure has a large content of unsaturated groups per molecule, and in many cases, it is preferably two or more functional groups. Further, from the viewpoint of improving the strength of the colored cured film, it is also effective to use a compound having a trifunctional or higher functional group in combination with a different functional number and a different polymerizable group (for example, an acrylate or a methyl group). A method of adjusting both sensitivity and strength, a compound of an acrylate, a styrene compound, or a vinyl ether compound. Further, the compatibility and dispersibility of other components (for example, a photopolymerization initiator, a colorant (pigment), a binder polymer, etc.) contained in the colored curable composition, and the selection of a polymerizable compound The method of use is also an important reason. For example, it is sometimes possible to increase the phase by using a low-purity compound or a combination of two or more. Solubility. Further, from the viewpoint of improving the adhesion to a hard surface such as a substrate, a specific structure may be selected.

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

[Photopolymerization initiator]

The color hardening composition of the present invention preferably contains at least one photopolymerization initiator. The photopolymerization initiator is not particularly limited as long as it can polymerize the above polymerizable compound, and is preferably selected from the viewpoints of characteristics, initial efficiency, absorption wavelength, availability, cost, and the like.

The photopolymerization initiator may, for example, be at least one active halogen compound selected from the group consisting of halomethyl oxadiazole compounds and halomethyl-s-triazine compounds, and 3-aryl-substituted coumarin ( Coumarin) compound, lophine dimer, benzophenone compound, acetophenone compound and its derivative, cyclopentadiene-benzene-iron complex and its salt, hydrazine Compounds, etc. Specific examples of the photopolymerization initiator include the initiators described in paragraphs [0070] to [0077] of JP-A-2004-295116. Among them, the oxime compound or the biimidazole compound is preferred in terms of the rapid polymerization reaction and the like.

The ruthenium compound (hereinafter also referred to as "an oxime-based photopolymerization initiator") is not particularly limited, and examples thereof include JP-A-2000-80068, WO02/100903A1, and JP-A-2001-233842. The hydrazine compound described in the above.

Specific examples thereof include 2-(O-benzylidene fluorenyl)-1-[4-(phenylthio)phenyl]-1,2-butanedione and 2-(O-benzylidene fluorenyl).肟)-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-phenyl醯 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-Methylbenzylidene)-9H-indazol-3-yl]ethanone, 1-(O-ethylindenyl)-1-[9-propyl-6-(2-methylbenzene Mercapto)-9H-indazol-3-yl]ethanone, 1-(O-ethylindenyl)-1-[9-ethyl-6-(2-ethylbenzylidene)-9H -oxazol-3-yl]ethanone, 1-(O-ethylindenyl)-1-[9-ethyl-6-(2-butylbenzylidene)-9H-indazole-3- Ethyl ketone, 2-(benzyl methoxyimino)-1-[4-(phenylthio)phenyl 1--1-octanone, 2-(ethoxylated imido)-4-(4-chlorophenylthio)-1-[9-ethyl-6-(2-methylbenzhydryl) -9H-carbazol-3-yl]-1-butanone and the like. However, it is not limited to these.

In addition, in the present invention, the compound represented by the following formula (1) is more preferable as the ruthenium compound from the viewpoint of the sensitivity, the stability at the time of the track, and the coloration at the time of the heating.

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

As R, in terms of high sensitivity, it is preferably a sulfhydryl group, specifically In other words, it is preferably an ethyl group, a propionyl group, a benzamidine group or a toluyl group.

As A, in terms of improving sensitivity and suppressing coloration caused by heating over time, an unsubstituted alkylene group or an alkyl group (e.g., methyl group, ethyl group, tert-butyl group, dodecane group) is preferred. Substituted alkylene, alkylene substituted by alkenyl (eg, vinyl, allyl), aryl (eg, phenyl, p-tolyl, xylyl, An alkylene group substituted with cumenyl, naphthyl, anthracenyl, phenanthryl, styryl.

As Ar, a substituted or unsubstituted phenyl group is preferred in terms of improving sensitivity and suppressing coloration caused by heating over time. In the case of a substituted phenyl group, as the substituent, for example, a halogen group such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom is preferable.

X is preferably an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkenyl group which may have a substituent, and may have a substitution in terms of improving solvent solubility and absorption efficiency in a long wavelength region. Alkynyl, alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, an arylthio group which may have a substituent, An amine group having a substituent.

Further, n in the formula (1) is preferably an integer of 1 to 2.

When the diimidazole-based compound is a dimer of an imidazole ring in which three aryl groups are substituted, the structure is not limited, and it is particularly preferable to have a formula represented by the following formula (II) or formula (III). Structure of the compound.

In the formula (II), X represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 9 carbon atoms, and A independently represents a group having one to twelve carbon atoms. a substituted or unsubstituted alkoxy group, or -COO-R ⁹ (wherein R ⁹ represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 9 carbon atoms), and n is an integer of 1 to 3, m It is an integer from 1 to 3.

In the formula (III), X ¹ , X ² and X ³ each independently represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 9 carbon atoms. Among them, there are no cases where two or more of X ¹ , X ² and X ³ are simultaneously a hydrogen atom.

Specific examples of the biimidazole-based compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole and 2,2'-double. (2-Chlorophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4' ,5,5'-tetrakis(4-phenoxycarbonylphenyl)biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetra (4 -ethoxycarbonylphenyl)biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetrakis(4-phenoxycarbonylphenyl) Imidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)biimidazole, 2,2'- Bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetrakis(4-phenoxycarbonylphenyl)biimidazole, 2,2'-bis(2-cyanophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)biimidazole, 2,2'-bis(2-cyano) Phenyl)-4,4',5,5'-tetrakis(4-phenoxycarbonylphenyl)biimidazole, 2,2'-bis(2-methylphenyl)-4,4',5, 5'-tetrakis(4-methoxycarbonylphenyl)biimidazole, 2,2'-bis(2-methylphenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonyl) Phenyl)biimidazole, 2,2'-bis(2-methylphenyl)-4,4',5,5'-tetrakis(4-phenoxycarbonylphenyl)biimidazole, 2,2'- Bis(2-ethylphenyl)-4,4',5,5'-tetrakis(4-methoxycarbonylphenyl)biimidazole, 2,2'-bis(2-ethylphenyl)-4 , 4',5,5'-tetrakis(4-ethoxycarbonylphenyl)biimidazole, 2,2'-bis(2-ethylphenyl)-4,4',5,5'-tetra 4-phenoxycarbonylphenyl)biimidazole, 2,2'-bis(2-phenylphenyl)-4,4',5,5'-tetrakis(4-methoxycarbonylphenyl)biimidazole , 2,2'-bis(2-phenylphenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)biimidazole, 2,2'-bis(2-benzene Biimidazole-based compound such as phenyl)-4,4',5,5'-tetrakis(4-phenoxycarbonylphenyl)biimidazole; 2,2'-bis(o-chlorophenyl)-4,4 ',5,5'-tetra-(p-methoxyphenyl)biimidazole, 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetra-(m-methoxy Phenyl) biimidazole, 2,2'-double (neighbor) Phenyl)-4,4',5,5'-tetra-(3,4-dimethoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4', 5,5'-tetrakis(4-methoxyphenyl)bisimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra-(3-methoxy Biphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra-(3,4-dimethoxyphenyl)biimidazole, 2, 2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,4,6-trichlorophenyl)- 4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,4-dibromophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2 , 2'-bis(2,4,6-tribromophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,4-dicyanophenyl) -4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,4,6-tricyanophenyl)-4,4',5,5'-tetraphenyl Base imidazole, 2,2'-bis(2,4-dimethylphenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis (2,4,6 -trimethylphenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,4-diethylphenyl)-4,4',5,5 '-Tetraphenylbiimidazole, 2,2'-bis(2,4,6-triethylphenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,4-diphenyl Phenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,4,6-triphenylphenyl)-4,4',5,5'- Tetraphenylbiimidazole, 2,2'-bis(2-fluorophenyl)-4,4',5,5'-tetraphenylbisimidazole, 2,2'-bis(o-fluorophenyl)-4 , a biimidazole compound such as 4', 5, 5'-tetraphenylbisimidazole or the like.

Among the above, preferred examples of the compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (a commercially available product is exemplified as B). -CIM, manufactured by Hodogaya Chemical Industry), 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetra-(3,4-dimethoxyphenyl)biimidazole ( HABI1311, Nihon Siber Hegner, 2,2'-bis(2-methylphenyl)-4,4',5,5'-tetraphenylbiimidazole (from Heijin Chemical Company) Sold).

Further, in the color hardening composition of the present invention, in addition to the above-mentioned photopolymerization initiator, other known photopolymerization initiations as described in Paragraph No. 0079 of JP-A-2004-295116 may be used. Agent.

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

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

[Organic solvents]

The color hardening composition of the present invention may contain at least one organic solvent.

The organic solvent is not particularly limited as long as it satisfies the solubility of each component to be coexisted or the coloring-curable composition, and it is particularly preferable to consider the solubility and coatability of the binder. Security to choose.

As the organic solvent, esters, ethers, ketones, and aromatics can be used. Specific examples of the aromatic hydrocarbons include the organic solvents described in Paragraph No. 0161 to Paragraph No. 0162 of JP-A-2012-032754.

Further, examples of the ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, and ethyl acetate. Kesailusu, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol single Propyl ether acetate and the like.

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

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

The organic solvent is preferably mixed in two or more kinds from the viewpoints of the solubility of each of the above components, the solubility of the alkali-soluble polymer, and the improvement of the coating surface. In this case, it is particularly preferred to use a solvent selected from the group consisting of methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl celecoxib acetate, ethyl lactate, diethylene glycol dimethyl ether, Butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether A mixed solution of two or more kinds of acid esters.

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

[alkali soluble binder]

The color hardening composition of the present invention preferably contains an alkali-soluble binder. Alkali The 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.

As the alkali-soluble binder, a linear organic polymer is preferable, and a binder which can be dissolved in an organic solvent and which can be developed with a weakly alkaline aqueous solution can be used. Examples of such a linear organic high molecular polymer include a polymer having a carboxylic acid in a side chain, for example, Japanese Patent Laid-Open No. Sho 59-44615, Japanese Patent Publication No. Sho 54-34327, and Japanese Patent Publication No. Sho 58-12577. A methacrylic acid copolymer, an acrylic copolymer, an itaconic acid copolymer described in each of the publications of Japanese Patent Laid-Open Publication No. Sho 54-25957, JP-A-59-53836, and JP-A-59-71048 Also useful as a crotonic acid copolymer, a maleic acid copolymer, a partially esterified maleic acid copolymer, etc., are acid cellulose derivatives having a carboxylic acid in a side chain.

In addition to the above, as the alkali-soluble binder in the present invention, a polymer having a hydroxyl group and an acid anhydride additive or a polyhydroxystyrene resin or a polysiloxane resin may be used. Poly(2-hydroxyethyl (meth)acrylate), polyvinylpyrrolidone or polyethylene oxide, polyvinyl alcohol, and the like. Further, the linear organic high molecular polymer may be a polymer obtained by copolymerizing a monomer having hydrophilicity. As such an example, an alkoxyalkyl (meth)acrylate, a hydroxyalkyl (meth)acrylate, a glyceryl (meth)acrylate, a (meth) acrylamide, and an N-hydroxymethyl group are mentioned. Acrylamide, secondary or tertiary alkyl acrylamide, dialkylaminoalkyl (meth)acrylate, morpholinyl (meth)acrylate, N-vinylpyrrolidone, N-vinyl N-Vinylcaprolactam, vinylimidazole, vinyltriazole, methyl (meth)acrylate, ethyl (meth)acrylate, branched or linear propyl (meth)acrylate, branch Chain or linear butyl (meth)acrylate, or phenoxyhydroxypropyl (meth)acrylate, and the like. In addition, as hydrophilic Monomers, also useful, include tetrahydrofurfuryl, phosphate, phosphate, ammonium, ethoxylated, propoxylated, sulfonic acid groups and derived therefrom A monomer such as a salt group or a morpholinoethyl group.

In addition, in order to improve the crosslinking efficiency, the alkali-soluble binder may also have a polymerizable group using a side chain, for example, the side chain contains an allyl group, a (meth) acryl (meth) acryl, an allyloxyalkyl group. A polymer or the like. Examples of the polymerizable group-containing polymer include commercially available KS Resist-106 (manufactured by Osaka Organic Chemical Industry Co., Ltd.) and Cyclomer P series (Daicel Chemical Industries). Company manufacturing) and so on. Further, in order to increase the strength of the hardened film, alcohol-soluble nylon (nylon) or 2,2-bis-(4-hydroxyphenyl)-propane and epichlorohydrin polyether are also useful.

Among these various alkali-soluble binders, polyhydroxystyrene resin, polyoxyalkylene resin, acrylic resin, acrylamide resin, acrylic acid/acrylamide are preferred from the viewpoint of heat resistance. The copolymer resin is preferably an acrylic resin, an acrylamide resin, or an acrylic/acrylamide copolymer resin from the viewpoint of controlling developability.

The acrylic resin preferably contains a copolymer of a monomer selected from the group consisting of benzyl (meth)acrylate, (meth)acrylic acid, hydroxyethyl (meth)acrylate, (meth)acrylamide, and the like. KS Resist-106 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series (manufactured by Daisy Chemical Industry Co., Ltd.), and the like are commercially available.

The alkali-soluble binder preferably has a weight average molecular weight (polystyrene-converted value measured by a gel permeation chromatograph (GPC) method) of 1000 to 2 from the viewpoints of developability, liquid viscosity, and the like. The polymer of ×10 ⁵ is more preferably a polymer of 2,000 to 1 × 10 ⁵ , particularly preferably a polymer of 5,000 to 5 × 10 ⁴ .

The amount of the alkali-soluble binder is preferably from 10% by mass to 80% by mass based on the total solid content, more preferably from 20% by mass to 60% by mass.

[crosslinking agent]

In the colored curable composition of the present invention, a crosslinking agent may be used in a complementary manner, and the hardness of the colored cured film obtained by curing the colored curable composition may be further improved.

The crosslinking agent is not particularly limited as long as it is a crosslinking agent which can be cured by a crosslinking reaction, and examples thereof include (a) an epoxy resin and (b) selected from a methylol group and an alkyl group. a melamine compound, a guanamine compound, a glycoluril compound or a urea compound, and (c) a substituted by at least one of an oxymethyl group and a decyloxymethyl group A phenolic compound, a naphthol compound or a hydroxyquinone compound substituted with at least one substituent selected from the group consisting of a methylol group, an alkoxymethyl group, and a decyloxymethyl group. Among them, a polyfunctional epoxy resin is preferred.

For details of specific examples of the crosslinking agent, etc., the descriptions of paragraph numbers 0134 to 0147 of JP-A-2004-295116 can be referred to.

[Surfactant]

The color hardening composition of the present invention may also contain a surfactant. The surfactant may be any of a nonion type, a cation type, and an anion type, and is preferably a fluorine-containing surfactant. Specifically, Japanese Patent Laid-Open No. Hei 2-54202 is exemplified.

The blending amount of the surfactant in the present invention is preferably from 0.0001% by mass to 0.1% by mass based on the total solid content.

The colored curable composition of the present invention may further contain various additives such as a filler, an antioxidant, an ultraviolet absorber, an anti-agglomerating agent, a sensitizer, or a light stabilizer, as needed.

[Method for Preparing Colored Curable Composition]

The colored curable composition of the present invention can be prepared by mixing the above components and optionally any of the components.

In addition, in the case of preparing a colored curable composition, each component constituting the color hardening composition may be blended together, or each component may be dissolved and dispersed in a solvent, and then successively formulated. In addition, the order of input or the operating conditions at the time of preparation are not particularly limited. For example, the components may be simultaneously dissolved and dispersed in a solvent to prepare a composition, and if necessary, each component may be prepared into a solution or a dispersion of two or more kinds as appropriate, and mixed at the time of use (at the time of coating) to prepare Composition.

The colored curable composition prepared in the above manner can be used for filtration by using a filter having a pore diameter of preferably 0.01 μm to 3.0 μm and a pore diameter of preferably 0.05 μm to 0.5 μm.

Since the colored curable composition of the present invention can form a colored cured film having excellent hue and contrast, it can be suitably used as a liquid crystal display device (LCD) or a solid-state imaging device (for example, a CCD (Charge-Coupled Device), CMOS. Production of color filters such as color filters used in (Complementary Metal Oxide Semiconductor), etc., and production of printing inks (Ink), ink jet inks, and paints. use. It is especially suitable for the formation of colored pixels for liquid crystal display devices.

[Color filter and method of manufacturing the same]

The color filter of the present invention is provided with a substrate, and the substrate comprises the present invention It is composed of a colored region of the colored curable composition. The colored region on the substrate is formed by a coloring film such as red (R), green (G), or blue (B) which forms each pixel of the color filter.

The color filter of the present invention can be formed by any method as long as it is a method of applying the colored curable composition of the present invention to a substrate to form a cured colored region (colored pattern). It is preferably produced by using the colored curable composition of the present invention.

The method for producing a color filter of the present invention comprises the steps of applying (preferably coating) the above-described colored curable composition to a substrate to form a colored layer (also referred to as a colored curable composition layer). Step (A); and step (B) of hardening the colored curable composition layer formed in the step (A).

The hardening step is preferably (preferably, masked) into a pattern, and the uncured portion of the coating film is removed by development with a developing solution to form a colored region (colored pattern). By passing through these steps, a coloring pattern containing pixels of three colors or four colors can be formed to obtain a color filter. Further, in the method for producing a color filter of the present invention, it is preferable to further provide a step (C) of irradiating the colored pattern formed in the step (B) with ultraviolet rays, and a coloring by ultraviolet irradiation in the step (C). The embodiment of the step (D) in which the pattern is subjected to heat treatment.

According to this method, the color filter used in the liquid crystal display element or the solid-state image sensor can be produced with less difficulty in the process, high quality, and low cost.

Hereinafter, a method of producing the color filter of the present invention will be described more specifically.

-Step (A)-

In the method for producing a color filter of the present invention, first, the above-described color hardening group of the present invention is applied directly or via another layer on a substrate by a desired coating method. The coating film (coloring curable composition layer) containing the coloring curable composition is formed, and then the coloring curable composition layer is dried by pre-hardening (prebake) as needed.

Examples of the substrate include an alkali-free glass, a soda glass, a Pyrex (registered trademark) glass, a quartz glass, and a substrate to which the transparent conductive film is attached, which are used in a liquid crystal display device or the like; or A photoelectric conversion element substrate used in a solid-state imaging device or the like, for example, a silicone substrate or a plastic substrate. Further, a black matrix for isolating the respective pixels may be formed on the substrates, or a transparent resin layer may be provided to promote adhesion or the like. Further, in order to improve the adhesion to the upper layer, prevent the diffusion of the substance, or planarize the surface, an undercoat layer may be provided on the substrate as needed.

Further, the plastic substrate preferably has a gas barrier layer and/or a solvent resistant layer on its surface.

In addition, as the substrate, a substrate for driving a thin film transistor (TFT) (hereinafter referred to as a "TFT-based liquid crystal driving substrate") in which a thin film transistor (TFT) type color liquid crystal display device is disposed can be used. On the substrate for driving, a coloring pattern using the colored curable composition of the present invention is also formed to form a color filter.

Examples of the substrate in the TFT liquid crystal driving substrate include glass, silicone, polycarbonate, polyester, aromatic polyamide, polyamidimide, and polyimine. Wait. If necessary, a chemical treatment such as a silane coupling agent, a plasma treatment, ion plating, sputtering, or a gas phase reaction method may be performed on the substrates. Suitable pre-treatment such as vacuum evaporation. For example, it can be used on the TFT side. A substrate of a passivation film such as a tantalum nitride film is formed on the surface of the liquid crystal driving substrate.

The colored curable composition of the present invention is applied to a substrate directly or via another layer. As the application method, coating is preferred, and it is preferably by spin coating, slit coating, cast coating, roll coating, bar coating, spraying Coating is performed by a coating method such as ink jet.

In the coating step, the method of applying the colored curable composition of the present invention to a substrate is not particularly limited, and is preferably a slit and spin method or a spinless coating method. A method of using a slit nozzle (hereinafter referred to as a slit nozzle coating method).

In the slit nozzle coating method, the slit, the spin coating method, and the non-spin coating method differ depending on the size of the coated substrate, and for example, the fifth-generation glass substrate is coated by a non-rotation coating method. In the case of (1100 mm × 1250 mm), the amount of the colored curable composition ejected from the slit nozzle is usually 500 μl/sec to 2000 μl/sec, preferably 800 μL/sec to 1500. The microliter/second, in addition, the coating speed is usually from 50 mm/s to 300 mm/s, preferably from 100 mm/s to 200 mm/s.

Further, the color hardening composition used in the coating step is usually 10% by mass to 20% by mass, preferably 13% by mass to 18% by mass, based on the solid content.

When a coating film using the colored curable composition of the present invention is formed on a substrate, the thickness of the coating film (after prebaking treatment) is usually 0.3 μm to 5.0 μm, preferably 0.5 μm to 4.0 μm. The most ideal is 0.5 μm to 3.0 μm.

Further, in the case of a color filter for a solid-state image sensor, the thickness of the coating film (after the prebaking treatment) is preferably in the range of 0.5 μm to 5.0 μm.

In the application step, the prebaking treatment is usually performed after the application. As needed, Vacuum treatment can also be carried out before prebaking. The vacuum drying condition is usually a vacuum of 0.1 torr to 1.0 torr, preferably about 0.2 torr to 0.5 torr.

Further, the prebaking treatment may be carried out in a temperature range of 50 ° C to 140 ° C, preferably in the range of 70 ° C to 110 ° C, using a hot plate, an oven or the like for 10 seconds to 300 seconds. Under the conditions of implementation. Further, in the prebaking treatment, high frequency processing or the like may be used in combination. High frequency processing can also be used alone.

The conditions for prebaking include heating at 70 ° C to 130 ° C for 0.5 minutes to 15 minutes using a hot plate or an oven.

Moreover, the thickness of the color hardening composition layer formed by the coloring curable composition can be appropriately selected according to the purpose. For the color filter for a liquid crystal display device, it is preferably in the range of 0.2 μm to 5.0 μm, more preferably in the range of 1.0 μm to 4.0 μm, and most preferably in the range of 1.5 μm to 3.5 μm. . Further, the color filter for a solid-state image sensor preferably has a range of 0.2 μm to 5.0 μm, more preferably 0.3 μm to 2.5 μm, and most preferably 0.3 μm to 1.5 μm. Within the scope.

Further, the thickness of the colored curable composition layer is the film thickness after prebaking.

-Step (B)-

Then, in the method of producing a color filter of the present invention, the film (colored curable composition layer) containing the colored curable composition formed as described above on the substrate is exposed to light, for example, via a photomask. As light or radiation which can be applied to exposure, it is preferably g-ray, h-ray, i-ray, j-ray, KrF light, ArF light, and particularly preferably i-ray. When i-rays are used for the irradiation light, it is preferable to irradiate with an exposure amount of 100 mJ/cm ² to 10000 mJ/cm ² .

In addition, as other exposure light, ultra high pressure, high pressure, medium can also be used. Pressure lamps, low pressure mercury lamps; chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, various laser sources for visible and ultraviolet light, and fluorescent lamps Light, tungsten (tungsten), sunlight, etc.

Exposure step using a laser source

In the exposure mode using a laser light source, an ultraviolet laser is used as a light source.

In terms of being consistent with the photosensitive wavelength of the resist, it is preferred that the irradiation light is preferably an ultraviolet laser having a wavelength in the range of 300 nm to 380 nm, and more preferably a wavelength of 300 nm. Ultraviolet lasers in the ~360 nm range. Specifically, it is particularly preferable to use a third high-frequency harmonic (355 nm) of a neon yttrium aluminum garnet (Nd: YAG, Neodymium Doped Yttrium Aluminum Garnet) that outputs a large, relatively low-cost solid laser. Or excimer laser XeCl (308 nm), XeF (353 nm).

The exposure amount of the object to be exposed (pattern) is in the range of 1 mJ/cm ² to 100 mJ/cm ² , and more preferably in the range of 1 mJ/cm ² to 50 mJ/cm ² . When the amount of exposure is within this range, it is preferable in terms of productivity in pattern formation.

The exposure apparatus is not particularly limited, and as a marketer, it is possible to use: Callisto (made by V Technology Co., Ltd.) or EGIS (made by V Technology Co., Ltd.), or DF2200G (Greater Japan) Screen (made by Dainippon Screen Mfg.), etc. Further, a device other than the above may be suitably used.

In the production of a color filter for a liquid crystal display device, exposure using h-rays and i-rays mainly by a proximity exposure machine or a mirror projection machine can be preferably used. Further, in the case of manufacturing a color filter for a solid-state image sensor, it is preferable to use a stepper exposure machine and mainly use i-rays. Further, when a color filter is manufactured using a TFT liquid crystal driving substrate, the photomask to be used may be used in addition to a photomask for forming a pattern of a pixel (colored pattern), and may be used to form a pass. Through hole or A mask of the pattern of the concave shape of the font.

The colored curable composition layer exposed in the above manner can be heated.

Further, in order to suppress oxidative fading of the colored material in the colored curable composition layer, the exposure can be carried out while flowing nitrogen gas in a chamber.

Then, the developed color-curable composition layer after exposure is developed using a developing solution. Thereby, a negative or positive coloring pattern (resist pattern) can be formed. In the developing step, the uncured portion of the exposed coating film is dissolved in the developing solution, and only the hardening component remains on the substrate.

Any desired solution may be used as long as it is a coating film (coloring curable composition layer) in which the color hardening composition of the uncured portion is dissolved, and the developer of the hardened portion is not dissolved. For example, a combination of various organic solvents or an aqueous alkaline solution can be used.

The organic solvent to be used for development includes the above-mentioned solvent which can be used in the preparation of the colored curable composition of the present invention.

The alkaline aqueous solution is, for example, dissolved in a concentration of 0.001% by mass to 10% by mass, preferably 0.01% by mass to 1% by mass, so as to dissolve sodium hydroxide, potassium hydroxide, sodium carbonate, or sodium hydrogencarbonate. Sodium citrate, sodium metasilicate, ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole a base of a basic compound such as piperididine or 1,8-dioxabicyclo-[5.4.0]-7-undecene (1,8-diazabicyclo-[5.4.0]-7-undecene) Sexual water soluble liquid. When the developer is an alkaline aqueous solution, it is preferred to adjust the alkali concentration to preferably a pH of 11 to 13, more preferably a pH of 11.5 to 12.5.

A water-soluble organic solvent such as methanol or ethanol or a surfactant may be added to an alkaline aqueous solution in an appropriate amount.

The development temperature is usually 20 ° C to 30 ° C, and the development time is 20 seconds to 90 seconds.

The development may be any of a dip method, a shower method, a spray method, or the like, and may be combined with a swing method, a rotation method, an ultrasonic method, or the like. The developed surface may be wetted with water before contact with the developer to prevent development unevenness. Alternatively, the substrate may be tilted for development.

Further, in the case of manufacturing a color filter for a solid-state image sensor, puddle development can also be used.

After the development treatment, in order to complete the hardening after the rinse treatment for removing the remaining developer by washing and drying is performed, heat treatment (post-bake) is performed.

The rinsing treatment is usually carried out using pure water, but in order to save the solution, the following method can also be used: pure water is used only in the final rinsing, used pure water is used at the beginning of rinsing, or the substrate is slanted for rinsing, or ultrasonic irradiation is used in combination. .

After the rinsing treatment, after removing moisture and drying, it is usually subjected to heat treatment at about 200 ° C to 250 ° C. This heat treatment (post-baking) is a continuous heating method using a heating plate, a convection oven (hot air circulation dryer), or a high-frequency heating device so that the coating film after development is subjected to the above conditions. Or batch (batch).

Repeating the above for each color in sequence according to the number of hue required In each step, a color filter formed by forming a cured film (colored pattern) of a plurality of colors can be produced.

Since the color filter of the present invention has high contrast, small color density unevenness, and good color characteristics, it can be suitably used for a solid-state image sensor or a liquid crystal display element.

-Step (C)-

In the method for producing a color filter of the present invention, in particular, a latent exposure by ultraviolet irradiation may be performed on a colored pattern (pixel) formed using a colored curable composition.

-Step (D)-

It is preferable to further heat-treat the colored pattern subjected to the post-exposure by ultraviolet irradiation as described above. The colored pattern can be further hardened by heat-treating the formed colored pattern (i.e., post-baking treatment). This heat treatment can be performed by, for example, a hot plate, various heaters, an oven, or the like.

The temperature at the time of heat treatment is preferably from 100 ° C to 300 ° C, more preferably from 150 ° C to 250 ° C. Further, the heating time is preferably from about 10 minutes to about 120 minutes.

The color pattern thus obtained constitutes a pixel on the color filter. In the production of a color filter having a plurality of hue of pixels, the step (A), the step (B), and the optional step (C) or step (D) are repeated as long as the number of colors required is repeated. can.

Furthermore, the above step (C) and/or step (D) may be performed after each (per color) formation, exposure, and development of the monochromatic color hardening composition layer, or all of the required ones may be used. After the formation of the color-curable composition layer of the number of colors, exposure, and development are completed, the above steps (C) and/or step (D) are performed together.

Since the color filter (color filter of the present invention) obtained by the method for producing a color filter of the present invention uses the color hardening composition of the present invention, it is excellent in hue and contrast.

The color filter of the present invention can be used for a liquid crystal display element or a solid-state image sensor, and is particularly suitable for use in a liquid crystal display device. In the case of use in a liquid crystal display device, a dye is used as a colorant to achieve a good hue, and an image display excellent in spectral characteristics and contrast can be obtained.

The use of the colored curable composition of the present invention is mainly described above for the purpose of forming the colored pattern of the color filter, but it can also be applied to isolating the colored pattern (pixel) constituting the color filter. The formation of the black matrix.

The black matrix on the substrate can be formed by applying a coloring curable composition containing a black pigment such as carbon black or titanium black, and applying steps such as coating, exposure, and development. After that, it is formed by post-baking as needed.

[Liquid Crystal Display Device]

The liquid crystal display element and the solid-state imaging element of the present invention are obtained by including the color filter of the present invention. More specifically, for example, an alignment film is formed on the inner surface side of the color filter so as to face the electrode substrate, and the liquid crystal is filled in the gap portion and sealed, whereby a panel as a liquid crystal display element of the present invention can be obtained ( Panel). Further, the solid-state imaging element of the present invention can be obtained, for example, by forming a color filter on the light-receiving element.

The definition of the liquid crystal display device or the details of each display device is described in, for example, "Electronic display device (sasaki Sasaki, Industrial Research Association, Inc., 1990)", "Display device (Ibuki Shunzhang, Industrial Book Co., Ltd.) Ltd. issued in 1989) and so on. In addition, regarding a liquid crystal display device, for example, It is contained in "Next Generation Liquid Crystal Display Technology (Editor Uchida Natsuo, Industrial Investigation Association, 1994)". The liquid crystal display device to which the present invention is applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the "next generation liquid crystal display technology".

Among them, the color filter of the present invention is particularly effective for a color TFT liquid crystal display device. A liquid crystal display device of a color TFT type is described, for example, in "Color TFT Liquid Crystal Display (Kyoritsu Publishing Co., Ltd., 1996)". Furthermore, the present invention can also be applied to a liquid crystal display device in which a viewing angle is expanded, such as a horizontal electric field driving method such as In Plane Switching (IPS), a multi-domain vertical alignment (MVA), or the like. , or Super Twisted Nematic (STN), Twisted Nematic (TN), Vertical Alignment (VA), Optical Circuit Switching (OCS), Fringe Field Switching , FFS), and Reflective-Optically Compensated Bend (R-OCB).

In addition, the color filter of the present invention can also be provided to a bright and high-definition Color-filter On Array (COA) method.

When the color filter of the present invention is used for a liquid crystal display element, high contrast can be achieved when combined with a three-wavelength tube of a previously known cold cathode tube, and the red, green, and blue LED light sources (RGB- LED) is used as a backlight device to increase the brightness, and a liquid crystal display device having high color reproducibility with high color purity can be provided.

[Examples]

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to the following examples as long as it does not exceed the gist of the invention. Furthermore, as long as there are no special regulations, Then "parts" are the quality benchmark.

Example 1

The components used in the preparation of the colored curable composition are shown below.

(Y-1) 12.8 parts of CI Pigment Yellow 150, 7.2 parts of methyl methacrylate/methacrylic acid (80/20) [mass ratio] copolymer (weight average molecular weight: 12,000) and 80.0 parts of propylene glycol single a pigment dispersion obtained by mixing methyl ether acetate and sufficiently dispersing the pigment using a beads mill

(Y-2) 10.0 parts of C.I. Solvent Yellow 162 was dissolved in 90.0 parts of propylene glycol monomethyl ether acetate (manufactured by Wako Pure Chemical Industries, Ltd.)

(Y-3) 10.0 parts of the following yellow dye was dissolved in tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) in 90.0 parts.

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

(U-1) Binder Resin: Benzyl methacrylate/methacrylic acid (85/15 [mass ratio] copolymer (weight average molecular weight: 12,000) propylene glycol monomethyl ether acetate solution (solid content 40.0% by mass) Acid value (100 mgKOH/g)

(V-1) Photopolymerization initiator: 2-(benzhydryloxyimino)-1-[4-(phenylthio) Phenyl]-1-octanone (manufactured by BASF)

(V-2) Photopolymerization initiator: 2-(ethyloxyimino)-4-(4-chlorophenylthio)-1-[9-ethyl-6-(2-methylbenzene Mercapto)-9H-carbazol-3-yl]-1-butanone (manufactured by BASF)

(V-3) Photopolymerization initiator: a lanthanide compound of the following structure

(V-4) Photopolymerization initiator: Irgacure 369 (manufactured by BASF: α-acyl amino compound)

(V-5) 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (manufactured by B-CIM Hodogaya Chemical Industry Co., Ltd.)

(W-1) Photopolymerization start aid: 4,4'-bis(diethylamino)benzophenone (manufactured by BASF)

(W-2) 2-mercaptobenzothiazole (manufactured by Tokyo Chemical Industry Co., Ltd.)

(X-1) Solvent: propylene glycol monomethyl ether acetate

(X-2) Solvent: ethyl 3-ethoxypropionate

(Z-1) Surfactant: Megafac F781-F (manufactured by Dainippon Ink Chemical Industry Co., Ltd.)

(A-101) C.I. Acid Blue 249, dodecyl amide amide synthesized by the method described in Japanese Patent No. 3476208

(A-102) The compound described in Example 38 of the specification of International Publication WO2011/105603

<Production of Colored Film> Preparation of colored curable composition (coating liquid)

The colored curable composition 1 was prepared by mixing the components in the following compositions.

<composition>

. Exemplary compound A-1...6.9 parts by mass

. Above (T-1)...103.4 parts by mass

. (U-1)...212.2 parts by mass (solid content converted value: 84.9 parts by mass)

. Above (V-1)...21.2 parts by mass

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

. Above (X-1)...71.9 parts by mass

. The above (X-2)...3.6 parts by mass

. The above (Z-1)...0.06 parts by mass

(Production of color film using a curable coloring curable composition)

The above-mentioned colored hardening composition (color) was applied to a 100 mm × 100 mm glass substrate (1737, manufactured by Corning) at a maximum absorbance of 600 to 700 nm of 1.5 to 2.0. The resist liquid was dried in an oven at 100 ° C for 180 seconds to form a colored film on the substrate.

(Evaluation of the color film using the curable coloring curable composition)

The substrate obtained above was subjected to the following evaluation.

<Evaluation of Hue>

For the colored film to be produced, the absorption at 450 nm to 800 nm was measured by an ultraviolet-visible spectrophotometer (UV2400-PC manufactured by Shimadzu Corporation), and the absorption intensity of λ max of the main absorption was calculated to be 1.0. The minimum absorption intensity near 500 nm is described in the following table.

[Other Embodiments and Comparative Examples]

In the above, the phthalocyanine compound was replaced by the following phthalocyanine compound, and the same procedure was carried out. The results are shown below.

Example 101 Production of green color film (Preparation of colored curable composition (coating liquid))

The components in the following compositions were mixed to prepare a colored curable composition.

<composition>

. Exemplary compound A-1...6 parts by mass

. The yellow coloring matter (the above (Y-2)) was adjusted so that the absorption intensity ratio (absorption at 450 nm / absorption at 650 nm) was in the range of 0.95 to 1.05, and the amount of the yellow coloring matter added was adjusted.

. Above (T-1)...103.4 parts by mass

. (U-1)...212.2 parts by mass (solid content converted value: 84.9 parts by mass)

. Above (V-1)...21.2 parts by mass

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

. Above (X-1)...71.9 parts by mass

. The above (X-2)...3.6 parts by mass

. The above (Z-1)...0.06 parts by mass

<Light resistance>

After the xenon lamp was irradiated to the colored film at 200,000 lux (lux) for 10 hours (corresponding to 2 million lux.h), the chromaticity change, that is, the ΔEab value was measured. The smaller ΔEab value shows excellent light resistance.

<heat resistance>

After heating the colored film at 230 ° C for 60 minutes, the change in color is measured as ΔEab value. The smaller ΔEab value shows excellent light resistance.

<residue>

A colored film was prepared in the same manner as in Example 1, and then immersed in a sodium hydrogencarbonate/sodium carbonate aqueous solution adjusted to a pH of 12.0 at 23 ° C as a developing solution for 60 seconds, followed by rinsing with ion-exchanged water at 23 ° C. A substrate for residue evaluation was produced.

The developed substrate was measured by an ultraviolet-visible spectrophotometer (UV2400-PC manufactured by Shimadzu Corporation), and the residue was evaluated by the maximum absorbance at 400 nm to 700 nm by the following method.

2: The maximum absorbance is less than 0.05

1: Maximum absorbance of 0.05 or more

[Other Embodiments and Comparative Examples]

In the above, the phthalocyanine compound, the photopolymerization initiator, the photopolymerization initiator adjuvant, and the yellow coloring matter were replaced in the same manner as those described in the following Table. The results are shown below.

The above phthalocyanine compound corresponds to the number of the above-exemplified compound.

From the above results, it is clear that the coloring-curable composition of the present invention can achieve a color filter having a small absorption minimum in the transmissive portion, excellent transmissivity, and excellent heat resistance.

Claims (20)

A colored hardening composition comprising a phthalocyanine compound represented by the following formula (1), (In the formula (1), R ¹ to R ⁴ are each a substituent represented by the following formula (2) or a halogen atom, and p, q, r, and s represent 0 to 4, respectively, in the formula (1) The number of substituents represented by the formula (2) is 1 to 12; R represents a hydrogen atom or a monovalent substituent, respectively; M represents Cu, Zn, V(=O), Mg, Ni, Ti(=O) , Mg, Sn or Si), (In the formula (2), X ¹ represents -O-, -S-, -NR ¹³ - or -SO ₂ -, and Ar ¹ represents an aromatic carbocyclic group which may have a substituent or an aromatic group which may have a substituent a heterocyclic group; R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and n1 represents an integer of 1 to 3; and in the case where n1 is 2 or 3, a plurality of R ^{11 's} may be the same or different; Y ¹ represents -O-, -S-, -NR ¹³ -, -SO ₂ -, or -C(=O)-, R ¹² represents a monovalent substituent; R ¹³ represents a hydrogen atom or an alkane having 1 to 4 carbon atoms, respectively base). The color hardening composition according to Item 1, wherein a halogen atom represented by R ¹ to R ⁴ represents Br or Cl, and M represents Cu or Zn. The colored hardening composition according to Item 1 or 2, wherein X ¹ of the formula (2) is -O-, Ar ¹ is a phenyl group which may have a substituent, and Y ¹ is - O-, R ¹² is an alkyl group which may have a substituent, a fluorenyl group which may have a substituent, or a sulfonyl group which may have a substituent. The colored hardening composition according to Item 1 or 2, wherein X ¹ of the formula (2) is -O-, Ar ¹ is a phenyl group which may have a substituent, and Y ¹ is - C (= O) -, R 12 is an optionally substituted alkoxy group, an alkoxy group or a substituent group. The colored hardening composition according to the first or second aspect of the invention, wherein the sum of p, q, r and s of the formula (1) is 12 to 16. The coloring curable composition according to the first or second aspect of the invention, further comprising a carboxylic acid binder. The colored curable composition according to Item 1 or 2 of the patent application, further comprising a polymerizable compound and a photopolymerization initiator. The colored hardening composition according to Item 7, wherein the photopolymerization initiator is an anthracene compound or a biimidazole compound. The color hardening composition according to Item 1 or Item 2 of the patent application, further comprising a yellow colorant. The color hardening composition according to claim 9, wherein the yellow colorant is an azo dye or a monomethine dye. The color hardening composition according to claim 9, wherein the yellow colorant is a monomethine dye represented by the following formula (5), (In the formula (5), R ¹¹ represents an alkyl group or a vinyl group, respectively, and R ¹² each represents an aromatic ring group having a substituent). The coloring curable composition according to the first aspect or the second aspect of the invention, wherein the compound represented by the formula (1) is a phthalocyanine compound represented by the following formula (1'). (In the formula (1'), R ¹ to R ⁴ are each a substituent represented by the following formula (2'), a bromine atom or a chlorine atom, and p, q, r, and s represent 0 to 4, respectively. The sum of p, q, r and s is 12 to 16; the number of substituents represented by the formula (2') in the formula (1') is 4 to 12; R represents a hydrogen atom; M represents Cu or Zn) , general formula (2') (In the formula (2'), X ¹ represents -O-, Ar ¹ represents a phenyl group; R ¹¹ represents a hydrogen atom or a methyl group, and n1 represents an integer of 1 to 3; and in the case where n1 is 2 or 3, A plurality of R ^{11 's} may be the same or different; in the case where Y ¹ represents -O-, R ¹² is an alkyl group or a fluorenyl group, and in the case where Y ¹ represents -C(=O)-, R ¹² is an alkoxy group. Base or alkylamino group). The colored hardening composition according to Item 1 or 2, wherein X ¹ of the formula (2) is -O-, Ar ¹ is a phenyl group which may have a substituent, and Y ¹ is - O-, R ¹² is an alkyl group which may have a substituent, a fluorenyl group which may have a substituent, or a sulfonyl group which may have a substituent, and the coloring curable composition further contains a carboxylic acid type binder, and the following a yellow colorant represented by the formula (5), (In the formula (5), R ¹¹ represents an alkyl group or a vinyl group, respectively, and R ¹² each represents an aromatic ring group having a substituent). The colored hardening composition according to Item 1 or 2, wherein X ¹ of the formula (2) is -O-, Ar ¹ is a phenyl group which may have a substituent, and Y ¹ is - C (= O) -, R 12 is an optionally substituted alkoxy group, an alkoxy group or a substituent group, and the colored curable composition further comprises a carboxylic acid-based binder, and the following formula ( 5) Yellow colorant represented, general formula (5) (In the formula (5), R ¹¹ represents an alkyl group or a vinyl group, respectively, and R ¹² each represents an aromatic ring group having a substituent). The colored hardening composition according to the first or second aspect of the invention, further comprising a carboxylic acid binder and a yellow colorant, and the compound represented by the formula (1) is a formula (1) '酞的所花青化合物, (In the formula (1'), R ¹ to R ⁴ are each a substituent represented by the following formula (2'), a bromine atom or a chlorine atom, and p, q, r, and s represent 0 to 4, respectively. The sum of p, q, r and s is 12 to 16; the number of substituents represented by the formula (2') in the formula (1') is 4 to 12; R represents a hydrogen atom; M represents Cu or Zn) , (In the formula (2'), X ¹ represents -O-, Ar ¹ represents a phenyl group; R ¹¹ represents a hydrogen atom or a methyl group, and n1 represents an integer of 1 to 3; and in the case where n1 is 2 or 3, A plurality of R ^{11 's} may be the same or different; in the case where Y ¹ represents -O-, R ¹² is an alkyl group or a fluorenyl group, and in the case where Y ¹ represents -C(=O)-, R ¹² is an alkoxy group. Base or alkylamino group). The color hardening composition according to claim 15, wherein the yellow colorant is a monomethine dye represented by the following formula (5), (In the formula (5), R ¹¹ represents an alkyl group or a vinyl group, respectively, and R ¹² each represents an aromatic ring group having a substituent). A color filter comprising a coloring layer obtained by using the colored curable composition as described in claim 1 of the patent application. A method of manufacturing a color filter, comprising the steps of: applying a color hardening composition as described in claim 1 on a substrate to form a coloring layer; and exposing the formed colored layer to The step of patterning and developing to form a colored region. A liquid crystal display device, an organic electroluminescence device, or a solid-state imaging device, comprising the color filter of claim 17 or the color filter of claim 18; The color filter produced by the method. a phthalocyanine compound represented by the following formula (1'), (In the formula (1'), R ¹ to R ⁴ are each a substituent represented by the following formula (2'), a bromine atom or a chlorine atom, and p, q, r, and s represent 0 to 4, respectively. The sum of p, q, r and s is 12 to 16; the number of substituents represented by the formula (2') in the formula (1') is 4 to 12; R represents a hydrogen atom; M represents Cu or Zn) , (In the formula (2'), X ¹ represents -O-, Ar ¹ represents a phenyl group; R ¹¹ represents a hydrogen atom or a methyl group, and n1 represents an integer of 1 to 3; and in the case where n1 is 2 or 3, A plurality of R ^{11 's} may be the same or different; in the case where Y ¹ represents -O-, R ¹² is an alkyl group or a fluorenyl group, and in the case where Y ¹ represents -C(=O)-, R ¹² is an alkoxy group. Base or alkylamino group).