JP2015183126A - Colorant and method of producing the same, and coloring composition and color filter using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coloring composition for obtaining a color filter having excellent storage stability and high contrast and a method of producing the same, and a coloring composition using the same.SOLUTION: This invention provides a method of producing a colorant obtained by the reaction between a phthalocyanine compound with an OH group bonding to the central metal and a reaction reagent represented by the formulae (2) and (3), where Z1 is -POR1R2, -COR3, or -SO2R4; Z2 is a substituent different from Z1, representing -POR5R6, -COR7, or -SO2R8; W1, W2 independently represent a halogen atom or a hydroxy group.

Description

  The present invention relates to a colorant used in the production of a color filter used in a color liquid crystal display device, a color image pickup tube element, and the like, a production method thereof, and a coloring composition using the same.

  In the liquid crystal display device, a liquid crystal layer sandwiched between two polarizing plates controls the amount of light passing through the first polarizing plate by controlling the degree of polarization of light passing through the first polarizing plate. The type using twisted nematic (TN) type liquid crystal is the mainstream. A liquid crystal display device is capable of color display by providing a color filter between two polarizing plates, and has recently been used in televisions, personal computer monitors, and the like. There is an increasing demand for higher quality and high color reproducibility.

  A color filter is a surface of a transparent substrate such as glass, in which two or more kinds of fine band (striped) filter segments of different hues are arranged in parallel or crossing each other, or fine filter segments are arranged vertically and horizontally. It is made up of those arranged in In general, it is often formed of three color filter segments of red, green, and blue. Each segment is as fine as several microns to several hundreds of microns, and is arranged in a predetermined arrangement for each hue. .

  Generally, in a color liquid crystal display device, a transparent electrode for driving a liquid crystal is formed on a color filter by vapor deposition or sputtering, and an alignment film for aligning the liquid crystal in a certain direction is further formed thereon. Yes. In order to sufficiently obtain the performance of these transparent electrodes and alignment films, the formation thereof must generally be performed at a high temperature of 200 ° C. or higher, preferably 230 ° C. or higher. For this reason, at present, as a method for producing a color filter, a method called a pigment dispersion method using a pigment having excellent heat resistance and light resistance as a colorant is mainly used.

  In the production of a green filter, it is common to use various phthalocyanine compounds as a colorant, and many proposals for color filter compositions containing these compounds have been made. For example, Patent Document 1 and Patent Document 2 disclose a color filter composition containing an aluminum phthalocyanine compound. However, the pigment composition containing these aluminum phthalocyanine compounds has a problem that the storage stability required for color filter applications is not sufficient. Further, when used as a color filter, there is a problem that high contrast cannot be obtained due to poor dispersibility.

  Patent Document 3 discloses an aluminum phthalocyanine compound that provides a color filter coloring composition having good heat resistance and light resistance, Patent Document 4 discloses an aluminum phthalocyanine compound using a carboxylic acid, and Patent Document 5 discloses a sulfone. An aluminum phthalocyanine compound using an acid is disclosed. However, when these aluminum phthalocyanine compounds are used for color filters, those that satisfy all the characteristics of heat resistance, light resistance, and high brightness have not been obtained.

  Furthermore, Patent Document 6 discloses an example in which a phthalocyanine compound produced by a reaction between a phosphate ester and an aluminum phthalocyanine compound is used as a color filter coloring composition. However, the reaction between the phosphate ester and the aluminum phthalocyanine compound produces three types of components. However, it is difficult to control the ratio of these components, and when used as a color filter, it satisfies lightness and tinting strength. Was not obtained.

JP 2003-4930 A JP 2004-333817 A JP 2012-155231 A JP 2013-145334 A JP 2013-145335 A JP 2013-171063 A

  An object of the present invention is to provide a colored composition for obtaining a color filter having excellent storage stability and high contrast, a method for producing the same, and a colored composition using the same. Moreover, the further subject of this invention is providing the color filter which has high brightness with the photosensitive coloring composition for color filters using said coloring composition.

The inventors of the present invention have made the present invention as a result of intensive studies to solve the above problems.
That is, an embodiment of the present invention is a method for producing a colorant obtained by reacting a phthalocyanine compound represented by the following general formula (1) with a reaction reagent, and at least two kinds of reaction reagents are used as reaction reagents. Is a method for producing a colorant.

[Wherein, X _{1 to} X ₄ are each independently an alkyl group which may have a substituent, an aryl group which may have a substituent, a cycloalkyl group which may have a substituent, or a substituent. A heterocyclic group which may have a group, an alkoxyl group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent or a substituent Represents an optionally substituted arylthio group.
Y _{1 to} Y ₄ each independently represent a halogen atom, a nitro group, an optionally substituted phthalimidomethyl group or an optionally substituted sulfamoyl group.
M ₁ represents Al.
m _{1 to} m ₄ and n _{1 to} n ₄ each independently represents an integer of 0 to 4. However, m ₁ + n ₁ , m ₂ + n ₂ , m ₃ + n ₃ and m ₄ + n ₄ are each 0 to 4, and may be the same or different. ]

  In addition, an embodiment of the present invention relates to the above production method, wherein two kinds of reaction reagents represented by the following general formula (2) and the following general formula (3) are used as the reaction reagents.

[Wherein, Z ₁ represents -POR ₁ R ₂ , -COR ₃ , -SO ₂ R _4] .
R ₁ and R ₂ are each independently a hydrogen atom, a hydroxyl group, an alkyl group that may have a substituent, an aryl group that may have a substituent, an alkoxyl group that may have a substituent, or a substituent. Represents an aryloxy group which may have a group, and R ₁ and R ₂ may be bonded to each other to form a ring.
R ₃ represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group, or an optionally substituted heterocyclic group. Represents a cyclic group.
R ₄ represents a hydroxyl group, an alkyl group that may have a substituent, an aryl group that may have a substituent, or a heterocyclic group that may have a substituent.
Z ₂ is a substituent different from Z ₁ and represents —POR ₅ R ₆ , —COR ₇ , —SO ₂ R ₈ .
R ₅ and R ₆ are each independently a hydrogen atom, a hydroxyl group, an alkyl group that may have a substituent, an aryl group that may have a substituent, an alkoxyl group that may have a substituent, or a substituent. Represents an aryloxy group which may have a group, and R ₅ and R ₆ may combine with each other to form a ring.
R ₇ is a hydrogen atom, an alkyl group that may have a substituent, a cycloalkyl group that may have a substituent, an aryl group that may have a substituent, or a heterocycle that may have a substituent. Represents a cyclic group.
R ₈ represents a hydroxyl group, an alkyl group that may have a substituent, an aryl group that may have a substituent, or a heterocyclic group that may have a substituent.
W ₁ and W ₂ each independently represent a halogen atom or a hydroxyl group. ]

An embodiment of the present invention also relates to the above production method, wherein Z ₁ is —POR ₁ R ₂ .

An embodiment of the present invention also relates to the above production method, wherein Z ₂ is —POR ₅ R ₆ .

  Moreover, the embodiment of this invention is related with the coloring agent obtained by the said manufacturing method.

Moreover, the embodiment of the present invention relates to a colored composition comprising at least a colorant, a binder resin and an organic solvent, wherein the colorant is the colorant.

  Moreover, the embodiment of this invention is related with the said coloring composition which contains a resin type dispersing agent further.

  Moreover, the embodiment of this invention is related with the said coloring composition further containing a yellow coloring agent.

  Also, in an embodiment of the present invention, the yellow colorant is C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150 and C.I. I. The present invention relates to the coloring composition which is at least one selected from CI Pigment Yellow 185.

  In addition, an embodiment of the present invention relates to the colored composition further comprising a photopolymerizable monomer and / or a photopolymerization initiator.

  In an embodiment of the present invention, in the color filter including at least one red filter segment, at least one green filter segment, and at least one blue filter segment, at least one green filter segment is formed by the coloring composition. Relates to the color filter.

According to the present invention, it is possible to obtain a coloring composition having good storage stability and high contrast. Moreover, the color filter which has high brightness can be provided with the photosensitive coloring composition for color filters using said coloring composition.

Hereinafter, the present invention will be described in detail.
In the present application, when “(meth) acryloyl”, “(meth) acryl”, “(meth) acrylic acid”, “(meth) acrylate”, or “(meth) acrylamide” is particularly described, Unless otherwise indicated, “acryloyl and / or methacryloyl”, “acrylic and / or methacrylic”, “acrylic acid and / or methacrylic acid”, “acrylate and / or methacrylate”, or “acrylamide and / or methacrylamide”, respectively. It shall represent. “CI” mentioned in the specification means a color index (CI). In the present specification, the “coloring composition for color filter” may be simply referred to as “coloring composition”.

(Coloring agent)
The colorant of the present invention is obtained by reacting the phthalocyanine compound represented by the general formula (1) with at least two kinds of reaction reagents.

(Phthalocyanine compound represented by the general formula (1))
First, each substituent in X < ₁ > -X < ₄ > in General formula (1) is demonstrated.
Examples of the alkyl group which may have a substituent include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a neopentyl group, an n-hexyl group, an n-octyl group, Linear or branched alkyl group such as stearyl group, 2-ethylhexyl group, trichloromethyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, 2,2-dibromoethyl group, 2,2 , 3,3-tetrafluoropropyl group, 2-ethoxyethyl group, 2-butoxyethyl group, 2-nitropropyl group, benzyl group, 4-methylbenzyl group, 4-tert-butylbenzyl group, 4-methoxybenzyl group , Alkyl groups having a substituent such as 4-nitrobenzyl group and 2,4-dichlorobenzyl group.
Among these, a linear or branched alkyl group is preferable, and a linear or branched alkyl group having 1 to 8 carbon atoms is more preferable.

As the aryl group which may have a substituent, the “aryl group” includes an aryl group such as a phenyl group, a p-tolyl group, a naphthyl group, a 6-methyl-2-naphthyl group, an anthryl group, p- Bromophenyl group, p-nitrophenyl group, p-methoxyphenyl group, 2,4-dichlorophenyl group, pentafluorophenyl group, 2-aminophenyl group, 2-methyl-4-chlorophenyl group, 4-hydroxy-1-naphthyl An aryl group having a substituent such as a group, 4,5,8-trichloro-2-naphthyl group, anthraquinonyl group, and 2-aminoanthraquinonyl group.
Among these, an aryl group or an aryl group substituted with one chlorine atom, bromine atom or nitro group is preferred, an aryl group is more preferred, a tolyl group or a phenyl group is further preferred, and a phenyl group is particularly preferred.

  Examples of the cycloalkyl group which may have a substituent include a cycloalkyl group such as a cyclopentyl group, a cyclohexyl group and an adamantyl group, a substituent such as a 2,5-dimethylcyclopentyl group and a 4-tert-butylcyclohexyl group. And a cycloalkyl group having the same.

Examples of the heterocyclic group that may have a substituent include a heterocyclic group such as a pyridyl group, an N-oxopyridyl group, a pyrazyl group, a piperidino group, a pyranyl group, a morpholino group, and an acridinyl group. Examples include a heterocyclic group having a substituent such as -methylpyridyl group, N-methylpiperidyl group, N-methylpyrrolyl group.
Of these, a pyridyl group or an N-oxopyridyl group is preferable.

Examples of the alkoxyl group which may have a substituent include methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, tert-butoxy group, neopentyloxy group, 2,3-dimethyl- Linear or branched alkoxyl group such as 3-pentyloxy group, n-hexyloxy group, n-octyloxy group, stearyloxy group, 2-ethylhexyloxy group, trichloromethoxy group, trifluoromethoxy group, 2,2 , 2-trifluoroethoxy group, 2,2,3,3-tetrafluoropropoxy group, 2,2-ditrifluoromethylpropoxy group, 2-ethoxyethoxy group, 2-butoxyethoxy group, 2-nitropropoxy group, benzyl The alkoxyl group which has substituents, such as an oxy group, is mentioned.
Among these, a linear or branched alkoxyl group is preferable, and a linear or branched alkoxyl group having 1 to 8 carbon atoms is more preferable.

As the aryloxy group which may have a substituent, aryloxy groups such as phenoxy group, p-methylphenoxy group, naphthyloxy group, anthryloxy group, p-nitrophenoxy group, p-methoxyphenoxy group, 2 , 4-dichlorophenoxy group, pentafluorophenoxy group, aryloxy group having a substituent such as 2-methyl-4-chlorophenoxy group.
Among these, an aryloxy group or an aryloxy group substituted with one chlorine atom, bromine atom or nitro group is preferred, an aryloxy group is more preferred, a p-methylphenoxy group or a phenoxy group is further preferred, and a phenoxy group is particularly preferred. preferable.

  Examples of the alkylthio group which may have a substituent include methylthio group, ethylthio group, propylthio group, butylthio group, pentylthio group, hexylthio group, octylthio group, decylthio group, dodecylthio group, octadecylthio group and other alkylthio groups, methoxyethyl Examples include an alkylthio group having a substituent such as a thio group, an aminoethylthio group, a benzylaminoethylthio group, a methylcarbonylaminoethylthio group, and a phenylcarbonylaminoethylthio group.

  As the arylthio group which may have a substituent, arylthio groups such as phenylthio group, 1-naphthylthio group, 2-naphthylthio group, 9-anthrylthio group, chlorophenylthio group, trifluoromethylphenylthio group, cyanophenylthio group , An arylthio group having a substituent such as a nitrophenylthio group, a 2-aminophenylthio group, and a 2-hydroxyphenylthio group.

Of each substituent in X _{1 to} X _4, an alkyl group which may have a substituent is preferable, a linear or branched alkyl group is more preferable, and a linear or branched alkyl group having 1 to 8 carbon atoms is preferable. Particularly preferred.

Next, each substituent in Y < ₁ > -Y < ₄ > in General formula (1) is demonstrated.
Examples of the halogen atom include halogen atoms such as fluorine, chlorine and bromine, and chlorine or bromine is preferable.
As the phthalimidomethyl group which may have a substituent, in addition to the phthalimidomethyl group (C ₆ H ₄ (CO) ₂ N—CH ₂ —), the groups mentioned as X _{1 to} X ₄ as substituents can be mentioned. It is done.
Examples of the sulfamoyl group which may have a substituent include the sulfamoyl group (H ₂ NSO ₂ —) and the groups listed as X _{1 to} X ₄ as substituents.

Of each substituent in Y _{1 to} Y ₄ , a halogen atom or a sulfamoyl group is preferable, a halogen atom is more preferable, and a chlorine atom or a bromine atom is further preferable.

m _{1 to} m ₄ and n _{1 to} n ₄ each independently represents an integer of 0 to 4.
As a preferred embodiment, it is preferable that m _{1 to} m ₄ are all 0 and / or n _{1 to} n ₄ are all 0. When m _{1 to} m ₄ and n _{1 to} n ₄ are all 0, that is, when there is no substituent on the phthalocyanine ring, it can be said to be one of particularly preferred embodiments.

As combinations of X _{1 to} X ₄ , Y _{1 to} Y ₄ , m _{1 to} m ₄ , and n _{1 to} n ₄ listed above, combinations of the above preferred embodiments are preferable. The following (A) to (C) can be exemplified as particularly preferred embodiments.
(A) When n _{1 to} n ₄ are 0 and m _{1 to} m ₄ are 0.
(B) X ₁ ~X ₄ alkyl group, when n ₁ ~n ₄ is 1, m ₁ ~m ₄ is zero.
(C) A case where Y _{1 to} Y ₄ are halogen atoms, n _{1 to} n ₄ are 0, and m _{1 to} m ₄ are 1.

(Reaction reagent)
The reaction reagent to be reacted with the phthalocyanine compound represented by the general formula (1) means a reaction reagent capable of reacting with a hydroxyl group bonded to M ₁ in the general formula (1). If it reacts with the hydroxyl group bonded to M ₁ , a part of the reaction reagent is a hydrogen atom on the phthalocyanine ring in the phthalocyanine compound represented by the general formula (1), or X _{1 to} X ₄ , Y _{1 to} Y ₄ . You may react with the group represented. In this production method, at least two kinds of reaction reagents are used as reaction reagents, but three or more kinds of reaction reagents may be used. The reaction reagent may be mixed in advance and reacted with the phthalocyanine compound represented by the general formula (1), or may be added sequentially while changing the order of addition during the reaction, but a colorant of uniform quality is obtained. Above, it is preferable to mix beforehand and make it react with the phthalocyanine compound represented by General formula (1).

  As the reaction reagent, it is preferable to use two kinds of reaction reagents represented by the general formula (2) and the general formula (3). Here, each substituent in General formula (2) and General formula (3) is demonstrated.

Here, the alkyl group that may have a substituent in R _{1 to} R ₈ has the same meaning as the alkyl group that may have a substituent.
Among these, a linear or branched alkyl group is preferable, and a linear or branched alkyl group having 1 to 8 carbon atoms is more preferable.

The aryl group which may have a substituent in R _{1 to} R ₈ has the same meaning as the aryl group which may have a substituent.
Among these, an aryl group or an aryl group substituted with one chlorine atom, bromine atom or nitro group is preferred, an aryl group is more preferred, a tolyl group or a phenyl group is further preferred, and a phenyl group is particularly preferred.

The alkoxyl group which may have a substituent in R ₁ , R ₂ , R ₅ and R ₆ has the same meaning as the alkoxyl group which may have a substituent.
Among these, a linear or branched alkoxyl group is preferable, and a linear or branched alkoxyl group having 1 to 8 carbon atoms is more preferable.

The aryloxy group which may have a substituent in R ₁ , R ₂ , R ₅ and R ₆ has the same meaning as the aryloxy group which may have a substituent.
Among these, an aryloxy group or an aryloxy group substituted by one with a chlorine atom, a bromine atom or a nitro group is preferable, an aryloxy group is more preferable, and a phenoxy group is particularly preferable.

The cycloalkyl group that may have a substituent in R ₃ and R ₇ has the same meaning as the cycloalkyl group that may have a substituent.

The heterocyclic group which may have a substituent in R ₃ , R ₄ , R ₇ and R ₈ has the same meaning as the heterocyclic group which may have a substituent.
Of these, a pyridyl group or an N-oxopyridyl group is preferable.

As the reaction agent represented by the general formula (2), it is preferable that Z ₁ is —POR ₁ R ₂ from the viewpoint of improving brightness and contrast when used in a color filter. Furthermore, from the viewpoint of dispersibility and color characteristics, at least one of R ₁ and R ₂ is preferably an aryl group that may have a substituent or an aryloxy group that may have a substituent. R ₁ and R ₂ are more preferably aryl groups or aryloxy groups, and R ₁ and R ₂ are more preferably phenyl groups or phenoxy groups.

As the reaction reagent represented by the general formula (3), it is preferable that Z ₂ is —POR ₅ R ₆ from the viewpoint of improving brightness and contrast when used in a color filter. Furthermore, from the viewpoint of dispersibility and color characteristics, at least one of R ₅ and R ₆ is preferably an aryl group that may have a substituent or an aryloxy group that may have a substituent. , R ₅ and R ₆ are more preferably aryl groups or aryloxy groups. However, since the production method of the present invention is characterized by using at least two types of reaction reagents, R ₅ and R ₆ are not the same as R ₁ and R ₂ .

As combinations of the above-mentioned reaction reagents, combinations of the above-described preferred embodiments are preferable. As a particularly preferred embodiment, in the reaction reagent represented by the general formula (2), Z ₁ is —POR ₁ R ₂ , and R ₁ and R ₂ are each an aryl group or a halogen group which may have a halogen group. has been is also an aryloxy group, W ₁ is hydroxyl group, the reaction reagent represented by the general formula (3), Z ₂ is -POR ₅ R _6, R ₅ and R ₆ are halogen group And an aryloxy group which may have a halogen group and W ₂ is a hydroxyl group.

  Therefore, specific examples of the reaction reagent represented by the general formula (2) and the following general formula (3) include diphenyl phosphate, di-p-tolyl phosphate, diphenylphosphinic acid, di-p-tolylphosphinic acid, Bis (4-chlorophenyl) phosphate, bis (4-bromophenyl) phosphate, bis (3,5-dichlorophenyl) phosphate, bis (4-nitrophenyl) phosphate, dimethyl phosphate, dibutyl phosphate, phosphoric acid Bis (2-ethylhexyl), nicotinic acid, nicotinic acid N-oxide, benzenesulfonic acid, p-toluenesulfonic acid and the like can be mentioned, but not limited thereto.

As an embodiment of the present invention, R ₁ and R _{2 in} the general formula (2) both have a phenyl group, and R ₅ and R _{6 in} the general formula (3) both have an aryl group or a substituent having a substituent. Particularly preferred is an aryloxy group which may be substituted. In this case, the reaction reagent represented by the general formula (2): The reaction reagent represented by the general formula (3) is preferably in the range of 95: 5 to 60:40 (molar ratio).

  The ratio of the phthalocyanine compound represented by the general formula (1) and the reaction reagent is within the range of the phthalocyanine compound represented by the general formula (1): reaction reagent = 1.0 to 1.2 (molar ratio). preferable.

  When two types of reaction reagents represented by general formula (2) and general formula (3) are used as reaction reagents, phthalocyanine represented by the following general formula (4) and general formula (5) as the main component A colorant containing the compound can be obtained.

[Wherein, X _{1 to} X ₄ are each independently an alkyl group which may have a substituent, an aryl group which may have a substituent, a cycloalkyl group which may have a substituent, or a substituent. A heterocyclic group which may have a group, an alkoxyl group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent or a substituent Represents an optionally substituted arylthio group.
Y _{1 to} Y ₄ each independently represent a halogen atom, a nitro group, an optionally substituted phthalimidomethyl group or an optionally substituted sulfamoyl group.
M ₁ represents Al.
m _{1 to} m ₄ and n _{1 to} n ₄ each independently represents an integer of 0 to 4. However, m ₁ + n ₁ , m ₂ + n ₂ , m ₃ + n ₃ and m ₄ + n ₄ are each 0 to 4, and may be the same or different.
Z _{1 is, -POR 1 R 2, -COR 3} , represents a -SO ₂ R _4.
R ₁ and R ₂ are each independently a hydrogen atom, a hydroxyl group, an alkyl group that may have a substituent, an aryl group that may have a substituent, an alkoxyl group that may have a substituent, or a substituent. Represents an aryloxy group which may have a group, and R ₁ and R ₂ may be bonded to each other to form a ring.
R ₃ represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group, or an optionally substituted heterocyclic group. Represents a cyclic group.
R ₄ represents a hydroxyl group, an alkyl group that may have a substituent, an aryl group that may have a substituent, or a heterocyclic group that may have a substituent.
Z ₂ is a substituent different from Z ₁ and represents —POR ₅ R ₆ , —COR ₇ , —SO ₂ R ₈ .
R ₅ and R ₆ are each independently a hydrogen atom, a hydroxyl group, an alkyl group that may have a substituent, an aryl group that may have a substituent, an alkoxyl group that may have a substituent, or a substituent. Represents an aryloxy group which may have a group, and R ₅ and R ₆ may combine with each other to form a ring.
R ₇ is a hydrogen atom, an alkyl group that may have a substituent, a cycloalkyl group that may have a substituent, an aryl group that may have a substituent, or a heterocycle that may have a substituent. Represents a cyclic group.
R ₈ represents a hydroxyl group, an alkyl group that may have a substituent, an aryl group that may have a substituent, or a heterocyclic group that may have a substituent. ]

The contents of the phthalocyanine compound represented by the general formula (4) and the phthalocyanine compound represented by the general formula (5) contained in the obtained colorant are represented by the general formula (2) and the general formula (3). It is possible to adjust by the ratio of the reaction reagent to be prepared.

(Solvent used during reaction)
An organic solvent used when reacting the phthalocyanine compound represented by the general formula (1) with at least two kinds of reaction reagents (referred to as a “reaction solvent” in order to distinguish it from an “organic solvent” used in a colored composition) Are) monohydric alcohol solvents such as methanol, ethanol, isopropanol, and t-butanol, ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, thiodiglycol, dithiodiglycol, 2-methyl- Polyhydric alcohol solvents such as 1,3-propanediol, 1,2,6-hexanetriol, acetylene glycol derivatives, glycerin or trimethylolpropane, 1-methyl-2-pyrrolidinone, 1,3-dimethyl -2-imidazolidinone, -Pyrrolidinone, ε-caprolactam, formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropanamide, hexamethylphosphoric triamide, urea, Alternatively, an amide solvent such as tetramethylurea, and other lower monohydric alcohols such as ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl (or ethyl) ether, or triethylene glycol monoethyl (or butyl) ether Alkyl ether solvents, ethylene glycol dimethyl ether (monoglyme), diethylene glycol dimethyl ether (diglyme), or triethylene glycol dimethyl ether Polyether solvents such as (triglyme), sulfur-containing solvents such as sulfolane, dimethyl sulfoxide, or 3-sulfolene, polyfunctional solvents such as diacetone alcohol and diethanolamine, acetic acid, maleic acid, docosahexaenoic acid, trichloroacetic acid, or Examples include carboxylic acid solvents such as trifluoroacetic acid, sulfonic acid solvents such as methanesulfonic acid or trifluorosulfonic acid, and aromatic hydrocarbon solvents such as benzene, toluene, and xylene. It is preferable to use a monovalent alcohol solvent such as methanol, ethanol or isopropyl alcohol, or an aprotic polar solvent such as dimethyl sulfoxide, N, N-dimethylformamide or 1-methyl-2-pyrrolidinone. Among them, dimethyl sulfoxide, N, N-dimethylformamide, 1-methyl-2-2, which has good solubility of the colorant produced by reacting with the phthalocyanine compound represented by the general formula (1) and two kinds of reaction reagents. More preferred are aprotic polar solvents such as pyrrolidinone. These reaction solvents can be used alone or in admixture of two or more.

  As a method for removing the reaction solvent after completion of the reaction, a method known in the art can be used. For example, after performing suction filtration or pressure filtration, there is a method in which the reaction solvent is compatible with the reaction solvent used, washed with another organic solvent having a low boiling point, and then dried and removed. When the reaction solvent is a water-soluble organic solvent, it is desirable that the reaction solution is mixed with water and then removed by filtration and washing with water.

  In order to obtain fine particles of the colorant, the colorant obtained by the above method is dissolved in a soluble solvent and then precipitated with a solvent insoluble in the colorant, or the reaction solution and the colorant Examples thereof include a method of mixing with an insoluble solvent.

(Coloring composition)
The colored composition of the present invention comprises at least the colorant of the present invention, a binder resin, and an organic solvent.

<Binder resin>
Examples of the binder resin contained in the coloring composition include conventionally known thermoplastic resins and thermosetting resins.

  Examples of the thermoplastic resin include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, and polyurethane resin. Polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, polyimide resins, and the like.

  When used as a coloring composition for a color filter, the spectral transmittance is preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. Moreover, when using with the form of an alkali image development type colored resist, it is preferable to use the alkali-soluble vinyl resin which copolymerized the acidic group containing ethylenically unsaturated monomer. In order to further improve the photosensitivity, an energy ray curable resin having an ethylenically unsaturated active double bond can also be used.

  Examples of the alkali-soluble resin obtained by copolymerizing an acidic group-containing ethylenically unsaturated monomer include resins having an acidic group such as a carboxyl group or a sulfone group. Specific examples of the alkali-soluble resin include an acrylic resin having an acidic group, an α-olefin / (anhydrous) maleic acid copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, or Examples include isobutylene / (anhydrous) maleic acid copolymer. Among these, at least one resin selected from an acrylic resin having an acidic group and a styrene / styrene sulfonic acid copolymer, particularly an acrylic resin having an acidic group, is preferably used because of its high heat resistance and transparency.

  Energy ray curable resins having ethylenically unsaturated active double bonds include reactive substitution of isocyanate groups, aldehyde groups, epoxy groups, etc. on polymers having reactive substituents such as hydroxyl groups, carboxyl groups, amino groups, etc. A resin in which a photo-crosslinkable group such as a (meth) acryloyl group or a styryl group is introduced into the polymer by reacting a (meth) acrylic compound having a group or cinnamic acid is used. In addition, polymers containing acid anhydrides such as styrene-maleic anhydride copolymer and α-olefin-maleic anhydride copolymer are half-esterified with a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. A modified version is also used.

  A thermoplastic resin having both alkali-soluble performance and energy ray curing performance is also preferable as the photosensitive coloring composition for color filters.

  The following are mentioned as a monomer which comprises the said thermoplastic resin. For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) Acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, or ethoxypolyethylene Glycol (meth) acrylate of (meth) acrylates,

  Alternatively, (meth) acrylamide (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, acryloylmorpholine, etc. Acrylamides, styrenes, styrenes such as α-methylstyrene, ethyl vinyl ethers, n-propyl vinyl ethers, isopropyl vinyl ethers, n-butyl vinyl ethers, vinyl ethers such as isobutyl vinyl ethers, fatty acid vinyls such as vinyl acetate or vinyl propionate Kind.

  Alternatively, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimide ethane 1,6-bismaleimidehexane, 3-maleimidopropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimide Coumarin, 4,4′-bismaleimide diphenylmethane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, N, N′-1,3-phenylenedimaleimide, N, N′-1,4- Phenylene dimaleimide, N- (1-pyrenyl) maleimide, N- (2,4,6-trichlorophenyl) maleimide, N- (4-aminophenyl) maleimide, N- (4-nitrophenyl) maleimide, N-benzyl Maleimide, N-bromomethyl-2,3-dichloromaleimide, N-sc N-imidyl-3-maleimidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N- [4- (2-benzimidazolyl) phenyl N-substituted maleimides such as maleimide and 9-maleimide acridine.

  In particular, it is preferable to have a structural unit derived from an N-substituted maleimide, and among them, cyclohexylmaleimide, methylmaleimide, ethylmaleimide, and 1,2-bismaleimideethane are preferable from the viewpoint of heat resistance, and cyclohexylmaleimide is particularly preferable.

  Examples of the thermosetting resin include epoxy resin, benzoguanamine resin, rosin-modified maleic acid resin, rosin-modified fumaric acid resin, melamine resin, urea resin, and phenol resin.

  When the coloring composition contains a thermosetting resin, it is preferable in terms of heat resistance. For example, an epoxy resin and a melamine resin can be more preferably used, and a melamine resin is particularly preferable, and a methylolimino group is particularly preferable. More preferred are melamine compounds having the above or condensates thereof.

  The thermosetting resin is preferably added in the range of 5 to 60 parts by weight with respect to 100 parts by weight of the colorant.

  The weight average molecular weight (Mw) of the binder resin is preferably in the range of 5,000 to 100,000, more preferably in the range of 8,000 to 50,000 in order to disperse the colorant preferably. The number average molecular weight (Mn) is preferably in the range of 2,500 to 50,000, and the value of Mw / Mn is preferably 10 or less.

  Here, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are connected to four separation columns in series in the gel permeation chromatography “HLC-8120GPC” manufactured by Tosoh Corporation. This is a polystyrene equivalent molecular weight measured using “TSK-GEL SUPER H5000”, “H4000”, “H3000”, and “H2000” manufactured by the company and using tetrahydrofuran as the mobile phase.

  When using a binder resin as a coloring composition for a color filter, from the viewpoint of dispersibility, developability, and heat resistance, a colorant adsorbing group and a carboxyl group that acts as an alkali-soluble group during development, a colorant carrier, and The balance of the aliphatic group and aromatic group acting as an affinity group for the organic solvent is important for dispersibility, developability, and durability, and it is preferable to use a resin having an acid value of 20 to 300 mgKOH / g.

The binder resin can be used in an amount of 20 to 500% by weight based on the total weight of the colorant.
<Organic solvent>
Examples of the organic solvent used in the coloring composition include ethyl lactate, benzyl alcohol, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, 3-ethoxypropion Ethyl acetate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone , M-xylene, m-diethylbenzene, m-dichlorobenzene, N, N-dimethyl Cetamide, N, N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene , Sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene Glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate Ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, Diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol Monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether , Propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, Down benzyl alcohol, methyl isobutyl ketone, methyl cyclohexanol, acetic acid n- amyl acetate n- butyl, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters.

  From the viewpoint of dispersibility, glycol acetates such as ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, aromatic alcohols such as benzyl alcohol, and cyclohexanone It is preferable to use ketones such as

  An organic solvent can be used individually by 1 type or in mixture of 2 or more types. In addition, since the organic solvent can adjust the colored composition to an appropriate viscosity to form a filter segment having a desired uniform film thickness, the total weight of the colorant is 100 to 100% by weight, and is 500 to 4000% by weight. It is preferable to use it in the quantity.

(Resin type dispersant)
The resin-type dispersant has a colorant affinity part that has the property of adsorbing to the added colorant, and a part that is compatible with the colorant carrier, and adsorbs to the added colorant to disperse in the colorant carrier. It works to stabilize. Specific examples of resin-type dispersants include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamine salts. , Polysiloxane, long-chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, modified products thereof, amides formed by reaction of poly (lower alkyleneimine) and polyester having a free carboxyl group, and salts thereof Oil-soluble dispersants such as, (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, etc. Resin, water-soluble polymer, polyester, modified poly Acrylate-based, ethylene oxide / propylene oxide adduct, phosphoric ester or the like is used, they may be used alone or in combination, it is not necessarily limited thereto.

  Among the above-mentioned dispersants, a polymer dispersant having a basic functional group is preferable because the viscosity of the dispersion is lowered and a high contrast is exhibited with a small addition amount, and a nitrogen atom-containing graft copolymer or side chain is preferable. Nitrogen atom-containing acrylic block copolymers and urethane polymer dispersants having functional groups including tertiary amino groups, quaternary ammonium bases, nitrogen-containing heterocycles and the like are preferred.

  The resin-type dispersant is preferably used in an amount of about 5 to 200% by weight based on the total amount of the colorant, and more preferably about 10 to 100% by weight from the viewpoint of film formability.

  Commercially available resin-type dispersants include Dsperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170 manufactured by Big Chemie Japan. 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155 or Anti-Terra-U, 203, 204, or BYK- P104, P104S, 220S, 6919, or SOLPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000 manufactured by Nihon Lubrizol Corporation, such as Lactimon, Lactimon-WS or Bykumen. 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc., Ciba Japan EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320 , 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 755 , 1101,120,150,1501,1502,1503, etc., Ajinomoto Fine-Techno Co., Ltd. of AJISPER PA111, PB711, PB821, PB822, PB824, and the like.

  The amount of the resin-type dispersant and surfactant added is preferably 0.1 to 55% by weight, more preferably 0.1 to 45% by weight, based on the total amount of the colorant (100% by weight). It is.

(Yellow colorant)
The colored composition of the present invention may further contain a yellow colorant within a range that does not impair the effects of the present invention in order to further adjust the chromaticity. Although there is no restriction | limiting in particular as a yellow coloring agent, Generally, a yellow dye or a yellow pigment is mentioned.

  As yellow dye, azo dye, azo metal complex dye, anthraquinone dye, indigo dye, thioindigo dye, phthalocyanine dye, diphenylmethane dye, triphenylmethane dye, xanthene dye, thiazine dye, cationic dye, cyanine dye, nitro dye, quinoline dye , Naphthoquinone dyes and oxazine dyes.

  Therefore, specific examples of yellow dyes include C.I. I. Acid Yellow 2,3, 4, 5, 6, 7, 8, 9, 9: 1, 10, 11, 11: 1, 12, 13, 14, 15, 16, 17, 17: 1, 18, 20, 21, 22, 23, 25, 26, 27, 29, 30, 31, 33, 34, 36, 38, 39, 40, 40: 1, 41, 42, 42: 1, 43, 44, 46, 48, 51, 53, 55, 56, 60, 63, 65, 66, 67, 68, 69, 72, 76, 82, 83, 84, 86, 87, 90, 94, 105, 115, 117, 122, 127, 131, 132, 136, 141, 142, 143, 144, 145, 146, 149, 153, 159, 166, 168, 169, 172, 174, 175, 178, 180, 183, 187, 188, 189, 190, 191, 192, 199 Etc.

  In addition, C.I. I. Direct Yellow 1, 2, 4, 5, 12, 13, 15, 20, 24, 25, 26, 32, 33, 34, 35, 41, 42, 44, 44: 1, 45, 46, 48, 49, 50, 51, 61, 66, 67, 69, 70, 71, 72, 73, 74, 81, 84, 86, 90, 91, 92, 95, 107, 110, 117, 118, 119, 120, 121, 126, 127, 129, 132, 133, 134 etc. are also mentioned.

  In addition, C.I. I. Basic Yellow 1, 2, 5, 11, 13, 14, 15, 19, 21, 24, 25, 28, 29, 37, 40, 45, 49, 51, 57, 79, 87, 90, 96, 103, 105, 106 and the like.

  In addition, C.I. I. Solvent Yellow 2, 3, 4, 7, 8, 10, 11, 12, 13, 14, 15, 16, 18, 19, 21, 22, 25, 27, 28, 29, 30, 32, 33, 34, 40, 42, 43, 44, 45, 47, 48, 56, 62, 64, 68, 69, 71, 72, 73, 77, 79, 81, 82, 83, 85, 88, 89, 90, 93, 94, 98, 104, 107, 114, 116, 117, 124, 130, 131, 133, 135, 138, 141, 143, 145, 146, 147, 157, 160, 162, 163, 167, 172, 174, 175, 176, 177, 179, 181, 182, 183, 184, 185, 186, 187, 188, 190, 191, 192, 194, 195 and the like are also included.

  In addition, C.I. I. Disperse Yellow 1, 2, 3, 5, 7, 8, 10, 11, 13, 13, 23, 27, 33, 34, 42, 45, 48, 51, 54, 56, 59, 60, 63, 64 67, 70, 77, 79, 82, 85, 88, 93, 99, 114, 118, 119, 122, 123, 124, 126, 163, 184, 184: 1, 202, 211, 229, 231, 232 233, 241, 245, 246, 247, 248, 249, 250, 251 and the like.

  As the yellow colorant, organic or inorganic pigments can be used alone or in admixture of two or more, and pigments having high color developability and high heat resistance, particularly pigments having high heat resistance, are preferred. Organic pigments are used. As the organic pigment, commercially available ones can be used, and natural pigments and inorganic pigments can be used in combination according to the desired hue of the filter segment.

Below, the specific example of the yellow organic pigment which can be used for the said coloring composition is shown. Examples of yellow pigments include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, Yellow pigments such as 182, 185, 187, 188, 192, 193, 194, 196, 198, 199, 213, 214 can be used. In particular, from the viewpoint of heat resistance, light resistance, and brightness of the filter segment, C.I. I. Pigment Yellow 138, 139, 150, and 185 are preferable.
These yellow colorants can be used alone or in combination of two or more depending on the desired color characteristics.

  A green colorant can also be added for the purpose of adjusting the hue. Examples of the green colorant include C.I. I. And green pigments such as CI Pigment Green 7, 10, 36, 37, and 58.

  When the yellow colorant is used in combination with the colorant obtained by the production method of the present invention, the mass ratio of yellow colorant / colorant obtained by the production method of the present invention is in the range of 40/60 to 90/10. preferable.

(Miniaturization of colorant)
In order to obtain high brightness and high contrast, the colorant can be suitably used as a color filter colorant by making the colorant particles finer by a salt milling process or the like as necessary. The primary particle diameter of the colorant is preferably 10 nm or more in order to improve dispersibility in the colorant carrier. Moreover, in order to obtain a filter segment with high contrast, the thickness is preferably 80 nm or less. A particularly preferred range is 20 to 60 nm.

  Salt milling is a process of heating a mixture of a colorant, a water-soluble inorganic salt, and a water-soluble organic solvent using a kneader such as a kneader, two-roll mill, three-roll mill, ball mill, attritor, or sand mill. After mechanically kneading, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt serves as a crushing aid, and the colorant is crushed using the high hardness of the inorganic salt during salt milling. By optimizing the conditions at the time of subjecting the colorant to salt milling, it is possible to obtain a colorant having a sharp particle size distribution in which the primary particle size is very fine and the width of the distribution is widened.

  As the water-soluble inorganic salt, sodium chloride, barium chloride, potassium chloride, sodium sulfate and the like can be used, but sodium chloride (salt) is preferably used from the viewpoint of cost. The water-soluble inorganic salt is preferably used in an amount of 50 to 2000% by weight, and most preferably 300 to 1000% by weight based on the total weight of the pigment (100% by weight) from the viewpoint of both processing efficiency and production efficiency.

  The water-soluble organic solvent functions to wet the colorant and water-soluble inorganic salt, and is not particularly limited as long as it dissolves (mixes) in water and does not substantially dissolve the inorganic salt to be used. However, since the temperature rises during salt milling and the solvent is likely to evaporate, those having a high boiling point of 120 ° C. or higher are preferable from the viewpoint of safety. Such as, for example, 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol , Triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol, etc. Is used. These water-soluble organic solvents are preferably used in an amount of 5 to 1000% by weight, and most preferably 50 to 500% by weight, based on the total weight of the colorant (100% by weight).

  When salt milling the colorant, a resin may be added as necessary. Here, the type of resin used is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like can be used. The resin used is solid at room temperature, preferably insoluble in water, and more preferably partially soluble in the water-soluble organic solvent. The amount of resin used is preferably in the range of 2 to 200% by weight based on the total weight of the colorant (100% by weight).

<Dispersing aid>
When dispersing the colorant in the colorant carrier, a dispersion aid such as a pigment derivative, a resin-type dispersant, and a surfactant can be appropriately used. The dispersion aid is excellent in dispersion of the colorant and has a large effect of preventing reaggregation of the colorant after dispersion. Therefore, a dispersion composition is used to disperse the colorant in the colorant carrier using the dispersion aid. When used, a color filter having a high spectral transmittance can be obtained.

(Dye derivative)
Examples of the dye derivative include a compound obtained by introducing a basic substituent, an acidic substituent, or a phthalimidomethyl group which may have a substituent into an organic pigment, anthraquinone, acridone, or triazine. 63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, etc. can be used. These can be used alone or in combination of two or more.

  The blending amount of the pigment derivative is preferably 0.5% by weight or more, more preferably 1% by weight or more, most preferably based on the total amount of the additive colorant (100% by weight) from the viewpoint of improving the dispersibility of the additive colorant. Preferably it is 3 weight% or more. Further, from the viewpoint of heat resistance and light resistance, the total amount of the added colorant is preferably 40% by weight or less, more preferably 35% by weight or less, based on the total amount (100% by weight).

(Surfactant)
Surfactants include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate , Anionic surfactants such as monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate ester, Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Nonionic surfactants such as alkyl ether phosphates, polyoxyethylene sorbitan monostearate and polyethylene glycol monolaurate, chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts, alkyldimethylamino Examples include amphoteric surfactants such as alkylbetaines such as betaine acetate and alkylimidazolines, and these can be used alone or in admixture of two or more, but are not necessarily limited thereto.

  The compounding amount in the case of adding the resin type dispersant and the surfactant is preferably 0.1 to 55% by weight, more preferably 0.1 to 45% by weight based on the total amount of the added colorant (100% by weight). %. When the blending amount of the resin-type dispersant and the surfactant is less than 0.1% by weight, it is difficult to obtain the added effect. When the blending amount is more than 55% by weight, the dispersion is adversely affected by the excessive dispersant. May affect.

<Method for producing colored composition>
The colored composition of the present invention is a mixture of a colorant obtained by reacting at least a phthalocyanine compound represented by the general formula (1) and a reaction reagent, a binder resin, an organic solvent, and if necessary, a resin-type dispersant. In addition, it can be produced by dispersing using various dispersing machines such as a three-roll mill, a two-roll mill, a sand mill, a kneader, or an attritor. Moreover, the coloring composition of this invention can also be manufactured by mixing the colorant separately dispersed in a binder resin and an organic solvent.

  In this way, when the colorant is dispersed in the binder resin using a disperser, the dispersed particle size becomes smaller as the dispersion proceeds, the transparency increases, and the contrast ratio increases. In particular, a good contrast ratio can be obtained from about 300 nm. On the other hand, when the dispersion progresses and the dispersed particle size becomes small, the viscosity of the dispersion increases and the thixotropic property tends to increase. When used as a photosensitive coloring composition for a color filter, it is required to have a low viscosity and a Newtonian flow because it is required to be coated with a thin film and to have a smooth coating surface. For this reason, it is preferable to suppress the dispersed particle size to about 100 nm in consideration of the viscosity and thixotropic property preferable for normal use. Thus, by using a colorant having an average primary particle size of 100 nm or less and controlling the degree of dispersion so that the average particle size of the dispersed particles is in the range of 50 nm to 150 nm, the increase in viscosity and thixotropic property are minimized. A colorant dispersion with a very high contrast ratio can be obtained.

<Removal of coarse particles>
The colored composition of the present invention is subjected to centrifugation or filtration using a sintered filter, a membrane filter, or the like, so that coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably coarse particles of 0.5 μm or more. It is preferable to remove the mixed dust. Thus, it is preferable that a coloring composition does not contain a particle | grain of 0.5 micrometer or more substantially. More preferably, it does not contain particles of 0.3 μm or less.

<Photosensitive coloring composition for color filter>
The colored composition of the present invention can be used as a photosensitive colored composition for a color filter by further adding a photopolymerizable monomer and / or a photopolymerization initiator.

(Photopolymerizable monomer)
Photopolymerizable monomers that can be added to the colored composition of the present invention include monomers or oligomers that are cured by ultraviolet rays or heat to produce a transparent resin, and these are used alone or in combination of two or more. It can be used by mixing. The amount of the monomer is preferably 5 to 400% by weight based on the total weight of the colorant (100% by weight), and more preferably 10 to 300% by weight from the viewpoint of photocurability and developability. preferable.

  Examples of monomers and oligomers that are cured by ultraviolet rays or heat to produce a transparent resin include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate. , Cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglycy Luether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodeca Nyl (meth) acrylate, ester acrylate, methylolated melamine (meth) acrylate ester, epoxy (meth) acrylate, urethane acrylate and other acrylic esters and methacrylate esters, (meth) acrylic acid, styrene, vinyl acetate, Hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl Examples include, but are not necessarily limited to, til (meth) acrylamide, N-vinylformamide, acrylonitrile and the like.

<Photopolymerization initiator>
When the colored composition of the present invention is cured by ultraviolet irradiation and a filter segment is formed by a photolithographic method, it is added in the form of a solvent development type or alkali development type colored resist material by adding a photopolymerization initiator or the like. Can be prepared. The blending amount when using the photopolymerization initiator is preferably 2 to 200% by weight based on the total amount of the colorant, and 5 to 150% by weight from the viewpoint of photocurability and developability. More preferred.

  Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- Hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1 Acetophenone compounds such as-[4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; benzoin, benzoin Methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or Benzoin compounds such as benzyl dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, or 3,3 ′, Benzophenone compounds such as 4,4′-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4-diethylthioxanthone Thioxanthone compounds such as 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-meth) Cyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloro Methyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2 -(4-Methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4-trichloromethyl- Triazine compounds such as (4′-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyloxime) )], Or oxime ester compounds such as O- (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4,6- Phosphine compounds such as trimethylbenzoyl) phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone; borate compounds; carbazole A imidazole compound; a titanocene compound, or the like.

  These photopolymerization initiators can be used alone or in combination of two or more at any ratio as required. These photopolymerization initiators are preferably 2 to 200% by weight based on the total amount of the colorant in the coloring composition (100% by weight), and 5 to 150% by weight from the viewpoint of photocurability and developability. % Is more preferable.

<Sensitizer>
Furthermore, the photosensitive coloring composition for a color filter of the present invention can contain a sensitizer.

  Sensitizers include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives , Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives, and other polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, Azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, Trapirazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine Derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes, or Michler's ketone derivatives, α-acyloxy esters, acylphosphine oxides, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl Anthraquinone, 4,4'-diethylisophthalophenone, 3,3 'or 4,4'-tetra (t-butylperoxycarbonyl) benzo Phenone, 4,4'-diethylaminobenzophenone, etc. are mentioned.

  More specifically, edited by Shin Okawara et al., “Dye Handbook” (1986, Kodansha), edited by Shin Okawara et al., “Chemistry of Functional Dye” (1981, CMC), edited by Tadasaburo Ikemori et al. Examples include, but are not limited to, sensitizers described in "Special Functional Materials" (1986, CMC). In addition, a sensitizer that absorbs light from the ultraviolet region to the near infrared region can also be contained.

  Two or more kinds of sensitizers may be used in any ratio as required. The blending amount when using the sensitizer is preferably 3 to 60% by weight based on the total weight of the photopolymerization initiator contained in the colored composition (100% by weight). From the viewpoint of developability, it is more preferably 5 to 50% by weight.

<Amine compound>
Moreover, the coloring composition for color filters of this invention can be made to contain the amine compound which has a function which reduces the dissolved oxygen.

  Such amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminobenzoate. Examples include ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, and N, N-dimethylparatoluidine.

<Leveling agent>
In order to improve the leveling property of the composition on the transparent substrate, it is preferable to add a leveling agent to the coloring composition for a color filter of the present invention. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in the main chain is preferable. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning, BYK-333 manufactured by Big Chemie. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK Chemie. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can be used in combination. In general, the leveling agent content is preferably 0.003 to 0.5% by weight based on the total weight of the coloring composition (100% by weight).

  Particularly preferred as a leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, having a hydrophilic group but low solubility in water, and when added to a coloring composition, It has the characteristics of low surface tension reduction ability, and it is useful to have good wettability to the glass plate despite its low surface tension reduction ability. Those that can sufficiently suppress the chargeability can be preferably used. As a leveling agent having such preferable characteristics, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. Examples of the polyalkylene oxide unit include a polyethylene oxide unit and a polypropylene oxide unit, and dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

  In addition, the bonding form of the polyalkylene oxide unit with dimethylpolysiloxane includes a pendant type in which the polyalkylene oxide unit is bonded in the repeating unit of dimethylpolysiloxane, a terminal-modified type in which the end of dimethylpolysiloxane is bonded, and dimethylpolysiloxane. Any of linear block copolymer types in which they are alternately and repeatedly bonded may be used. Dimethylpolysiloxane having a polyalkylene oxide unit is commercially available from Toray Dow Corning Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ. -2207, but is not limited thereto.

  An anionic, cationic, nonionic or amphoteric surfactant can be supplementarily added to the leveling agent. Two or more kinds of surfactants may be mixed and used.

  Anionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, alkyl diphenyl ether disulfonic acid Sodium, lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Examples include esters.

  Examples of the chaotic surfactant that is supplementarily added to the leveling agent include alkyl quaternary ammonium salts and their ethylene oxide adducts. Nonionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate And amphoteric surfactants such as alkyl dimethylamino acetic acid betaine and alkylimidazolines, and fluorine-based and silicone-based surfactants.

<Curing agent, curing accelerator>
Moreover, in order to assist hardening of a thermosetting resin, the coloring composition for color filters of this invention may contain the hardening | curing agent, the hardening accelerator, etc. as needed. As the curing agent, phenolic resins, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like are effective, but are not particularly limited to these, and thermosetting resins. Any curing agent may be used as long as it can react with the. Among these, a compound having two or more phenolic hydroxyl groups in one molecule and an amine curing agent are preferable. Examples of the curing accelerator include amine compounds (for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl). -N, N-dimethylbenzylamine etc.), quaternary ammonium salt compounds (eg triethylbenzylammonium chloride etc.), blocked isocyanate compounds (eg dimethylamine etc.), imidazole derivative bicyclic amidine compounds and salts thereof (eg Imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2- D Ru-4-methylimidazole, etc.), phosphorus compounds (eg, triphenylphosphine, etc.), guanamine compounds (eg, melamine, guanamine, acetoguanamine, benzoguanamine, etc.), S-triazine derivatives (eg, 2,4-diamino-6) -Methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6 Methacryloyloxyethyl-S-triazine / isocyanuric acid adduct, etc.) can be used. These may be used alone or in combination of two or more. As content of the said hardening accelerator, 0.01 to 15 weight% is preferable with respect to the thermosetting resin whole quantity.

<Other additive components>
The colored composition of the present invention can contain a storage stabilizer in order to stabilize the viscosity of the composition over time. Moreover, in order to improve adhesiveness with a transparent substrate, adhesion improving agents, such as a silane coupling agent, can also be contained.

  Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and methyl ethers thereof, t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Organic phosphines, phosphites and the like can be mentioned. The storage stabilizer can be used in an amount of 0.1 to 10% by weight based on the total amount of the colorant (100% by weight).

  Examples of the adhesion improver include vinyl silanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane and vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (amino Ethyl) γ-aminopropyltrie Xisilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl Examples include silane coupling agents such as aminosilanes such as -γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. The adhesion improver can be used in an amount of 0.01 to 10% by weight, preferably 0.05 to 5% by weight, based on the total amount of the colorant in the coloring composition (100% by weight).

<Color filter>
The color filter of this invention comprises the filter segment formed using the coloring composition of this invention. Examples of the color filter include those comprising a red filter segment, a green filter segment, and a blue filter segment, and the filter segment is coated with a photosensitive coloring composition for a color filter by a spin coating method or a die coating method, By irradiating active energy rays such as ultraviolet rays, the portion to be a filter segment is cured, and then developed to form on the substrate.

  The colored composition produced according to the present invention is used to form a green filter segment, and the other filter segments of each color are formed using a conventionally used red photosensitive coloring composition and blue photosensitive coloring composition. can do.

  As each color photosensitive coloring composition other than the photosensitive coloring composition in the present invention, each color photosensitive coloring composition, the resin, the photopolymerizable composition, and the like are used to form each color photosensitive coloring composition. Can do.

  The red filter segment can be formed using a normal red coloring composition containing a red pigment and a pigment carrier. Examples of the red coloring composition include C.I. I. Pigment Red 7, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 57: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 122, 146, 168, 169, 177, 178, 184, 185, 187, 200, 202, 208, 210, 242, 246, 254, 255, 264, 270, 272, 273, 274, 276, 277, 278, 279, 280, Red pigments such as 281, 282, 283, 284, 285, 286, or 287 are used. Further, a basic dye or a salt-forming compound of an acid dye exhibiting a red color can also be used.

  The red coloring composition includes C.I. I. Pigment orange 43, 71, 73 or the like and / or C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181 182,185,187,188,193,194,198,199,213, or may be used in combination of a yellow pigment 214, and the like.

  Examples of the blue coloring composition include C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64 and the like are used, and C.I. I. Purple violet pigments such as CI Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, and 50 can be used in combination. Further, a basic dye or a salt forming compound of an acidic dye that exhibits blue or purple can be used.

  As the transparent substrate, glass plates such as soda lime glass, low alkali borosilicate glass and non-alkali alumino borosilicate glass, and resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate are used. In addition, a transparent electrode made of indium oxide, tin oxide, or the like may be formed on the surface of the glass plate or the resin plate in order to drive the liquid crystal after forming the panel.

<Color filter manufacturing method>
The color filter of the present invention can be produced by a printing method or a photolithography method.

  The formation of filter segments by printing methods allows patterning by simply printing and drying the colored composition prepared as a printing ink, making it a low cost and excellent mass productivity as a color filter manufacturing method. Yes. Furthermore, it is possible to print a fine pattern having high dimensional accuracy and smoothness by the development of printing technology. In order to perform printing, it is preferable that the ink does not dry and solidify on the printing plate or on the blanket. Further, it is important to control the fluidity of the ink on the printing press, and the viscosity of the ink can be adjusted with a dispersant or extender pigment.

  When forming a filter segment by a photolithography method, the photosensitive coloring composition prepared as the solvent developing type or alkali developing type coloring resist material is spray coated, spin coated, slit coated, roll coated, etc. on a transparent substrate. The coating method is applied so that the dry film thickness is 0.2 to 5 μm. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film. Then, after immersing in a solvent or alkali developer or spraying the developer by spraying or the like to remove the uncured portion to form a desired pattern, the same operation is repeated for other colors to produce a color filter. be able to. Furthermore, in order to accelerate the polymerization of the colored resist material, heating can be performed as necessary. According to the photolithography method, a color filter with higher accuracy than the above printing method can be manufactured.

In development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution.
In order to increase the UV exposure sensitivity, after coating and drying the colored resist material, a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. Then, ultraviolet exposure can be performed.

  The color filter of the present invention can be produced by an electrodeposition method, a transfer method or the like in addition to the above method, but the color filter coloring composition of the present invention can be used in any method. The electrodeposition method is a method for producing a color filter by using a transparent conductive film formed on a substrate and forming each color filter segment on the transparent conductive film by electrophoresis of colloidal particles. . The transfer method is a method in which a filter segment is formed in advance on the surface of a peelable transfer base sheet, and this filter segment is transferred to a desired substrate.

  A black matrix can be formed in advance before forming each color filter segment on a transparent substrate or a reflective substrate. As the black matrix, a chromium, chromium / chromium oxide multilayer film, an inorganic film such as titanium nitride, or a resin film in which a light-shielding agent is dispersed is used, but is not limited thereto. In addition, a thin film transistor (TFT) may be formed in advance on the transparent substrate or the reflective substrate, and then each color filter segment may be formed. In addition, an overcoat film, a transparent conductive film, or the like is formed on the color filter of the present invention as necessary.

  Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In Examples and Comparative Examples, “parts” means “parts by mass” and “%” means “% by mass” unless otherwise specified. The values shown as preparation ratio and production ratio mean molar ratio. “PGMAC” means propylene glycol monomethyl ether acetate, and “Me” means a methyl group.

  In the following examples, the number average molecular weight and the weight average molecular weight were determined by connecting four separation columns in series in a gel permeation chromatography (GPC) “HLC-8120GPC” manufactured by Tosoh Corporation. It is a value in terms of polystyrene measured using “TSK-GEL SUPER H5000”, “H4000”, “H3000”, and “H2000” manufactured by Tosoh Corporation in this order and using tetrahydrofuran as the mobile phase.

<Particle size of colorant>
The average primary particle diameter of the colorant (hereinafter sometimes simply referred to as “particle diameter”) was measured (calculated) by the method shown below. A sample for measurement was prepared by adding propylene glycol monomethyl ether acetate to the colorant powder, adding a small amount of Disperbyk-161 as a resin-type dispersant, and dispersing the mixture in a water bath of an ultrasonic cleaner for 1 minute. This sample was photographed with a transmission electron microscope (TEM) to photograph six leaves (for six fields of view) at a magnification of 50,000 to 100,000, allowing observation of primary particles of 200 or more colorants. The size was measured. Specifically, the minor axis diameter and major axis diameter of primary particles of each colorant were measured in units of 1 nm, and the average value was defined as the particle diameter of the colorant of each particle.

<Analysis of colorants>
The identification of the compound contained in the colorant and the determination of the ratio were performed using a MALDI mass spectrometer autoflex III (hereinafter referred to as TOF-MS) manufactured by Bruker Daltonics. The identification was made by matching the molecular ion peak of the mass spectrum obtained by mass spectrometry with the mass number obtained by calculation. In addition, regarding the composition, in the obtained mass spectrum, each molecular ion peak intensity (relative intensity) with respect to the sum of all molecular ion peak intensity was calculated, and the relative intensity ratio was regarded as a molar ratio.

<Manufacture of binder resin>
233 parts of propylene glycol monomethyl ether acetate was charged into a separable four-necked flask equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe and a stirring device, and the temperature was raised to 80 ° C. From the tube, 20 parts of methacrylic acid, 30 parts of paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 19 parts of benzyl methacrylate, 16 parts of methyl methacrylate, 15 parts of 2-hydroxyethyl methacrylate, and 2, A mixture of 1.33 parts of 2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the mixture was further heated and stirred at 80 ° C. for 3 hours to obtain a binder resin solution. After cooling to room temperature, about 2 g of binder resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. Propylene glycol monomethyl was added to the previously synthesized resin solution so that the nonvolatile content was 20% by weight. Ether ether was added to prepare a binder resin solution. As a result of GPC measurement, this binder resin solution had a weight average molecular weight (Mw) of 16000.

<Method for producing colorant>

First, prior to the production of the colorant, the production of the phthalocyanine compound represented by the general formula (1) will be described.
(Production of phthalocyanine compound (a))
While introducing nitrogen gas into a flask equipped with a thermometer, cooling pipe, nitrogen gas introduction pipe, and stirring device, 1250 parts of n-amyl alcohol, 225 parts of phthalodinitrile, and 78 parts of anhydrous aluminum chloride were added and stirred. did. To this was added 266 parts of DBU (1,8-Diazabicclo [5.4.0] undec-7-ene), and the mixture was refluxed at 136 ° C. for 5 hours under a nitrogen atmosphere. The reaction solution cooled to 30 ° C. with stirring was poured into a mixed solvent consisting of 5000 parts of methanol and 10,000 parts of water to obtain a blue slurry. This slurry was filtered, washed with a mixed solvent consisting of 2000 parts of methanol and 4000 parts of water, and dried to obtain 135 parts of chloroaluminum phthalocyanine.
Next, 100 parts of chloroaluminum phthalocyanine was added to 1200 parts of concentrated sulfuric acid at 25 ° C. in a reaction vessel. The mixture was stirred at 40 ° C. for 3 hours, and the sulfuric acid solution was poured into 24000 parts of cold water at 3 ° C. The blue precipitate was filtered, washed with water and dried to obtain 92 parts of a phthalocyanine compound (a) having the following structure.

(Production of phthalocyanine compound (b))
In the production of the phthalocyanine compound (a), a phthalocyanine compound (b) was obtained in the same manner except that 250 parts of 4-methylphthalodinitrile was used instead of phthalodinitrile. The structure of the phthalocyanine compound (b) obtained is shown below.

(Production of phthalocyanine compound (c))
In the production of the phthalocyanine compound (a), a phthalocyanine compound (c) was obtained in the same manner except that 285 parts of 4-chlorophthalodinitrile was used instead of phthalodinitrile. The structure of the phthalocyanine compound (c) obtained is shown below.

[Example 1]
While introducing nitrogen gas into a flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirring device, 500 parts of N, N-dimethylformamide, 45 parts of a phthalocyanine compound (a), diphenyl phosphate 16 as a reaction reagent 2 parts and 3.5 parts of diphenylphosphinic acid were added, and the reaction was carried out by heating at 50 ° C. for 4 hours under a nitrogen atmosphere. In addition, the reaction reagent used here (19.7 parts in total) has a molar ratio of diphenyl phosphate: diphenylphosphinic acid = 80: 20. After completion of the reaction, the reaction solution was sucked into an aspirator in which water was passed at a water pressure of 3.5 kg / cm ² , and the produced colorant was precipitated to obtain a slurry. The obtained slurry was filtered, washed with water, dried and pulverized to obtain 58 parts of blue colorant 1 (PB-1). From the measurement result of TOF-MS, PB-1 obtained was a mixture of the phthalocyanine compound of Compound 1 and Compound 2, and the component ratio (molar ratio) of Compound 1 and Compound 2 was 82:18. The average primary particle diameter of the obtained colorant was 24 nm.

[Example 2]
Example 1 was repeated except that 16.2 parts diphenyl phosphate and 3.5 parts diphenylphosphinic acid were changed to 19.2 parts diphenyl phosphate and 0.9 parts diphenylphosphinic acid, and 60 parts blue Colorant 2 (PB-2) was obtained.

[Example 3]
Production of blue colorant 1 (PB-1) except that 16.2 parts diphenyl phosphate and 3.5 parts diphenylphosphinic acid were changed to 12.2 parts diphenyl phosphate and 17.5 parts diphenylphosphinic acid In the same manner, 59 parts of blue colorant 3 (PB-3) was obtained.

[Example 4]
Except for changing 3.5 parts of diphenylphosphinic acid to 5.2 parts of bis (4-chlorophenyl) phosphate, it was carried out in the same manner as in the production of blue colorant 1 (PB-1), and 62 parts of blue colorant 4 ( PB-4) was obtained.

[Example 5]
Except for changing 3.5 parts of diphenylphosphinic acid to 5.5 parts of bis (4-nitrophenyl) phosphate, this was carried out in the same manner as in the production of blue colorant 1 (PB-1), and 58 parts of blue colorant 5 (PB-5) was obtained.

[Example 6]
Blue Colorant 1 (PB-1) except that 16.2 parts diphenyl phosphate was changed to 18.2 parts and 3.5 parts diphenylphosphinic acid was changed to 3.3 parts bis (4-bromophenyl) phosphate. In the same manner as in the above, 62 parts of blue colorant 6 (PB-6) was obtained.

[Example 7]
Blue Colorant 1 (PB) except that 16.2 parts diphenyl phosphate was changed to 3.6 parts diphenylphosphinic acid and 3.5 parts diphenylphosphinic acid was changed to 6.6 parts bis (4-bromophenyl) phosphate. -1) was carried out in the same manner as in Example 1 to obtain 60 parts of blue colorant 7 (PB-7).

[Example 8]
Blue Colorant 1 (PB-1) except that 3.5 parts of diphenylphosphinic acid are changed to 2.6 parts of bis (4-chlorophenyl) phosphate and 3.2 parts of bis (3,5-dichlorophenyl) phosphate In the same manner as in the above, 61 parts of blue colorant 8 (PB-8) was obtained.

[Example 9]
Except for changing 45 parts of the phthalocyanine compound (a) to 50 parts of the phthalocyanine compound (b), the same procedure as in the production of the blue colorant 1 (PB-1) was carried out, and 63 parts of the blue colorant 9 (PB-9) was added. Obtained.

[Example 10]
Except for changing 45 parts of phthalocyanine compound (a) to 56 parts of phthalocyanine compound (c), the same procedure as in the production of blue colorant 1 (PB-1) was carried out, and 64 parts of blue colorant 10 (PB-10) was added. Obtained.

[Example 11]
Blue Colorant 1 (PB--) except that 16.2 parts diphenyl phosphate was changed to 13.7 parts dibutyl phosphate and 3.5 parts diphenylphosphinic acid was changed to 5.2 parts bis (2-ethylhexyl) phosphate. It carried out similarly to manufacture of 1), and obtained 57 parts of blue coloring agents 11 (PB-11).

[Example 12]
Production of blue colorant 1 (PB-1), except that 16.2 parts of diphenyl phosphate were changed to 9.0 parts of nicotinic acid N-oxide and 3.5 parts of diphenylphosphinic acid were changed to 2.0 parts of nicotinic acid. And 51 parts of blue colorant 12 (PB-12) was obtained.

[Example 13]
Except for changing 16.2 parts of diphenyl phosphate to 9.0 parts of benzenesulfonic acid and 3.5 parts of diphenylphosphinic acid to 4.2 parts of p-toluenesulfonic acid, the blue colorant 1 (PB-1) It carried out similarly to manufacture and obtained 50 parts of blue colorants 13 (PB-13).

[Comparative Example 1]
Except for changing 16.2 parts of diphenyl phosphate and 3.5 parts of diphenylphosphinic acid to 20.3 parts of diphenyl phosphate, the same procedure as in the production of blue colorant 1 (PB-1) was carried out, 58 parts Of blue colorant 14 (PB-14) was obtained.

[Comparative Example 2]
Except for changing 16.2 parts of diphenyl phosphate and 3.5 parts of diphenylphosphinic acid to 17.7 parts of diphenylphosphine, it was carried out in the same manner as in the production of blue colorant 1 (PB-1), and 56 parts of Blue colorant 15 (PB-15) was obtained.

For the colorants (pigment compositions) prepared in Examples 1 to 13 and Comparative Examples 1 and 2, the reaction reagents used, the charge ratio, the product and its component ratio, and the particle size are shown in Table 1.

<Other colorant production methods>
(Production of colorant (A-1))
C. I. 100 parts of Pigment Green 58 (“FASTGEN GREEN A110” manufactured by DIC), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 6 hours. This kneaded product is poured into 3000 parts of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 24 hours to color. Agent (A-1) was obtained. The average primary particle size was 32.5 nm.

(Production of colorant (A-2))
To 200 parts of methyl benzoate, 47.5 parts of 8-aminoquinaldine, 90.1 parts of tetrachlorophthalic anhydride, and 183.2 parts of benzoic acid are added and heated to 120 ° C. for 4 hours while distilling off water. Stirring was performed. Next, 62.4 parts of 2,3-naphthalenedicarboxylic anhydride was further added to the reaction mixture, heated to 180 ° C., and stirred for 4 hours while distilling off water. After cooling to room temperature, the reaction mixture was added to 1200 parts of ethanol and stirred at room temperature for 1 hour. The precipitated crystals were separated by filtration, further washed with ethanol, and dried under reduced pressure to obtain 174.6 parts (yield: 96%) of the quinophthalone compound (1). As a result of mass spectrometry by TOF-MS, it was identified as the quinophthalone compound (1). Furthermore, C.I. used in the colorant (A-1). I. 100 parts of CI Pigment Green 58 I. Colorant (A-2) was the same as Colorant (A-1) except that it was changed to a mixture of 20 parts of Pigment Yellow 138 (trade name Paliotol Yellow K0961HD, manufactured by BASF) and 80 parts of Quinophthalone Compound (1). ) The average primary particle size was 24.5 nm.

(Production of colorant (A-3))
C.I. used in the colorant (A-1) I. Pigment Green 58 is a C.I. I. A colorant (A-3) was obtained in the same manner as the colorant (A-1) except that it was changed to CI Pigment Yellow 150 (trade name E4GN manufactured by LANXESS). The average primary particle size was 25.5 nm.

(Production of colorant (A-4))
C.I. used in the colorant (A-1) I. Pigment Green 58 is a C.I. I. A colorant (A-4) was obtained in the same manner as the colorant (A-1) except that it was changed to CI Pigment Yellow 185 ("Paliogen Yellow D1155" manufactured by BASF). The average primary particle size was 29.8 nm.

(Production of colorant (A-5))
C.I. used in the colorant (A-1) I. Pigment Green 58 is a C.I. I. A colorant (A-5) was obtained in the same manner as the colorant (A-1), except that it was changed to CI Pigment Yellow 139 ("Paliotol Yellow L 2140 HD" manufactured by BASF). The average primary particle size was 30.9 nm.

<Method for producing pigment derivative>
(Production of dye derivative (Q-1))
According to the synthesis method described in JP-A-2004-067715, a dye derivative (Q-1) was obtained.

(Production of dye derivative (Q-2))
According to the synthesis method described in JP-A-2007-156395, a quinophthalone compound (Q-2) was obtained.

<Method for producing colored composition>
[Example 14]
(Production of colored composition (D-1))
A mixture having the following composition was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 5 hours using zirconia beads having a diameter of 0.5 mm. It filtered with a 0.0 micrometer filter and the coloring composition (D-1) was produced.
Colorant (PB-1) 7.7 parts Colorant (A-1) 3.3 parts Resin-type dispersant solution 1 6.9 parts Acrylic resin solution 2 31.2 parts Propylene glycol monomethyl ether acetate 50.9 parts

[Examples 15 to 32, Comparative Examples 3 to 6]
(Production of colored composition (D-2 to 23))
Coloring is performed in the same manner as in Example 14 except that the total content of the colorant and the pigment derivative is fixed at 11.0 parts, and the types and mass ratios of the colorant and the pigment derivative are changed as described in Table 2. Compositions (D-2 to 23) were obtained.

[Example 33]
(Production of colored composition (D-24))
A mixture having the following composition was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 5 hours using zirconia beads having a diameter of 0.5 mm. It filtered with a 0.0 micrometer filter and the coloring composition (D-24) was produced.
Colorant (PB-1) 7.2 parts Colorant (A-4) 2.7 parts Dye derivative (Q-2) 1.1 parts Resin-type dispersant solution 6.9 parts Acrylic resin solution 1 31.2 Parts Propylene glycol monomethyl ether acetate 50.9 parts

[Example 34, Comparative Examples 7 to 8]
(Production of colored composition (D-25 to 27))
Coloring is performed in the same manner as in Example 33 except that the total content of the colorant and the pigment derivative is fixed to 11.0 parts, and the type and mass ratio of the colorant and the pigment derivative are changed as described in Table 2. A composition (D-25 to 27) was obtained.

<The manufacturing method of a yellow coloring composition>
(Production of colored composition (D-101))
A mixture having the following composition was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 5 hours using zirconia beads having a diameter of 0.5 mm. It filtered with a 0.0 micrometer filter and the coloring composition (D-101) was produced.
Colorant (A-2) 9.9 parts Dye derivative (Q-1) 1.1 parts Resin type dispersant solution 1 6.9 parts Acrylic resin solution 1 31.2 parts Propylene glycol monomethyl ether acetate 50.9 parts

<Evaluation of coloring composition>
The contrast, initial viscosity, and storage stability of the obtained colored composition (D-1 to 27) were evaluated by the following methods. Table 3 shows the evaluation results.

(Contrast evaluation)
The obtained colored composition was formed on a glass substrate having a size of 100 mm × 100 mm and a thickness of 1.1 mm by using a spin coater and changing the number of revolutions so that the film thickness after heat treatment at 230 ° C. was about 1.2 μm. Three coated substrates were prepared so as to be. The drying conditions were 70 ° C. for 20 minutes after coating and further 30 minutes at 230 ° C. The film thickness and contrast ratio were measured, respectively, and the contrast at a film thickness of 1.2 μm was determined from the three points of data by the primary correlation method. It was.

(Evaluation of initial viscosity)
As for the viscosity of the coloring composition, an initial viscosity at 25 ° C. was measured using an E-type viscometer (“ELD viscometer” manufactured by Toki Sangyo Co., Ltd.).
(Evaluation of storage stability)
The obtained colored composition was stored in a thermostat at 40 ° C. for 1 week and accelerated over time, and then the viscosity of the colored composition after aging was measured by the same method as the viscosity measurement, and stored at 40 ° C. for 1 week. The change rate of the viscosity before and after the calculation was calculated and evaluated in two stages according to the following criteria.
○: When the viscosity change rate is within ± 10% and no sediment is formed.
X: When the viscosity change rate exceeds ± 10%, or when a precipitate is generated even when the viscosity change rate is within ± 10%.

  Aluminum phthalocyanine and C.I. I. Examples 14 to 26 in combination with Pigment Green 58 had better contrast ratio, initial viscosity, and storage stability than Comparative Examples 3 to 4. Moreover, the comparison between Examples 27 to 31 and Comparative Example 5 in which the aluminum phthalocyanine of the present invention and the quinophthalone pigment were combined, the aluminum phthalocyanine of the present invention and C.I. I. Comparison between Example 32 and Comparative Example 6 in which CI Pigment Yellow 150 was combined; I. Pigment Yellow 185 in combination with Example 33 and Comparative Example 7, and aluminum phthalocyanine of the present invention with C.I. I. The same result was obtained when Example 34 and Comparative Example 8 were combined with Pigment Yellow 139.

<Method for producing photosensitive coloring composition>
[Example 35]
(Production of photosensitive coloring composition (R-1))
A mixture having the following composition was stirred and mixed uniformly, and then filtered through a 1.0 μm filter to obtain a green photosensitive coloring composition (R-1).
Colored composition (D-1) 24.2 parts Colored composition (D-101) 23.6 parts Acrylic resin solution 2 7.1 parts Photopolymerizable monomer ("Aronix M402" manufactured by Toagosei Co., Ltd.) 3.3 Part Photopolymerization initiator (“Irgacure OXE02” manufactured by Ciba Japan Co., Ltd.) 0.8 part Propylene glycol monomethyl ether acetate 41.0 parts

[Examples 36 to 37, Comparative Examples 9 to 10]
(Production of photosensitive coloring composition (R-2 to 5))
The photosensitive coloring composition was the same as in Example 35 except that the total content of the coloring composition was fixed at 47.8 parts, and the type and blending amount of the coloring composition were changed as described in Table 4. A product (R-2 to 5) was obtained.

<Evaluation of photosensitive coloring composition>
Evaluation of the brightness, contrast, and storage stability of the obtained photosensitive coloring composition (R-1 to 5) was performed by the following methods. Table 4 shows the evaluation results.

(Evaluation of brightness)
The photosensitive coloring composition (R-1 to 5) is applied on a glass substrate of 100 mm × 100 mm and 1.1 mm thickness using a spin coater, and then dried at 70 ° C. for 20 minutes, and an ultra-high pressure mercury lamp Was used, and was exposed to ultraviolet light at an integrated light quantity of 150 mJ / cm ² and developed with an alkaline developer at 23 ° C. to obtain a coated substrate. Then, after heating and cooling at 230 ° C. for 30 minutes, the brightness Y (C) of the obtained coating film substrate was measured using a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.). In the case of the green coated substrate, after the heat treatment at 230 ° C., the chromaticity of y = 0.660 was matched with the C light source. As an alkali developer, sodium carbonate 1.5% by weight, sodium hydrogen carbonate 0.5% by weight, an anionic surface active agent (“Perex NBL” manufactured by Kao Corporation) 8.0% by weight and water 90% by weight Was used. Regarding brightness Y (C), it can be said that there is a clear difference if it is 0.2 points or more.

(Contrast evaluation)
Contrast measurement was performed using the substrate used in the brightness evaluation.

(Evaluation of storage stability)
About the obtained photosensitive coloring composition, the viscosity after an initial stage and acceleration | stimulation with time was measured on 25 degreeC conditions using the E-type viscosity meter ("ELD type viscosity meter" by the Toki Sangyo company). The conditions for aging promotion were stored for 1 week in a 40 ° C. thermostat. The rate of change in viscosity before and after storage at 40 ° C. for 1 week was calculated and evaluated in two stages according to the following criteria.
○: When the viscosity change rate is within ± 10% and no sediment is formed.
X: When the viscosity change rate exceeds ± 10%, or when a precipitate is generated even when the viscosity change rate is within ± 10%.

  As shown in Table 4, the colored composition of the present invention had good brightness, contrast, and storage stability as compared with the conventionally known comparative examples.

<Production of color filter>
First, blue and red photosensitive coloring compositions used for the production of the color filter were produced.

(Preparation of blue photosensitive coloring composition (R-201))
A mixture having the following composition was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 5 hours using zirconia beads having a diameter of 0.5 mm. It filtered with a 0.0 micrometer filter, and produced the blue coloring composition (D-201).
Blue pigment (CI Pigment Blue 15: 6) 7.2 parts Purple Pigment (CI Pigment Violet 23) 4.8 parts Resin Type Dispersant ("EFKA4300" manufactured by Ciba Japan) 1.0 part Acrylic resin solution 1 35.0 parts Propylene glycol monomethyl ether acetate 52.0 parts

Subsequently, the mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1.0 μm filter to prepare a blue photosensitive coloring composition (R-201).
Blue coloring composition (D-201) 34.0 parts Acrylic resin solution 2 15.2 parts Photopolymerizable monomer (“Aronix M400” manufactured by Toagosei Co., Ltd.) 3.3 parts Photopolymerization initiator (Ciba Japan) "Irgacure 907") 2.0 parts Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.4 parts 45.1 parts ethylene glycol monomethyl ether acetate

(Preparation of red photosensitive coloring composition (R-301))
A mixture having the following composition was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 5 hours using zirconia beads having a diameter of 0.5 mm. It filtered with a 0.0 micrometer filter, and produced the red coloring composition (D-301).
Red pigment (CI Pigment Red 254) 6.6 parts Red Pigment (CI Pigment Red 177) 5.4 parts Resin type dispersant ("EFKA4300" manufactured by Ciba Japan) 1.0 part Acrylic resin Solution 1 35.0 parts Propylene glycol monomethyl ether acetate 52.0 parts

Subsequently, a mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1.0 μm filter to prepare a red photosensitive coloring composition (R-301).
Red coloring composition (D-301) 42.0 parts Acrylic resin solution 2 13.2 parts Photopolymerizable monomer (“Aronix M400” manufactured by Toagosei Co., Ltd.) 2.8 parts Photopolymerization initiator (Ciba Japan) "Irgacure 907") 2.0 parts Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.4 parts Ethylene glycol monomethyl ether acetate 39.6 parts

(Production of color filter)
A black matrix was patterned on a glass substrate, and the red photosensitive coloring composition (R-301) of the present invention was applied onto the substrate with a spin coater to form a colored film. The film was irradiated with ultraviolet rays of 150 mJ / cm ² through a photomask using an ultrahigh pressure mercury lamp. Next, spray development was performed with an alkaline developer composed of a 0.2% by weight aqueous sodium carbonate solution to remove unexposed portions, followed by washing with ion-exchanged water. The substrate was heated at 230 ° C. for 30 minutes to obtain a red filter segment. Formed. Here, the red filter segment was adjusted to a chromaticity of x = 0.665 in a C light source (hereinafter also used for green and blue) after heat treatment at 230 ° C. Further, by the same method, the green filter segment is matched with the chromaticity of y = 0.660 using the green photosensitive coloring composition (R-1) of the present invention, and the blue filter segment is blue-sensitive. The color filter was obtained by using the chromatic coloring composition (R-201) so as to meet the chromaticity of y = 0.082 and forming each filter segment.

  By using the photosensitive coloring composition (R-1) of the present invention for forming the green filter segment, it is possible to increase the brightness and contrast of the color filter, and it can be suitably used without any other physical properties. We were able to.

Claims (11)

A method for producing a colorant obtained by reacting a phthalocyanine compound represented by the following general formula (1) with a reaction reagent, wherein at least two kinds of reaction reagents are used as the reaction reagent: Manufacturing method.

[Wherein, X _{1 to} X ₄ are each independently an alkyl group which may have a substituent, an aryl group which may have a substituent, a cycloalkyl group which may have a substituent, or a substituent. A heterocyclic group which may have a group, an alkoxyl group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent or a substituent Represents an optionally substituted arylthio group.
Y _{1 to} Y ₄ each independently represent a halogen atom, a nitro group, an optionally substituted phthalimidomethyl group or an optionally substituted sulfamoyl group.
M ₁ represents Al.
m _{1 to} m ₄ and n _{1 to} n ₄ each independently represents an integer of 0 to 4. However, m ₁ + n ₁ , m ₂ + n ₂ , m ₃ + n ₃ and m ₄ + n ₄ are each 0 to 4, and may be the same or different. ] The method for producing a colorant according to claim 1, wherein two kinds of reaction reagents represented by the following general formula (2) and the following general formula (3) are used as the reaction reagents.

[Wherein, Z ₁ represents -POR ₁ R ₂ , -COR ₃ , -SO ₂ R _4] .
R ₁ and R ₂ are each independently a hydrogen atom, a hydroxyl group, an alkyl group that may have a substituent, an aryl group that may have a substituent, an alkoxyl group that may have a substituent, or a substituent. Represents an aryloxy group which may have a group, and R ₁ and R ₂ may be bonded to each other to form a ring.
R ₃ represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group, or an optionally substituted heterocyclic group. Represents a cyclic group.
R ₄ represents a hydroxyl group, an alkyl group that may have a substituent, an aryl group that may have a substituent, or a heterocyclic group that may have a substituent.
Z ₂ is a substituent different from Z ₁ and represents —POR ₅ R ₆ , —COR ₇ , —SO ₂ R ₈ .
R ₅ and R ₆ are each independently a hydrogen atom, a hydroxyl group, an alkyl group that may have a substituent, an aryl group that may have a substituent, an alkoxyl group that may have a substituent, or a substituent. Represents an aryloxy group which may have a group, and R ₅ and R ₆ may combine with each other to form a ring.
R ₇ is a hydrogen atom, an alkyl group that may have a substituent, a cycloalkyl group that may have a substituent, an aryl group that may have a substituent, or a heterocycle that may have a substituent. Represents a cyclic group.
R ₈ represents a hydroxyl group, an alkyl group that may have a substituent, an aryl group that may have a substituent, or a heterocyclic group that may have a substituent.
W ₁ and W ₂ each independently represent a halogen atom or a hydroxyl group. ] The method for producing a colorant according to claim 1 or 2, wherein Z ₁ is -POR ₁ R ₂ . Z ₂ The method for producing a colorant according to any one of claims 1 to 3, a -POR ₅ R _6. The coloring agent obtained by the manufacturing method in any one of Claims 1-4. A coloring composition comprising at least a coloring agent, a binder resin and an organic solvent, wherein the coloring agent is the coloring agent according to claim 5.   Furthermore, the coloring composition of Claim 6 formed by containing a resin type dispersing agent.   The colored composition according to claim 6 or 7, further comprising a yellow colorant.   The yellow colorant is C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150 and C.I. I. The coloring composition according to claim 8, wherein the coloring composition is at least one selected from CI Pigment Yellow 185.   Furthermore, the coloring composition in any one of Claims 6-9 formed by containing a photopolymerizable monomer and / or a photoinitiator.   11. A color filter comprising at least one red filter segment, at least one green filter segment and at least one blue filter segment, wherein at least one green filter segment is formed by the colored composition according to any one of claims 6 to 10. Color filter that becomes.