JP5885542B2 - Colored curable composition and color filter - Google Patents

Description

  The present invention relates to a colored curable composition and a color filter using the colored curable composition. Furthermore, it is related with the liquid crystal display device, organic electroluminescent element, and solid-state image sensor which used this color filter. Moreover, it is related with the manufacturing method of a color filter.

  Conventionally, color filters are colored curable compositions by containing a pigment dispersion composition in which an organic pigment or an inorganic pigment is dispersed, a polyfunctional monomer, a polymerization initiator, an alkali-soluble resin, and other components as necessary. It is manufactured by forming a colored pattern by using a photolithography method, an ink jet method or the like.

  In recent years, color filters are used not only for monitors but also for televisions (TVs) in liquid crystal display (LCD) applications, and there is a demand for lower power consumption as well as larger screens and higher image quality. In response to these demands, color filters are required to have advanced color characteristics such as chromaticity, contrast, and high transmittance. Similarly, color filters for image sensors (solid-state imaging devices) are required to further improve color characteristics, such as reduction of color unevenness, improvement of color resolution, and transmittance.

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

  Therefore, conventionally, as a colorant, it has been studied to use not only a pigment but also a dye (for example, see Patent Document 1). When a dye is used as a colorant, the hue and brightness of a display image when an image is displayed can be increased due to the color purity of the dye itself and the vividness of the hue, and contrast can be improved because coarse particles are eliminated. It is useful in terms.

  As examples of dyes, compounds having a wide variety of pigment bases such as phthalocyanine dyes, dipyrromethene dyes, pyrimidine azo dyes, pyrazole azo dyes, xanthene dyes are known (see, for example, Patent Documents 2 to 7).

JP-A-6-75375 JP 2008-292970 A JP 2007-039478 A Japanese Patent Laid-Open No. 9-157536 JP-A-6-51115 Japanese Patent Laid-Open No. 11-152415 International Publication No. WO2011 / 105603

  Here, the colored curable composition used for a color filter or the like is required to have high color purity and no absorption (high transmittance) in an unnecessary portion as a color filter. Moreover, high heat resistance and light resistance are also required. The present invention aims to reconcile such problems, and is a colored curable composition capable of producing a color filter having high heat resistance and light resistance without absorption in unnecessary portions as a color filter. The purpose is to provide goods. In particular, it is an object to provide a useful thing as a colored material for a green filter.

  Under such circumstances, as a result of intensive studies by the present inventors, a colored curable composition having high transmittance and excellent light resistance can be obtained by using a halogen-substituted phthalocyanine compound having a specific substituent. I found. In other words, by introducing an alkylene group at a specific position on the side chain of the phthalocyanine ring, the solubility is improved and aggregation between compounds can be suppressed, and the transmittance is improved while maintaining heat resistance and light resistance. I succeeded in making it happen. Furthermore, the present inventors have found that pattern formability can be improved and have completed the present invention. In particular, it has been found that when blended with a carboxylic acid binder, a remarkable effect is exhibited.

Specifically, the above problem has been solved by the following means.
<1> A colored curable composition containing a phthalocyanine compound represented by the following general formula (1).
General formula (1)
(In General Formula (1), R ^{1 to} R ⁴ are each a substituent represented by the following General Formula (2) or a halogen atom, and p, q, r, and s are each 0 to 4, the number of substituents represented by the general formula (2) in the general formula (1) is 1 to 12. R represents a hydrogen atom or a monovalent substituent, and M is Cu. Zn, V (= O), Mg, Ni, Ti (= O), Mg, Sn, or Si.)
General formula (2)
(In the general formula (2), X ¹ represents —O—, —S—, —NR ¹³ — or —SO ₂ —, and Ar ¹ represents an aromatic carbocyclic group or substituent which may have a substituent. R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, n1 represents an integer of 1 to 3. When 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 group. R ¹³ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
<2> The colored curable composition according to <1>, wherein the halogen atom represented by R ^{1 to} R ⁴ represents Br or Cl, and M represents Cu or Zn.
<3> X ^{1 in the} general formula (2) is —O—, Ar ¹ is a phenylene group that may have a substituent, Y ¹ is —O—, and R ¹² is an alkyl group that may have a substituent. The colored curable composition according to <1> or <2>, which is an acyl group which may have a substituent or a sulfonyl group which may have a substituent.
<4> In general formula (2), X ¹ is —O—, Ar ¹ is an optionally substituted phenylene group, Y ¹ is —C (═O) —, and R ¹² is substituted. The colored curable composition according to <1> or <2>, which is a good alkoxy group or an alkylamino group which may have a substituent.
<5> The colored curable composition according to any one of <1> to <4>, wherein the sum of p, q, r and s in the general formula (1) is 12 to 16.
<6> The colored curable composition according to any one of <1> to <5>, further comprising a carboxylic acid binder.
<7> 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.
<9> The colored curable composition according to any one of <1> to <8>, further including a yellow colorant.
<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 general formula (5).
General formula (5)
(In General Formula (5), R ¹¹ represents an alkyl group or a vinyl group, and R ¹² represents an aromatic ring group having a substituent.)
<12> The colored curable composition according to any one of <1> to <11>, wherein the compound represented by the general formula (1) is a phthalocyanine compound represented by the following general formula (1 ′).
General formula (1 ')
(In the general formula (1 ′), R ^{1 to} R ⁴ are each a substituent, a bromine atom, or a chlorine atom represented by the following general formula (2 ′), and p, q, r, and s are: Each represents 0 to 4, and the sum of p, q, r, and s is 12 to 16. The number of substituents represented by the general formula (2 ′) in the general formula (1 ′) is 4 to 12. R represents a hydrogen atom, and M represents Cu or Zn.)
General formula (2 ')
(In General Formula (2 ′), X ¹ represents —O—, Ar ¹ represents a phenylene group, R ¹¹ represents a hydrogen atom or a methyl group, n1 represents an integer of 1 to 3, and n1 is 2. Or a plurality of R ¹¹ may be the same or different in the case of 3. When Y ¹ represents —O—, R ¹² represents an alkyl group or an acyl group, and Y ¹ represents —C (═O) —. When represented, R ¹² is an alkoxy group or an alkylamino group.)
<13> A color filter having a colored layer using the colored curable composition according to any one of <1> to <12>.
<14> Applying the colored curable composition according to any one of <1> to <13> on a substrate, forming a colored layer, exposing the formed colored layer in a pattern, and developing And a step of forming a colored region.
<15> A liquid crystal display device, an organic electroluminescence element, or a solid-state imaging device having the color filter according to <13> or the color filter produced by the method for producing a color filter according to <14>.
<16> A phthalocyanine compound represented by the following general formula (1 ′).
General formula (1 ')
(In the general formula (1 ′), R ^{1 to} R ⁴ are each a substituent, a bromine atom, or a chlorine atom represented by the following general formula (2 ′), and p, q, r, and s are: Each represents 0 to 4, and the sum of p, q, r, and s is 12 to 16. The number of substituents represented by the general formula (2 ′) in the general formula (1 ′) is 4 to 12. R represents a hydrogen atom, and M represents Cu or Zn.)
General formula (2 ')
(In General Formula (2 ′), X ¹ represents —O—, Ar ¹ represents a phenylene group, R ¹¹ represents a hydrogen atom or a methyl group, n1 represents an integer of 1 to 3, and n1 is 2. Or a plurality of R ¹¹ may be the same or different in the case of 3. When Y ¹ represents —O—, R ¹² represents an alkyl group or an acyl group, and Y ¹ represents —C (═O) —. When represented, R ¹² is an alkoxy group or an alkylamino group.)

  According to the present invention, it is possible to provide a colored curable composition having high color purity, having no absorption in a portion unnecessary as a color filter (high transmittance), and excellent in light resistance. Therefore, it can be preferably used as a color filter, particularly as a green color filter. Furthermore, according to the present invention, it is possible to provide a liquid crystal display device and a solid-state imaging device in which the display image is vividly colored and exhibits high contrast.

  Hereinafter, the contents of the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value. In the present specification, a “group” such as an alkyl group may or may not have a substituent unless otherwise specified. Further, in the case of a group having a limited number of carbons, the number of carbons means a number including the number of carbons that the substituent has.

<Colored curable composition>
The colored curable composition of the present invention is characterized by containing a phthalocyanine compound represented by the general formula (1). Usually, two or more types of phthalocyanine compounds represented by the general formula (1) are included.
General formula (1)
(In General Formula (1), R ^{1 to} R ⁴ are each a substituent represented by the following General Formula (2) or a halogen atom, and p, q, r, and s are each 0 to 4, the number of substituents represented by the general formula (2) in the general formula (1) is 1 to 12. R represents a hydrogen atom or a monovalent substituent, and M is Cu. Zn, V (= O), Mg, Ni, Ti (= O), Mg, Sn, or Si.)
General formula (2)
(In the general formula (2), X ¹ represents —O—, —S—, —NR ¹³ — or —SO ₂ —, and Ar ¹ represents an aromatic carbocyclic group or substituent which may have a substituent. R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, n1 represents an integer of 1 to 3. When n1 is 2 or 3, A plurality of R ¹¹ may be the same or different, Y ¹ represents —O—, —S—, —N—R ¹³ —, —SO ₂ —, or mC (═O) —, and R ¹² represents Represents a monovalent substituent.)

Many studies have been made on the use of phthalocyanine compounds as colorants for color filters (Patent No. 3476208, International Publication No. WO2011 / 105603 pamphlet). A colored curable composition satisfying heat resistance, light resistance, curing sensitivity, and resist storage stability has not been obtained. From the viewpoint that the colored curable composition of the present invention can satisfy all of these points, the significance of the present invention is great.
Furthermore, since the phthalocyanine compound used in the present invention has excellent solubility, high compatibility with a carboxylic acid-containing binder, and excellent heat resistance, high transmittance can be realized. further,
In the phthalocyanine compound used in the present invention, the ratio of the minimum value of the absorption intensity around 500 nm to the maximum value of the main absorption (absorption intensity minimum value near 500 nm / main absorption maximum value) is 0 to 0.1. It is preferably in the range, and more preferably in the range of 0 to 0.02.
When the phthalocyanine compound represented by the general formula (1) used in the present invention is a mixture of two or more types, p, q, r, s and a substituent represented by the general formula (2) in the general formula (1) The number of means the average value of the substituents in the mixture.
Hereinafter, the details of the phthalocyanine compound represented by the general formula (1) will be described.

In general formula (1), R ^{1 to} R ⁴ are each a substituent represented by the following general formula (2) or a halogen atom.
The halogen atom is preferably a bromine atom or a chlorine atom, and the halogen atom is preferably a bromine atom or a chlorine atom, and particularly preferably a chlorine atom.
In the above general formula (1), when the substitution position of the halogen atom is the α-position of the phthalocyanine skeleton, the absorption wavelength becomes long wave, which can be suitably used for a green filter. The α-position substitution number is preferably 4 to 8 as the total number of α-positions in the phthalocyanine.

p, q, r, and s each represent 0 to 4, preferably any three of p, q, r, and s represent 3 to 4, and particularly preferably any of p, q, r, and s Or 3 represents 4.
The number of substituents represented by the general formula (2) in the general formula (1) is 1 to 12, preferably 2 to 10, and more preferably 4 to 8.
R represents a hydrogen atom or a monovalent substituent, respectively. Examples of the substituent include a substituent T described later, preferably an alkyl group or an alkoxy group, and 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 or 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), particularly preferably Cu or Zn is represented.

In the general 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, and 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 carbocycle is preferably an aryl group having 6 to 24 carbon atoms, and represents, for example, a phenylene group or a naphthylene group, and may further have a substituent. The aromatic heterocyclic ring is preferably a heterocyclic group having 1 to 18 carbon atoms, for example, 2-thienyl group, 4-pyridyl group, 2-furyl group, 2-pyrimidinyl group, 1-pyridyl group, 2-benzothiazolyl. Represents a group, 1-imidazolyl group, 1-pyrazolyl group, benzotriazol-1-yl group and the like, and may further have a substituent. Examples of the substituent include a substituent T described later. Ar ¹ is more preferably a phenylene group which may have a substituent and a naphthylene group which may have a substituent, and particularly preferably a phenylene 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, and more preferably a hydrogen atom.
n1 represents an integer of 1 to 3, and 1 or 2 is more preferable. When n1 is 2 or 3, the plurality of R ¹¹ may be the same or different.
Y ¹ represents —O—, —S—, —N—R ¹³ —, —SO ₂ —, or —C (═O) —, and represents —O—, —SO ₂ —, or —C (= O)-is preferable, and -O- or -C (= O)-is more preferable.
R ¹² represents a monovalent substituent, and examples of the substituent include a substituent T described later, and these substituents may be further substituted with a substituent. R ¹² is preferably an alkyl group which may have a substituent, an acyl group which may have a substituent, a sulfonyl group which may have a substituent, an alkoxy group which may have a substituent, Or an alkylamino group which may have a substituent, more preferably an alkyl group having 1 to 12 carbon atoms which may have a substituent, and 1 to 12 carbon atoms which may have a substituent. Or an alkylamino group having 1 to 12 carbon atoms which may have a substituent.
The mass of the R ¹² portion per molecule of the phthalocyanine compound represented by the general formula (1) is preferably 200 to 2500, and more preferably 250 to 1500.

Examples of the substituent T are shown below.
An alkyl group (preferably a linear, branched or cyclic alkyl group having 1 to 24 carbon atoms, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, tert-butyl group, pentyl group, Hexyl group, heptyl group, octyl group, 2-ethylhexyl group, dodecyl group, hexadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, 1-norbornyl group, 1-adamantyl group), alkenyl group (preferably having 2 to 2 carbon atoms) 18 alkenyl groups such as vinyl group, allyl group and 3-buten-1-yl group), aryl groups (preferably aryl groups having 6 to 24 carbon atoms such as phenyl group and naphthyl group), heterocyclic ring Group (preferably a heterocyclic group having 1 to 18 carbon atoms such as 2-thienyl group, 4-pyridyl group, 2-furyl group, 2- Limidinyl group, 1-pyridyl group, 2-benzothiazolyl group, 1-imidazolyl group, 1-pyrazolyl group, benzotriazol-1-yl group), silyl group (preferably a silyl group having 3 to 18 carbon atoms, for example, trimethylsilyl Group, triethylsilyl group, tributylsilyl group, tert-butyldimethylsilyl group, tert-hexyldimethylsilyl group), hydroxyl group, cyano group, nitro group, alkoxy group (preferably an alkoxy group having 1 to 24 carbon atoms, Methoxy group, ethoxy group, 1-butoxy group, 2-butoxy group, isopropoxy group, tert-butoxy group, dodecyloxy group, and cycloalkyloxy group, for example, cyclopentyloxy group, cyclohexyloxy group) An aryloxy group (preferably having 6 to 2 carbon atoms) An aryloxy group of, for example, phenoxy group, 1-naphthoxy group), a heterocyclic oxy group (preferably a heterocyclic oxy group having 1 to 18 carbon atoms, such as 1-phenyltetrazole-5-oxy group, 2- Tetrahydropyranyloxy group), silyloxy group (preferably a silyloxy group having 1 to 18 carbon atoms, for example, trimethylsilyloxy group, tert-butyldimethylsilyloxy group, diphenylmethylsilyloxy group), acyloxy group (preferably carbon number) An acyloxy group having 2 to 24, for example, an acetoxy group, a pivaloyloxy group, a benzoyloxy group, a dodecanoyloxy group, an alkoxycarbonyloxy group (preferably an alkoxycarbonyloxy group having 2 to 24 carbon atoms, for example, ethoxycarbonyloxy Group, tert-butoki In the case of a sicarbonyloxy group or a cycloalkyloxycarbonyloxy group, for example, a cyclohexyloxycarbonyloxy group, an aryloxycarbonyloxy group (preferably an aryloxycarbonyloxy group having 7 to 24 carbon atoms, for example, phenoxy Carbonyloxy group), carbamoyloxy group (preferably a carbamoyloxy group having 1 to 24 carbon atoms, such as N, N-dimethylcarbamoyloxy group, N-butylcarbamoyloxy group, N-phenylcarbamoyloxy group, N- Ethyl-N-phenylcarbamoyloxy group), sulfamoyloxy group (preferably a sulfamoyloxy group having 1 to 24 carbon atoms, for example, N, N-diethylsulfamoyloxy group, N-propylsulfamoyl group) Oxy group), alkyl A sulfonyloxy group (preferably an alkylsulfonyloxy group having 1 to 24 carbon atoms, for example, a methylsulfonyloxy group, a hexadecylsulfonyloxy group, a cyclohexylsulfonyloxy group), an arylsulfonyloxy group (preferably having 6 to 24 carbon atoms) An arylsulfonyloxy group such as a phenylsulfonyloxy group, an acyl group (preferably an acyl group having 1 to 24 carbon atoms, such as a formyl group, acetyl group, pivaloyl group, benzoyl group, tetradecanoyl group, cyclohexa Noyl group), alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 24 carbon atoms, such as methoxycarbonyl group, ethoxycarbonyl group, octadecyloxycarbonyl group, cyclohexyloxycarbonyl group, 2,6-di-ter -Butyl-4-methylcyclohexyloxycarbonyl group), aryloxycarbonyl group (preferably an aryloxycarbonyl group having 7 to 24 carbon atoms, such as phenoxycarbonyl group), carbamoyl group (preferably carbamoyl having 1 to 24 carbon atoms) Groups such as carbamoyl, N, N-diethylcarbamoyl, N-ethyl-N-octylcarbamoyl, N, N-dibutylcarbamoyl, N-propylcarbamoyl, N-phenylcarbamoyl, N-methylN -Phenylcarbamoyl group, N, N-dicyclohexylcarbamoyl group), amino group (preferably an amino group having 24 or less carbon atoms, for example, amino group, methylamino group, N, N-dibutylamino group, tetradecylamino group) Group, 2-ethylhexylamino group, cyclohexyl Silamino group), anilino group (preferably 6 to 24 anilino group, for example, anilino group, N-methylanilino group), heterocyclic amino group (preferably 1 to 18 heterocyclic amino group, for example, 4-pyridylamino Group), a carbonamide group (preferably a carbonamide group having 2 to 24 carbon atoms, for example, an acetamido group, a benzamide group, a tetradecanamide group, a pivaloylamide group, a cyclohexaneamide group), a ureido group (preferably a ureido having 1 to 24 carbon atoms). Group, for example, ureido group, N, N-dimethylureido group, N-phenylureido group), imide group (preferably an imide group having 24 or less carbon atoms, for example, N-succinimide group, N-phthalimide group), An alkoxycarbonylamino group (preferably an alkoxycarbonyl group having 2 to 24 carbon atoms) Group, for example, methoxycarbonylamino group, ethoxycarbonylamino group, tert-butoxycarbonylamino group, octadecyloxycarbonylamino group, cyclohexyloxycarbonylamino group), aryloxycarbonylamino group (preferably having 7 to 24 carbon atoms). An aryloxycarbonylamino group such as a phenoxycarbonylamino group, a sulfonamide group (preferably a sulfonamide group having 1 to 24 carbon atoms, such as a methanesulfonamide group, a butanesulfonamide group, a benzenesulfonamide group, hexadecane A sulfonamido group, a cyclohexanesulfonamido group), a sulfamoylamino group (preferably a sulfamoylamino group having 1 to 24 carbon atoms, such as N, N-dipropylsulfamoylamino group, N Ethyl-N-dodecylsulfamoylamino group), azo group (preferably an azo group having 1 to 24 carbon atoms, for example, phenylazo group, 3-pyrazolylazo group), alkylthio group (preferably having 1 to 24 carbon atoms). An alkylthio group, for example, a methylthio group, an ethylthio group, an octylthio group, a cyclohexylthio group, an arylthio group (preferably an arylthio group having 6 to 24 carbon atoms, for example, a phenylthio group), a heterocyclic thio group (preferably a carbon number) 1 to 18 heterocyclic thio groups, for example, 2-benzothiazolylthio group, 2-pyridylthio group, 1-phenyltetrazolylthio group), alkylsulfinyl group (preferably an alkylsulfinyl group having 1 to 24 carbon atoms) , For example, dodecanesulfinyl group), arylsulfinyl group (preferably having 6 to 2 carbon atoms) 4 arylsulfinyl group, for example, phenylsulfinyl group), alkylsulfonyl group (preferably an alkylsulfonyl group having 1 to 24 carbon atoms, for example, methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, butylsulfonyl group, isopropyl Sulfonyl group, 2-ethylhexylsulfonyl group, hexadecylsulfonyl group, octylsulfonyl group, cyclohexylsulfonyl group), arylsulfonyl group (preferably arylsulfonyl group having 6 to 24 carbon atoms, such as phenylsulfonyl group, 1-naphthylsulfonyl group) Group), a sulfamoyl group (preferably a sulfamoyl group having 24 or less carbon atoms, such as a sulfamoyl group, an N, N-dipropylsulfamoyl group, an N-ethyl-N-dodecylsulfamoyl group, an N-ethyl group). Ru-N-phenylsulfamoyl group, N-cyclohexylsulfamoyl group), sulfo group, phosphonyl group (preferably phosphonyl group having 1 to 24 carbon atoms, such as phenoxyphosphonyl group, octyloxyphosphonyl group, Phenylphosphonyl group) and a phosphinoylamino group (preferably a phosphinoylamino group having 1 to 24 carbon atoms such as a diethoxyphosphinoylamino group and a dioctyloxyphosphinoylamino group).

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

  In particular, for the purpose of improving developability with respect to an alkaline developer, an alkaline aqueous solution solubilized part, for example, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a sulfonimide group, a phenolic hydroxyl group, an acetoacetamide group, an acetoacetate group And substituents such as an alkyl group, an alkyloxy group, an alkylthio group, an aryloxy group, an arylthio group, an alkylsulfonyl group, and an arylsulfonyl group, which are substituted with these groups are preferably used.

In the present invention, the following embodiments are particularly preferable.
(First aspect)
An embodiment in which the halogen atom represented by R ^{1 to} R ⁴ represents Br or Cl, and M represents Cu or Zn.
(Second aspect)
In general formula (2), X ¹ is —O—, Ar ¹ is a phenylene group that may have a substituent, Y ¹ is —O—, and R ¹² is an alkyl group that may have a substituent. The aspect which is the sulfonyl group which may have an acyl group which may have or a substituent.
(Third aspect)
In formula (2), X ¹ is —O—, Ar ¹ is a phenylene group which may have a substituent, Y ¹ is —C (═O) —, and R ¹² is an alkoxy which may have a substituent. The aspect which is the alkylamino group which may have a group or a substituent.
(Fourth aspect)
A combination of the first aspect and the second or third aspect.

The phthalocyanine compound represented by the general formula (1) in the present invention is preferably a phthalocyanine compound represented by the following general formula (1 ′).
General formula (1 ')
(In the general formula (1 ′), R ^{1 to} R ⁴ are each a substituent, a bromine atom, or a chlorine atom represented by the following general formula (2 ′), and p, q, r, and s are: Each represents 0 to 4, and the sum of p, q, r, and s is 12 to 16. The number of substituents represented by the general formula (2 ′) in the general formula (1 ′) is 4 to 12. R represents a hydrogen atom, and M represents Cu or Zn.)
General formula (2 ')
(In General Formula (2 ′), X ¹ represents —O—, Ar ¹ represents a phenylene group, R ¹¹ represents a hydrogen atom or a methyl group, n1 represents an integer of 1 to 3, and n1 is 2. Or a plurality of R ¹¹ may be the same or different in the case of 3. When Y ¹ represents —O—, R ¹² represents an alkyl group or an acyl group, and Y ¹ represents —C (═O) —. When represented, R ¹² is an alkoxy group or an alkylamino group.)
The preferred range of each group of the general formula (1 ′) is the same as that of the general formula (1).

Although the example of the substituent represented by General formula (2) used by this invention below is given, this invention is not limited to these.

  The molecular weight of the phthalocyanine compound represented by the general formula (1) is preferably 900 to 4000, more preferably 1000 to 2500.

Next, a method for synthesizing the phthalocyanine of the present invention will be described.
The phthalocyanine compound can be synthesized according to the methods described in “Issued by Phthalocyanine Co., Ltd. as a functional dye”, “Phthalocyanine—Chemistry and Function—Issued by IPC Co., Ltd.” and the like.

  In particular, since the compound of the present invention is a halogenated phthalocyanine, it can be synthesized by cyclizing a halide intermediate and synthesizing phthalocyanine or halogenating a phthalocyanine compound as described below.

  Moreover, the phthalocyanine of the present invention generally gives a complicated 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 them.
As an example, the case where halogenated phthalonitrile is used as a starting material is shown. However, the substituent may be introduced at either the α-position or β-position of the halogenated phthalonitrile, and when one is introduced, α1 or β1 is introduced. When two are introduced, a mixture such as α1-β1, α1-β2, α1-α2, β1-β2 is given. In the present invention, the ratio of those introduced at the β-position is preferably high. Specifically, it is preferable that four or more of the eight β-positions have a substituent represented by the general formula (2).

2) Formation of isomer mixture by asymmetry of intermediate The following shows an example of formation of a phthalocyanine mixture when a cyclization reaction is carried out using an asymmetric intermediate having a different β-position substituent. A mixture of at least four or more isomers is provided as follows. However, this does not apply to the case where an intermediate is synthesized by halogenating phthalonitrile, phthalic anhydride or phthalimide having a substituent R.

3) When two or more kinds of intermediates are mixed and subjected to a cyclization reaction The following shows an example in which two kinds of intermediates having different substituents are used, and the number of substitutions of each intermediate, It gives a mixture with different substitution positions. In addition, when the mixing ratio of the intermediate is changed or when the reactivity of the intermediate is different, the substitution position and the number of substitution of the mixed product are also different.

As described above, since the phthalocyanine compound is a mixture having different substitution positions and substitution numbers, it is difficult to uniquely describe it as a structural formula. Further, the number of substitutions shown in the following table is a value obtained by approximating the average value of the number of substituents in the mixture, and may be a small number.
Examples of the phthalocyanine compound used in the present invention will be given below, but the present invention is not limited thereto.

  The content of the phthalocyanine compound represented by the general formula (1) in the colored curable composition varies depending on the molecular weight and its extinction coefficient, but is 1 to 70 with respect to the total solid content of the colored curable composition. % By mass is preferable, and 10 to 50% by mass is more preferable. When the dye content is 10% by mass or more, a good color density (for example, a color density suitable for liquid crystal display) can be obtained, and when it is 50% by mass or less, pixel patterning becomes good. Is advantageous.

[Coloring compounds]
Further, the colored curable composition of the present invention may contain dye compounds and pigment compounds having other structures and dispersions thereof. The dye compound may have any structure as long as it does not affect the hue of the colored image. Anthraquinone compounds), phthalocyanine compounds (for example, phthalocyanine compounds described in US 2008 / 0076044A1), xanthene compounds (for example, CI Acid Red 289), triarylmethanes Series (for example, CI Acid Blue 7), CI Acid Blue 83, CI Acid Blue 90, CI Solvent Blue 38 (CISolvent Blue38), CI Acid Violet 17, Over Eye Acid Violet 49 (CIAcid Violet49), CI Acid Green 3 (CIAcid Green3), methine dyes, monomethine dye (CIsolvent / yellow93)
Etc.

  Examples of pigment compounds include perylene, perinone, quinacridone, quinacridonequinone, anthraquinone, anthanthrone, benzimidazolone, disazo condensation, disazo, azo, indanthrone, phthalocyanine, triarylcarbonium, dioxazine, aminoanthraquinone, diketopyrrolopyrrole, Indigo, thioindigo, isoindoline, isoindolinone, pyranthrone, isoviolanthrone and the like. More specifically, for example, perylene compound pigments such as Pigment Red 190, Pigment Red 224, and Pigment Violet 29, perinone compound pigments such as Pigment Orange 43, and Pigment Red 194, Pigment Violet 19, and Pigment Violet. 42, quinacridone such as 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 Quinone compound pigment, anthraquinone compound pigment such as pigment yellow 147, anthanthrone compound pigment such as pigment red 168, pigment Benzimidazolone compound pigments such as Pigment Brown 25, Pigment Violet 32, Pigment Orange 36, Pigment Yellow 120, Pigment Yellow 180, Pigment Yellow 181, Pigment Orange 62, or Pigment Red 185; 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, Pigment Red Red 220, Pigment Red 221, Pigment Red 242, Pigment Red 248, Pigment Red 262, or Pigment Disazo condensation compound pigments such as Brown 23, Pigment Yellow 13, Pigment Yellow 83, or Disazo Compound Pigments such as Pigment Yellow 188, Pigment Red 187, Pigment Red 170, Pigment Yellow 74, Pigment Yellow 150, Pigment Red 48, Pigment Red 53, Pigment Orange 64, Pigment Red 247 and other azo compound pigments, Pigment Blue 60 and other indanthrone compound pigments, Pigment Green 7, Pigment Green 36, Pigment Green 37, phthalocyanine compound pigments such as Pigment Green 58, Pigment Blue 16, Pigment Blue 75, and Pigment Blue 15, Pigment Blue 56 Or triarylcarbonium compound pigments such as Pigment Blue 61, dioxazine compound pigments such as Pigment Violet 23 or Pigment Violet 37, aminoanthraquinone compound pigments such as Pigment Red 177, Pigment Red 254, Pigment Red 255, pigment red 264, pigment red 272, pigment orange 71, or diketopyrrolopyrrole compound pigment such as pigment orange 73, thioindigo compound pigment such as pigment red 88, pigment yellow 139, pigment orange 66 Isoindoline compound pigments such as Pigment Yellow 109, Pigment Orange 61, and Pigment Oren 40, or pyranthrone compound pigments such as Pigment Red 216 or isoviolanthrone compound pigments, such as Pigment Violet 31, and the like.

  The colorant is preferably a yellow colorant in the present invention, more preferably a pigment yellow 150 or pigment yellow 139 as a pigment, and a preferred dye is C.I. I. Solvent Yellow 4, C.I. I. Solvent Yellow 88, C.I. I. Solvent Yellow 14, C.I. I. Solvent Yellow 15, C.I. I. Solvent Yellow 24, C.I. I. Solvent Yellow 94, C.I. I. Solvent Yellow 98, C.I. I. Solvent Yellow 162, C.I. I. Solvent Yellow 82, C.I. I. Solvent Yellow 93.

In the present invention, the yellow colorant is preferably a monomethine dye, and the yellow colorant is more preferably a monomethine dye represented by the following general formula (5).
(In General Formula (5), R ¹¹ represents an alkyl group or a vinyl group, and R ¹² represents an aromatic ring group having a substituent.)
R ¹¹ is preferably an alkyl group having 1 to 12 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms.
R ¹² is preferably a phenyl group or a naphthyl group, and the substituent is preferably an alkylsulfonylamino group, a vinylsulfonylamino group, an arylsulfonylamino group, an alkylcarbonylamino group, a vinylcarbonylamino group, or an arylcarbonylamino group. Alkylsulfonylamino groups are preferred but preferred. The C 1-12 alkyl group may have an unsaturated bond, and examples of such a substituent include an allylsulfonylamino group.

When the dye or pigment is blended as a dispersion, it can be adjusted according to the descriptions in JP-A-9-197118 and JP-A-2000-239544.
Content of the said dye or pigment can be used in the range which does not impair the effect of this invention, and is 0.5 mass%-70 mass% with respect to the total solid of the colored curable composition of this invention. preferable. Further, it is preferably added to the colored curable composition so that the absorption intensity ratio (absorption at 450 nm / absorption at 650 nm) is in the range of 0.95 to 1.05.

[Polymerizable compound]
The colored curable composition of the present invention preferably contains at least one polymerizable compound. Examples of the polymerizable compound include addition polymerizable compounds having at least one ethylenically unsaturated double bond.

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

  Examples of monomers and their (co) polymers include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), their esters, amides, and these (Co) polymers, preferably esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, amides of unsaturated carboxylic acids and aliphatic polyhydric amine compounds, and these (co) polymers It is a polymer. Also, addition reaction products of monofunctional or polyfunctional isocyanates or epoxies with unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as hydroxyl group, amino group, mercapto group, monofunctional or polyfunctional. A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amine, or thiol, and a halogen group A substitution reaction product of an unsaturated carboxylic acid ester or amide having a detachable substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid.

Specific examples of the ester monomer of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, tetra Methylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol Diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol tria Relate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer, isocyanur Examples include acid EO-modified triacrylate.
Examples of methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, and 1,3-butanediol. Dimethacrylate, hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3- Methacryloxy-2-hi Rokishipuropokishi) phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane, and the like.

Further, as itaconic acid ester, for example, ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol Diitaconate, sorbitol tetritaconate, etc., and crotonic acid esters such as ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, sorbitol tetradicrotonate, etc. For example, ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, sorbitol tetraisocrotonate, etc. As, for example, ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, sorbitol tetra malate, and the like.
Examples of other esters include aliphatic alcohol esters described in JP-B-51-47334 and JP-A-57-196231, JP-A-59-5240, and JP-A-59-5241. And those having an aromatic skeleton described in JP-A-2-226149 and those containing an amino group described in JP-A-1-165613. Furthermore, the ester monomers described above can also be used as a mixture.

Specific examples of amide monomers of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis. -Methacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide and the like.
Examples of other preferable amide monomers include those having a cyclohexylene structure described in JP-B No. 54-21726.

Further, urethane-based addition polymerizable compounds produced by using an addition reaction of isocyanate and hydroxyl group are also suitable. Specific examples thereof include, for example, one molecule described in JP-B-48-41708. Vinyl urethane containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group represented by the following general formula (A) to a polyisocyanate compound having two or more isocyanate groups Compounds and the like.
CH ₂ = C (R) COOCH ₂ CH (R ′) OH (A)
[In General Formula (A), R and R ′ each independently represent H or CH ₃ . ]

  About these polymerizable compounds, the structure, details of usage such as single use or combination, addition amount, etc. can be arbitrarily set according to the final performance design of the colored curable composition. For example, from the viewpoint of sensitivity, a structure having a high unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. Also, from the viewpoint of increasing the strength of the colored cured film, those having three or more functionalities are preferable, and those having different functional numbers and different polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrene compound, vinyl ether compound) are used in combination. Thus, a method of adjusting both sensitivity and intensity is also effective. In addition, the selection of the polymerizable compound is also possible with respect to the compatibility and dispersibility with other components (for example, photopolymerization initiator, colorant (pigment), binder polymer, etc.) contained in the colored curable composition. The method of use is an important factor. For example, compatibility may be improved by using a low-purity compound or using two or more kinds in combination. In addition, a specific structure may be selected from the viewpoint of improving adhesion to a hard surface such as a substrate.

  The content of the polymerizable compound in the total solid content of the colored curable composition (total content in the case of 2 or more types) is not particularly limited, and is 10 from the viewpoint of more effectively obtaining the effects of the present invention. % By mass to 80% by mass is preferable, 15% by mass to 75% by mass is more preferable, and 20% by mass to 60% by mass is particularly preferable.

[Photopolymerization initiator]
The colored curable 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 polymerizable compound, and is preferably selected from the viewpoints of characteristics, initiation efficiency, absorption wavelength, availability, cost, and the like.

  Examples of the photopolymerization initiator include at least one active halogen compound selected from a halomethyl oxadiazole compound and a halomethyl-s-triazine compound, a 3-aryl-substituted coumarin compound, a lophine dimer, a benzophenone compound, and an acetophenone compound. And derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, oxime compounds, and the like. Specific examples of the photopolymerization initiator include those described in paragraphs [0070] to [0077] of JP-A No. 2004-295116. Among these, an oxime compound or a biimidazole compound is preferable from the viewpoint of rapid polymerization reaction.

The oxime compound (hereinafter also referred to as “oxime-based photopolymerization initiator”) is not particularly limited, and is described in, for example, JP-A No. 2000-80068, WO 02 / 100903A1, JP-A No. 2001-233842, and the like. These oxime compounds are mentioned.
Specific examples include 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-butanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio). Phenyl] -1,2-pentanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-hexanedione, 2- (O-benzoyloxime) -1- [4 -(Phenylthio) phenyl] -1,2-heptanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 2- (O-benzoyloxime)- 1- [4- (methylphenylthio) phenyl] -1,2-butanedione, 2- (O-benzoyloxime) -1- [4- (ethylphenylthio) phenyl] -1, -Butanedione, 2- (O-benzoyloxime) -1- [4- (butylphenylthio) phenyl] -1,2-butanedione, 1- (O-acetyloxime) -1- [9-ethyl-6- ( 2-Methylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9-methyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone 1- (O-acetyloxime) -1- [9-propyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9- Ethyl-6- (2-ethylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9-ethyl-6- (2-butylbenzoyl) 9H-carbazol-3-yl] ethanone, 2- (benzoyloxyimino) -1- [4- (phenylthio) phenyl] -1-octanone, 2- (acetoxyimino) -4- (4-chlorophenylthio) -1 -[9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1-butanone and the like. However, it is not limited to these.

  Moreover, in this invention, the compound represented by following General formula (1) is more preferable as an oxime compound from a viewpoint of a sensitivity, the time stability, and the coloring at the time of post-heating.

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

  R is preferably an acyl group from the viewpoint of increasing sensitivity, and specifically, an acetyl group, a propionyl group, a benzoyl group, and a toluyl group are preferable.

  A is an alkylene group substituted with an unsubstituted alkylene group or an alkyl group (for example, a methyl group, an ethyl group, a tert-butyl group, or a dodecyl group) from the viewpoint of increasing sensitivity and suppressing coloration due to heat aging, An alkylene group substituted with an alkenyl group (for example, vinyl group, allyl group), an aryl group (for example, phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl group, styryl group) A substituted alkylene group is preferred.

  Ar is preferably a substituted or unsubstituted phenyl group from the viewpoint of increasing sensitivity and suppressing coloring due to heating. In the case of a substituted phenyl group, the substituent is preferably a halogen group such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

X is an alkyl group that may have a substituent, an aryl group that may have a substituent, or an alkenyl that may have a substituent from the viewpoint of improving solvent solubility and absorption efficiency in the long wavelength region. Group, an alkynyl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthioxy group which may have a substituent, a substituent An arylthioxy group which may have a substituent and an amino group which may have a substituent are preferred.
Moreover, n in General formula (1) has a preferable integer of 1-2.

  As the biimidazole compound, there is no limitation on the structure as long as it is a dimer of an imidazole ring substituted with three aryl groups, and in particular, in the following general formula (II) or general formula (III) Compounds having the structure represented are preferred.

In the general 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 each A independently represents 1 to 12 carbon atoms. Or a substituted or unsubstituted alkoxy group having — 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 represents 1 to 1 3 is an integer of 3, and m is an integer of 1 to 3.

In the general 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. However, two or more of X ¹ , X ² and X ³ do not take a hydrogen atom at the same time.

  Specific examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole and 2,2′-bis (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′-tetrakis (4-ethoxycarbonylphenyl) biimidazole, 2,2′-bis (2 , 4-Dichlorophenyl) -4,4 ′, 5,5′-tetrakis (4-phenoxycarbonylphenyl) biimidazole, 2,2′-bis (2,4,6-trichloro Enyl) -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-cyanophenyl) -4,4 ', 5,5'-tetrakis (4-phenoxycarbonylphenyl) biimidazole, 2,2'-bis (2-methylphenyl) -4,4', 5,5'-tetrakis (4-methoxycarbonylphenyl) biimidazole Imidazole, 2,2′-bis (2-methylphenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) 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′-tetrakis (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-Phenylphenyl) -4,4 ′, 5,5′-tetrakis (4-phenoxycarbonylphenyl) biimidazole Things;

2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra- (p-methoxyphenyl) bisimidazole, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra- (m-methoxyphenyl) bisimidazole, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra- (3,4-dimethoxyphenyl) bisimidazole 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra- (4-methoxyphenyl) bisimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′ , 5,5′-tetra- (3-methoxyphenyl) bisimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra- (3,4-dimethoxyphenyl) bis Imidazole

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′-tetra Phenylbiimidazole, 2,2′-bis (2,4,6-tricyanophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,4-dimethylphenyl) ) -4,4 ', 5,5'-tetraphenylbiimi Sol, 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-diphenylphenyl) -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)- 4,4 ', 5,5'-tetrapheny And the like biimidazole compound bis imidazole.

  Among these, as a particularly preferable compound, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole (commercially available products are B-CIM, manufactured by Hodogaya Chemical Co., Ltd.) 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra- (3,4-dimethoxyphenyl) biimidazole (HABI 1311, Nippon Sebel Hegner), 2,2 Examples include '-bis (2-methylphenyl) -4,4', 5,5'-tetraphenylbiimidazole (commercially available from Kurokin Kasei Co., Ltd.).

  In addition to the above photopolymerization initiator, other known photopolymerization initiators described in paragraph No. 0079 of JP-A No. 2004-295116 may be used in the colored curable composition of the present invention. Good.

A photoinitiator can be contained individually by 1 type or in combination of 2 or more types.
The content (total content in the case of two or more) of the colored curable composition of the photopolymerization initiator in the total solid content is 3% by mass to 20% by mass from the viewpoint of obtaining the effect of the present invention more effectively. % Is preferable, 4% by mass to 19% by mass is more preferable, and 5% by mass to 18% by mass is particularly preferable.

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

  As the organic solvent, esters, ethers, ketones, and aromatic hydrocarbons are used, and specific examples thereof include those described in JP-A-2012-032754, paragraph numbers 0161 to 0162.

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

  It is also preferable to mix two or more of these organic solvents from the viewpoints of the solubility of each of the above-described components, and the solubility of the above-described components and the improvement of the coating surface state when an alkali-soluble polymer is included. In this case, particularly preferably, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol It is a mixed solution composed of two or more selected from acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate.

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

[Alkali-soluble binder]
The colored curable composition of the present invention preferably contains an alkali-soluble binder. The alkali-soluble binder is not particularly limited except that it has alkali solubility, and can be preferably selected from the viewpoints of heat resistance, developability, availability, and the like.

  The alkali-soluble binder is preferably a linear organic high molecular polymer that is soluble in an organic solvent and can be developed with a weak alkaline aqueous solution. Examples of such linear organic high molecular polymers include polymers having a carboxylic acid in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, and JP-B-54-. No. 25957, JP-A-59-53836, JP-A-59-71048, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, etc. Examples thereof include polymers, maleic acid copolymers, partially esterified maleic acid copolymers, and acidic cellulose derivatives having a carboxylic acid in the side chain are also useful.

  In addition to the above, the alkali-soluble binder in the present invention includes a polymer having a hydroxyl group added with an acid anhydride, a polyhydroxystyrene resin, a polysiloxane resin, poly (2-hydroxyethyl (meth)), and the like. Acrylate), polyvinylpyrrolidone, polyethylene oxide, polyvinyl alcohol, and the like are also useful. Further, the linear organic high molecular polymer may be a copolymer of hydrophilic monomers. Examples include alkoxyalkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, glycerol (meth) acrylate, (meth) acrylamide, N-methylol acrylamide, secondary or tertiary alkyl acrylamide, dialkylaminoalkyl (meth). Acrylate, morpholine (meth) acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, vinyltriazole, methyl (meth) acrylate, ethyl (meth) acrylate, branched or linear propyl (meth) acrylate, branched or straight Examples include chain butyl (meth) acrylate, phenoxyhydroxypropyl (meth) acrylate, and the like. Other hydrophilic monomers include tetrahydrofurfuryl group, phosphoric acid group, phosphoric ester group, quaternary ammonium base, ethyleneoxy chain, propyleneoxy chain, sulfonic acid group and groups derived from salts thereof, morpholinoethyl group, etc. Monomers comprising it are also useful.

  The alkali-soluble binder may have a polymerizable group in the side chain in order to improve the crosslinking efficiency, and includes, for example, an allyl group, a (meth) acryl group, an allyloxyalkyl group, etc. in the side chain. Polymers and the like are also useful. Examples of the polymer containing the above-described polymerizable group include commercially available KS resist-106 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), cyclomer P series (manufactured by Daicel Chemical Industries, Ltd.), and the like. In addition, in order to increase the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are also useful.

  Among these various alkali-soluble binders, from the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferable, and from the viewpoint of development control. Are preferably acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins.

  Examples of the acrylic resin include a copolymer made of a monomer selected from benzyl (meth) acrylate, (meth) acrylic acid, hydroxyethyl (meth) acrylate, (meth) acrylamide, and the like, and a commercially available KS resist 106 ( Osaka Organic Chemical Industry Co., Ltd.) and Cyclomer P Series (Daicel Chemical Industries, Ltd.) are preferred.

The alkali-soluble binder is preferably a polymer having a weight average molecular weight (polystyrene equivalent value measured by GPC method) of 1000 to 2 × 10 ⁵ from the viewpoint of developability, liquid viscosity, etc., and a weight of 2000 to 1 × 10 ⁵ A coalescence is more preferable, and a polymer of 5000 to 5 × 10 ⁴ is particularly preferable.

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

[Crosslinking agent]
The colored curable composition of the present invention can be supplemented with a crosslinking agent to further increase the hardness of the colored cured film obtained by curing the colored curable composition.
The crosslinking agent is not particularly limited as long as the film can be cured by a crosslinking reaction. For example, at least selected from (a) an epoxy resin, (b) a methylol group, an alkoxymethyl group, and an acyloxymethyl group. Substituted with at least one substituent selected from a melamine compound, a guanamine compound, a glycoluril compound or a urea compound, (c) a methylol group, an alkoxymethyl group, and an acyloxymethyl group, which is substituted with one substituent; Phenol compounds, naphthol compounds or hydroxyanthracene compounds. Of these, polyfunctional epoxy resins are preferred.
For details such as specific examples of the crosslinking agent, reference can be made to the descriptions in paragraph numbers 0134 to 0147 of JP-A No. 2004-295116.

[Surfactant]
The colored curable composition of the present invention may contain a surfactant. The surfactant may be any of nonionic, cationic, or anionic, and a fluorine-containing surfactant is preferable. Specifically, JP-A-2-54202 is exemplified.
The blending amount of the surfactant in the present invention is preferably 0.0001 to% by mass of 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 aggregation inhibitor, a sensitizer and a light stabilizer, as necessary.

[Method for preparing colored curable composition]
The colored curable composition of the present invention is prepared by mixing the above-described components and optional components as necessary.
In preparing the colored curable composition, the components constituting the colored curable composition may be combined at once, or may be sequentially added after each component is dissolved and dispersed in a solvent. In addition, there are no particular restrictions on the charging order and working conditions when blending. For example, the composition may be prepared by dissolving and dispersing all components in a solvent at the same time. If necessary, each component may be suitably used as two or more solutions / dispersions at the time of use (at the time of application). ) May be mixed to prepare a composition.
The colored curable composition prepared as described above is preferably filtered using a filter having a pore size of 0.01 μm to 3.0 μm, more preferably a pore size of about 0.05 μm to 0.5 μm. Can be used for use.

  Since the colored curable composition of the present invention can form a colored cured film excellent in hue and contrast, a color filter used in a liquid crystal display (LCD) or a solid-state imaging device (for example, CCD, CMOS, etc.) It can be suitably used for forming colored pixels such as printing inks, inkjet inks, and paints. In particular, it is suitable for use in forming colored pixels for liquid crystal display devices.

[Color filter and manufacturing method thereof]
The color filter of the present invention is configured by providing a substrate and a colored region containing the colored curable composition of the present invention on the substrate. The colored region on the substrate is composed of colored films such as red (R), green (G), and blue (B) that form each pixel of the color filter.

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

In the method for producing a color filter of the present invention, the above-described colored curable composition is applied (preferably applied) on a substrate to form a colored layer (also referred to as a colored curable composition layer) (A And a step (B) of curing the colored curable composition layer formed in the step (A).
The curing step is preferably performed in a pattern (preferably through a mask), and the uncured portion of the coating film is developed and removed with a developer to form a colored region (colored pattern). By passing through these steps, a colored pattern composed of pixels of each color (3 colors or 4 colors) is formed, and a color filter can be obtained. In the method for producing a color filter of the present invention, in particular, the step (C) of irradiating the colored pattern formed in the step (B) with ultraviolet rays and the colored pattern irradiated with the ultraviolet rays in the step (C) are applied. On the other hand, the aspect which further provided the process (D) which heat-processes is preferable.
By such a method, a color filter used for a liquid crystal display element or a solid-state imaging element can be manufactured with low process difficulty, high quality, and low cost.
Hereinafter, the manufacturing method of the color filter of the present invention will be described more specifically.

-Process (A)-
In the method for producing a color filter of the present invention, first, the above-described colored curable composition of the present invention is applied onto a substrate directly or via another layer by a desired coating method, and then the colored curable composition is prepared. A coating film (colored curable composition layer) is formed, and then pre-cured (prebaked) as necessary, and the colored curable composition layer is dried.

As the substrate, for example, alkali-free glass, sodium glass, Pyrex (registered trademark) glass, quartz glass used for liquid crystal display elements and the like, and those obtained by attaching a transparent conductive film thereto, solid-state imaging elements, and the like are used. Examples of the photoelectric conversion element substrate include a silicone substrate and a plastic substrate. On these substrates, a black matrix for isolating each pixel may be formed, or a transparent resin layer may be provided for promoting adhesion. Further, if necessary, an undercoat layer may be provided on the substrate in order to improve adhesion to the upper layer, prevent diffusion of substances, or flatten the surface.
The plastic substrate preferably has a gas barrier layer and / or a solvent resistant layer on its surface.

In addition, a driving substrate on which a thin film transistor (TFT) of a thin film transistor (TFT) type color liquid crystal display device is disposed (hereinafter referred to as “TFT type liquid crystal driving substrate”) is used as the substrate. Furthermore, a color pattern formed using the colored curable composition of the present invention can be formed to produce a color filter.
Examples of the substrate in the TFT type liquid crystal driving substrate include glass, silicone, polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide. These substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc., if desired. For example, a substrate in which a passivation film such as a silicon nitride film is formed on the surface of the TFT liquid crystal driving substrate can be used.

  The colored curable composition of the present invention is applied to the substrate directly or via other layers. As a method to be applied, coating is preferable, and coating is preferably performed by a coating method such as spin coating, slit coating, cast coating, roll coating, bar coating, and inkjet.

In the coating step, the method for applying the colored curable composition of the present invention to the substrate is not particularly limited, but a method using a slit nozzle such as a slit-and-spin method or a spinless coating method (hereinafter, Slit nozzle coating method) is preferable.
In the slit nozzle coating method, the slit-and-spin coating method and the spinless coating method have different conditions depending on the size of the coated substrate. For example, a fifth generation glass substrate (1100 mm × 1250 mm) is coated by the spinless coating method. In this case, the discharge amount of the colored curable composition from the slit nozzle is usually 500 microliter / second to 2000 microliter / second, preferably 800 microliter / second to 1500 microliter / second. The speed is usually 50 mm / second to 300 mm / second, preferably 100 mm / second to 200 mm / second.
Further, the solid content of the colored curable composition used in the coating step is usually 10% to 20%, preferably 13% to 18%.

When forming the coating film by the colored curable composition of this invention on a board | substrate, as thickness (after a prebaking process) of this coating film, it is generally 0.3 micrometer-5.0 micrometers, Preferably 0.5 micrometer-4 0.0 μm, most desirably 0.5 μm to 3.0 μm.
In the case of a color filter for a solid-state image sensor, the thickness of the coating film (after pre-baking) is preferably in the range of 0.5 μm to 5.0 μm.

In the application process, usually, a pre-bake treatment is performed after application. If necessary, vacuum treatment can be performed before pre-baking. The vacuum drying conditions are such that the degree of vacuum is usually about 0.1 to 1.0 torr, preferably about 0.2 to 0.5 torr.
The pre-bake treatment is performed in a temperature range of 50 ° C. to 140 ° C., preferably about 70 ° C. to 110 ° C. using a hot plate, an oven, etc., and can be performed under conditions of 10 seconds to 300 seconds. Note that high-frequency treatment or the like may be used in combination with the pre-bake treatment. The high frequency treatment can be used alone.

Examples of the pre-baking condition include a condition of heating at 70 ° C. to 130 ° C. for about 0.5 minutes to 15 minutes using a hot plate or an oven.
The thickness of the colored curable composition layer formed from the colored curable composition is appropriately selected according to the purpose. In the color filter for liquid crystal display devices, the range of 0.2 μm to 5.0 μm is preferable, the range of 1.0 μm to 4.0 μm is more preferable, and the range of 1.5 μm to 3.5 μm is most preferable. Moreover, in the color filter for solid-state image sensors, the range of 0.2 micrometer-5.0 micrometers is preferable, The range of 0.3 micrometer-2.5 micrometers is more preferable, The range of 0.3 micrometer-1.5 micrometers is the most preferable.
In addition, the thickness of the colored curable composition layer is a film thickness after pre-baking.

-Process (B)-
Subsequently, in the method for producing a color filter of the present invention, the film (colored curable composition layer) formed of the colored curable composition formed on the substrate as described above is exposed through, for example, a photomask. Is done. As light or radiation applicable to exposure, g-line, h-line, i-line, j-line, KrF light and ArF light are preferable, and i-line is particularly preferable. When using the i-line to the irradiation light is preferably irradiated at an exposure dose of ^{100mJ / cm 2 ~10000mJ / cm 2} .

  Other exposure rays include ultra high pressure, high pressure, medium pressure, low pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, various visible and ultraviolet laser light sources, fluorescent lamps, tungsten lamps, solar Light or the like can also be used.

Exposure process using a laser light source In an exposure method using a laser light source, an ultraviolet laser is used as the light source.
The irradiation light is preferably an ultraviolet laser having a wavelength in the range of 300 nm to 380 nm, more preferably an ultraviolet laser having a wavelength in the range of 300 nm to 360 nm matches the photosensitive wavelength of the resist. Is preferable. Specifically, the Nd: YAG laser third harmonic (355 nm), which is a relatively inexpensive solid output, and the excimer laser XeCl (308 nm), XeF (353 nm) can be suitably used. .
The exposure amount of the exposure object (pattern), in the range of ^{1mJ / cm 2 ~100mJ / cm 2} , the range of 1mJ / cm ² ~50mJ / cm ² is more preferable. An exposure amount within this range is preferable from the viewpoint of pattern formation productivity.

There are no particular restrictions on the exposure apparatus, but commercially available devices such as Callisto (buoy technology), EGIS (buoy technology), DF2200G (Dainippon Screen) can be used. It is. Further, devices other than those described above are also preferably used.
When manufacturing a color filter for a liquid crystal display device, exposure using mainly h-line and i-line is preferably used by a proximity exposure machine and a mirror projection exposure machine. Further, when manufacturing a color filter for a solid-state image sensor, it is preferable to mainly use i-line in a stepper exposure machine. When manufacturing a color filter using a TFT type liquid crystal driving substrate, the photomask used has a through hole or a U-shaped depression in addition to a pattern for forming a pixel (colored pattern). The thing in which the pattern for forming is provided is used.

The colored curable composition layer exposed as described above can be heated.
The exposure can be performed while flowing nitrogen gas in the chamber in order to suppress oxidation fading of the coloring material in the colored curable composition layer.

Subsequently, the colored curable composition layer after exposure is developed with a developer. Thereby, a negative type or positive type coloring pattern (resist pattern) can be formed. In the development step, the uncured portion of the coating film after exposure is eluted in the developer, and only the cured portion remains on the substrate.
Any developer can be used as long as it dissolves the coating film (colored curable composition layer) of the colored curable composition in the uncured portion while not dissolving the cured portion. For example, combinations of various organic solvents and alkaline aqueous solutions can be used.
Examples of the organic solvent used for development include the above-described solvents that can be used when preparing the colored curable composition of the present invention.
Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethyl. Concentrations of alkaline compounds such as ammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene are 0.001% by mass to 10% by mass, preferably 0.01 The alkaline aqueous solution melt | dissolved so that it may become 1 mass%-1 mass% is mentioned. When the developer is an alkaline aqueous solution, the alkali concentration is preferably adjusted to be pH 11 to 13, more preferably pH 11.5 to 12.5.
An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline aqueous solution.

The development temperature is usually 20 ° C. to 30 ° C., and the development time is 20 seconds to 90 seconds.
Development may be any of a dip method, a shower method, a spray method, and the like, and may be combined with a swing method, a spin method, an ultrasonic method, or the like. It is also possible to prevent development unevenness by previously moistening the surface to be developed with water or the like before touching the developer. It is also possible to develop with the substrate tilted.
Further, when manufacturing a color filter for a solid-state image sensor, paddle development is also used.

After the development process, a rinsing process for washing and removing excess developer is performed, followed by drying, followed by heat treatment (post-baking) to complete the curing.
The rinsing process is usually performed with pure water, but in order to save liquid, pure water is used in the final cleaning, and used pure water is used in the initial stage of cleaning, or the substrate is inclined and cleaned. Alternatively, a method of using ultrasonic irradiation together may be used.

  After the rinse treatment, after draining and drying, a heat treatment of about 200 ° C. to 250 ° C. is usually performed. In this heat treatment (post-bake), the coating film after development is continuously or batch-treated using a heating means such as a hot plate, a convection oven (hot air circulation dryer) or a high-frequency heater so as to satisfy the above conditions. It can be done with an expression.

By sequentially repeating the above steps for each color according to the desired number of hues, it is possible to produce a color filter in which a cured film (colored pattern) colored in a plurality of colors is formed.
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 imaging device or a liquid crystal display device.

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

-Process (D)-
It is preferable to further heat-treat the colored pattern that has been post-exposed by ultraviolet irradiation as described above. The colored pattern can be further cured by subjecting the formed colored pattern to heat treatment (so-called post-bake treatment). This heat treatment can be performed by, for example, a hot plate, various heaters, an oven, or the like.
As temperature in the case of heat processing, it is preferable that it is 100 to 300 degreeC, More preferably, it is 150 to 250 degreeC. The heating time is preferably about 10 minutes to 120 minutes.

The colored pattern thus obtained constitutes a pixel in the color filter. In the production of a color filter having a plurality of hue pixels, the above steps (A), (B), and if necessary, the steps (C) and (D) are repeated according to the desired number of colors. Good.
The process (C) and / or the process (D) may be performed every time the formation, exposure, and development of the monochromatic colored curable composition layer is completed (for each color), or a desired color. After the formation, exposure, and development of all the colored curable composition layers are completed, the step (C) and / or the step (D) may be performed collectively.

The color filter obtained by the method for producing a color filter of the present invention (the color filter of the present invention) is excellent in hue and contrast since the colored curable composition of the present invention is used.
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. When used in a liquid crystal display device, it is possible to display an image excellent in spectral characteristics and contrast while achieving a good hue using a dye as a colorant.

As described above, the use of the colored curable composition of the present invention has been described mainly focusing on the formation of the color filter color pattern. Can also be applied.
The black matrix on the substrate is a colored curable composition containing a black pigment processed pigment such as carbon black, titanium black, etc., and is subjected to coating, exposure, and development steps. It can be formed by baking.

[Liquid Crystal Display]
The liquid crystal display element and the solid-state image sensor of the present invention are provided with the color filter of the present invention. More specifically, for example, by forming an alignment film on the inner surface side of the color filter, facing the electrode substrate, and filling the gap with liquid crystal and sealing, a panel which is the liquid crystal display element of the present invention is obtained. . For example, the solid-state image sensor of this invention is obtained by forming a color filter on a light receiving element.

  For the definition of liquid crystal display devices and details of each display device, refer to, for example, “Electronic Display Devices (Akio Sasaki, published by Kogyo Kenkyukai 1990)”, “Display Devices (written by Junaki Ibuki, Sangyo Tosho) Issued in 1989) ”. The liquid crystal display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by Kogyo Kenkyukai 1994)”. The liquid crystal display device to which the present invention can be 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”.

The color filter of the present invention is particularly effective for a color TFT liquid crystal display device. The color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”. Furthermore, the present invention is applied to a liquid crystal display device with a wide viewing angle such as a horizontal electric field driving method such as IPS and a pixel division method such as MVA, STN, TN, VA, OCS, FFS, and R-OCB. it can.
The color filter of the present invention can also be used for a bright and fine COA (Color-filter On Array) system.

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

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

Example 1
Each component used for preparation of a colored curable composition is shown below.
(Y-1) C.I. I. Pigment Yellow 150 (12.8 parts) and methyl methacrylate / methacrylic acid (80/20) [mass ratio] copolymer (weight average molecular weight: 12,000) (7.2 parts) are mixed with propylene glycol monomethyl ether acetate (80.0). And a pigment dispersion (Y-2) C. obtained by sufficiently dispersing the pigment using a bead mill. I. Solvent Yellow 162) Dissolved in 10.0 parts of propylene glycol monomethyl ether acetate (manufactured by Wako Pure Chemical Industries, Ltd.) (Y-3) 10.0 parts by weight of the following yellow dye was tetrahydrofuran (Wako Pure Chemical Industries, Ltd.) Made in 90.0 parts
(T-1) Photopolymerizable compound: Kayalad DPHA (manufactured by Nippon Kayaku Co., Ltd., 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) in propylene glycol monomethyl ether acetate solution (solid content: 40.0 mass%) Value (100mgKOH / g)
(V-1) Photopolymerization initiator: 2- (benzoyloxyimino) -1- [4- (phenylthio) phenyl] -1-octanone (manufactured by BASF)
(V-2) Photopolymerization initiator: 2- (acetoxyimino) -4- (4-chlorophenylthio) -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1-butanone (made by BASF)
(V-3) Photopolymerization initiator: an oxime compound having the following structure
(V-4) Photopolymerization initiator: Irgacure 369 (manufactured by BASF: α-acylamino compound)
(V-5) 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole (B-CIM manufactured by Hodogaya Chemical Co., Ltd.)
(W-1) Photopolymerization initiation assistant: 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 & Chemicals, Inc.)
(A-101) C.I. synthesized by the method described in Japanese Patent No. 3476208. I. Acid Blue 249 dodecyl amidated compound (A-102) Compound described in Example 38 of International Publication WO 2011/105603 Pamphlet

<Preparation of colored film>
Preparation of colored curable composition (coating liquid) Components in the following composition were mixed to prepare a colored curable composition 1.
<Composition>
-Exemplified Compound A-1 ... 6.9 parts by mass-(T-1) ... 103.4 parts by mass-(U-1) ... 212.2 parts by mass (in terms of solid content) (Value: 84.9 parts by mass)
-(V-1)-21.2 parts by mass-(W-1)-3.5 parts by mass-(X-1)-71.9 parts by mass- (X-2) ... 3.6 parts by mass, (Z-1) ... 0.06 parts by mass

(Preparation of colored film by curable colored curable composition)
The colored curable composition (color resist solution) obtained above is placed on a 100 mm × 100 mm glass substrate (1737, manufactured by Corning) so that the maximum absorbance at 600 to 700 nm is 1.5 to 2.0. And dried in an oven at 100 ° C. for 180 seconds to produce a colored film on the substrate.

(Evaluation of colored film by curable colored curable composition)
The following evaluation was performed about the board | substrate obtained above.
<Evaluation of hue>
Absorption in the vicinity of 500 nm when the absorption at 450 nm to 800 nm is measured with an ultraviolet-visible spectrophotometer (Shimadzu Corporation UV2400-PC) and the λmax absorption intensity of the main absorption is normalized to 1.0. The minimum intensity was calculated and listed in the table below.

Other Examples and Comparative Examples In the above, the same procedure was followed except that the phthalocyanine compound was replaced with the following phthalocyanine compound. The results are shown below.

Example 101
Preparation of green colored film (Preparation of colored curable composition (coating solution))
Components in the following composition were mixed to prepare a colored curable composition.
<Composition>
-Exemplified compound A-1 ... 6 parts by mass-Yellow colored product (said (Y-2)) ... Absorption intensity ratio (absorption at 450 nm / absorption at 650 nm) is in the range of 0.95 to 1.05. The amount of yellow coloring was adjusted and added to fit.
-(T-1) ... 103.4 parts by mass-(U-1) ... 212.2 parts by mass (solid content conversion value: 84.9 parts by mass)
-(V-1)-21.2 parts by mass-(W-1)-3.5 parts by mass-(X-1)-71.9 parts by mass- (X-2) ... 3.6 parts by mass, (Z-1) ... 0.06 parts by mass

<Light resistance>
The colored film was irradiated with a xenon lamp at 200,000 lux for 10 hours (equivalent to 2 million lux · h), and then the chromaticity change, that is, ΔEab value was measured. A smaller ΔEab value indicates better light resistance.

<Heat resistance>
After the colored film was heated at 230 ° C. for 60 minutes, the chromaticity change, that is, ΔEab value was measured. A smaller ΔEab value indicates better light resistance.

<Residue>
A colored film was prepared in the same manner as in Example 1, then immersed in a sodium bicarbonate / sodium carbonate aqueous solution adjusted to 23 ° C. and pH 12.0 as a developer for 60 seconds, and then washed with ion-exchanged water at 23 ° C. Then, a substrate for residue evaluation was prepared.
The substrate after development was measured with 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 as follows.
2: Maximum absorbance less than 0.05 1: Maximum absorbance 0.05 or more

Other Examples and Comparative Examples In the above, the phthalocyanine compound, the photopolymerization initiator, the photopolymerization initiator auxiliary agent, and the yellow colored substance were replaced with those described in the following table, and the others were performed in the same manner. The results are shown below.

The said phthalocyanine compound respond | corresponds to the number of the above-mentioned exemplary compound.
As is clear from the above results, it was found that by using the colored curable composition of the present invention, a color filter having a small minimum absorption value of the transmission part, excellent transparency and good heat resistance can be realized.

Claims (15)

A colored curable composition containing a halogen-substituted phthalocyanine compound represented by the following general formula (1).
General formula (1)
(In General Formula (1), R ^{1 to} R ⁴ are each a substituent represented by the following General Formula (2) or a halogen atom, and p, q, r, and s are each 0 to 4, the number of substituents represented by the general formula (2) in the general formula (1) is 1 to 12. R represents a hydrogen atom or a monovalent substituent, and M is Cu. Zn, V (= O), Mg, Ni, Ti (= O), Mg, Sn, or Si.)
General formula (2)
(In General Formula (2), X ¹ represents —O—, Ar ¹ represents a phenylene group which may have a substituent, R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, n1 represents an integer of 1 to 3. When n1 is 2 or 3, a plurality of R ¹¹ may be the same or different, and Y ¹ is —O— and R ¹² may have a substituent. Or a sulfonyl group having a substituent, or Y ¹ is —C (═O) — and R ¹² has an alkoxy group which may have a substituent, or a substituent. Is a good alkylamino group.) The colored curable composition according to claim 1, wherein the halogen atom represented by R ^{1 to} R ⁴ represents Br or Cl, and M represents Cu or Zn. The colored curable composition of Claim 1 or 2 whose sum of p, q, r, and s of General formula (1) is 12-16. Furthermore, the colored curable composition of any one of Claims 1-3 containing a carboxylic acid type | system | group binder. Furthermore, the colored curable composition of any one of Claims 1-4 containing a polymeric compound and a photoinitiator. The colored curable composition according to claim 5, wherein the photopolymerization initiator is an oxime compound or a biimidazole compound. Furthermore, the colored curable composition of any one of Claims 1-6 containing a yellow coloring agent. The colored curable composition according to claim 7, wherein the yellow colorant is an azo dye or a monomethine dye. The colored curable composition according to claim 7, wherein the yellow colorant is a monomethine dye represented by the following general formula (5).
General formula (5)
(In General Formula (5), R ¹¹ represents an alkyl group or a vinyl group, and R ¹² represents an aromatic ring group having a substituent.) The halogen-substituted phthalocyanine compound is R in the general formula (1) ¹ ~ R ^Four The colored curable composition according to any one of claims 1 to 9, wherein 4 to 12 of them are halogen atoms. The colored curable composition according to any one of claims 1 to 10 , wherein the compound represented by the general formula (1) is a halogen-substituted phthalocyanine compound represented by the following general formula (1 ').
General formula (1 ')
(In the general formula (1 ′), R ^{1 to} R ⁴ are each a substituent, a bromine atom, or a chlorine atom represented by the following general formula (2 ′), and p, q, r, and s are: Each represents 0 to 4, and the sum of p, q, r and s is 12 to 16. Of R ^{1 to} R ^{4 in} the general formula (1 ′) , 4 to 12 are bromine atoms or chlorine atoms In general formula (1 ′), the number of substituents represented by general formula (2 ′) is 4 to 12. R represents a hydrogen atom, and M represents Cu or Zn.)
General formula (2 ')
(In the general formula (2 '), X ¹ represents -O-, Ar ¹ is table a phenylene group, Y ¹ is -O- or -C (= O) - represents, R ¹¹ is a hydrogen atom or Represents a methyl group, and n1 represents an integer of 1 to 3. When n1 is 2 or 3, a plurality of R ¹¹ may be the same or different, and when Y ¹ represents —O—, R ¹² represents an alkyl And when Y ¹ represents —C (═O) —, R ¹² represents an alkoxy group or an alkylamino group.) A color filter having a colored layer using the colored curable composition according to any one of claims 1 to 11. A colored curable composition according to any one of claims 1 to 11 is applied on a substrate to form a colored layer, and the formed colored layer is exposed in a pattern, developed and colored. Forming a region, and a method of manufacturing a color filter. The liquid crystal display device, organic electroluminescent element, or solid-state image sensor which has a color filter of Claim 12 . A phthalocyanine compound represented by the following general formula (1 ′).
General formula (1 ')
(In the general formula (1 ′), R ^{1 to} R ⁴ are each a substituent, a bromine atom, or a chlorine atom represented by the following general formula (2 ′), and p, q, r, and s are: Each represents 0 to 4, and the sum of p, q, r and s is 12 to 16. Of R ^{1 to} R ^{4 in} the general formula (1 ′) , 4 to 12 are bromine atoms or chlorine atoms In general formula (1 ′), the number of substituents represented by general formula (2 ′) is 4 to 12. R represents a hydrogen atom, and M represents Cu or Zn.)
General formula (2 ')
(In the general formula (2 '), X ¹ represents -O-, Ar ¹ is table a phenylene group, Y ¹ is -O- or -C (= O) - represents, R ¹¹ is a hydrogen atom or Represents a methyl group, and n1 represents an integer of 1 to 3. When n1 is 2 or 3, a plurality of R ¹¹ may be the same or different, and when Y ¹ represents —O—, R ¹² represents an alkyl And when Y ¹ represents —C (═O) —, R ¹² represents an alkoxy group or an alkylamino group.)