JP5583334B2 - Coloring composition for color filter, color filter, and method for producing color filter - Google Patents

Description

  The present invention relates to a color filter coloring composition, a color filter using the color filter coloring composition, and a method for producing the color filter.

  The color filter is a colored photosensitive composition obtained by mixing a polyfunctional monomer, a photopolymerization initiator, an alkali-soluble resin, and other components in a pigment dispersion composition in which an organic pigment or an inorganic pigment is dispersed. In general, it is produced by forming a colored pattern by a photolithography method or the like using this.

In recent years, the use of color filters in liquid crystal display (LCD) applications has tended to expand not only to monitors but also to televisions (TVs). With this trend of expanding applications, advanced color characteristics such as chromaticity and contrast. Has come to be required.
In addition, in the image sensor (solid-state imaging device) application, a device having high color characteristics is also demanded.

It is effective to use a pigment whose primary particle diameter is miniaturized to meet the above requirements. As a method for reducing the primary particle diameter of the pigment, for example, the pigment is combined with a water-soluble inorganic salt such as a synthetic resin that is solid and water-insoluble at room temperature, sodium chloride, and a water-soluble organic solvent that at least partially dissolves the synthetic resin. After kneading mechanically with a kneader or the like (hereinafter, kneading a mixture containing a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent is called salt milling), and then washing with water, the water-soluble inorganic salt and the water-soluble organic There is a method for removing the solvent (see, for example, Patent Document 1).
In this method, since the primary particle pulverization and crystal growth occur in parallel with each other, the final particle size distribution is narrow, and a pigment with a small surface area is obtained in spite of a small average particle size. This method is suitable for applications where a pigment having a large diameter needs to be dispersed at a high concentration.

However, the pigments thus produced often cause severe aggregation in the drying process after desalting, and thus the dispersibility and dispersion stability are often not good. When the dispersibility of the pigment is insufficient, fringes (jagged edges) and surface irregularities occur in the formed coloring pattern, and the chromaticity and dimensional accuracy of the produced color filter are reduced, and the contrast is low. There is a problem that it deteriorates remarkably. In addition, when the dispersion stability of the pigment is insufficient, in the color filter manufacturing process, in particular, the uniformity of the film thickness in the coating process of the colored photosensitive composition is reduced, or in the exposure process. There is a tendency that the sensitivity is lowered and the alkali solubility in the developing process is lowered. Further, when the dispersion stability of the pigment is poor, there is also a problem that the constituent components of the colored photosensitive composition are aggregated with the passage of time, the viscosity is increased, and the pot life is extremely shortened.
As one method for solving such a problem, for example, a method of adding rosin or a rosin derivative or a synthetic polymer compound during salt milling has been proposed (for example, see Patent Document 2).

In recent years, color filters having high brightness as well as contrast have been demanded. As a method for obtaining a color filter with high luminance and high contrast, a conventional C.I. I. Pigment Green 36 and C.I. A method of using polyhalogenated zinc phthalocyanine instead of I pigment green 7 has been proposed (see, for example, Patent Documents 3 and 4).
Japanese Patent Laid-Open No. 7-13016 JP-A-8-179111 JP 2004-70342 A JP 2008-19383 A

However, by using the polyhalogenated zinc phthalocyanine as described above, a certain degree of improvement is obtained by focusing only on the contrast and brightness of the color filter. There is a problem that a development residue is generated in the development of the colored photosensitive composition containing phthalocyanine.
In other words, the reality is that a technique capable of forming a pixel portion with high contrast and high brightness and realizing a coloring composition for a color filter having excellent developability has not yet been established.

Then, this invention is made | formed in view of said point, and makes it a subject to achieve the following objectives.
That is, a first object of the present invention is to provide a coloring composition for a color filter that is excellent in developability and can form a pixel portion excellent in contrast and luminance.
A second object of the present invention is to provide a color filter excellent in contrast and brightness and further reduced in pixel defects, and a method for manufacturing the color filter.

Means for solving the above-mentioned problems are as follows.
That is, the coloring composition for a color filter of the present invention comprises polyhalogenated zinc phthalocyanine having an average primary particle diameter of 10 nm to 40 nm and C.I. I. An organic pigment (A) composed of CI Pigment Yellow 150, a copolymer (B) comprising a repeating unit represented by the following general formula (I) and a repeating unit derived from (meth) acrylic acid, a bifunctional monomer Polymerizable compound (C), photopolymerization initiator (D), organic solvent (E) containing a monomer and at least one monomer selected from pentafunctional monomers and hexafunctional monomers And a dye derivative (G) which is a compound in which a basic or acidic substituent is introduced into an organic dye.

In the general formula (I), R ¹ represents a hydrogen atom or a methyl group, R ² represents a C 2 or C ³ alkylene group, R ³ represents a hydrogen atom or a C 1-20 alkyl group, n represents an integer of 1 to 15.

In the present invention, it is a preferred embodiment that the polyhalogenated zinc phthalocyanine is polybrominated zinc phthalocyanine.
The copolymer (B) preferably further contains a repeating unit derived from n-butyl (meth) acrylate and / or hydroxyethyl (meth) acrylate, and the copolymer (B) is benzyl. It is also preferable to further include a repeating unit derived from (meth) acrylate.
It is also one of the preferable aspects that the coloring composition for color filters of this invention contains a dispersing agent (F) further .

The color filter of the present invention has a pixel portion formed using the coloring composition for a color filter of the present invention.
In addition, the color filter manufacturing method of the present invention is a method for forming a coating film by applying the coloring composition for a color filter of the present invention on a substrate, and then applying a photolithography method to the coating film to form a pixel portion. It is characterized by forming.

In general, polyhalogenated zinc phthalocyanine and C.I. I. It is known that it is difficult to impart excellent developability to a color filter coloring composition containing an organic pigment composed of CI Pigment Yellow 150, and in particular, development residue is often a problem.
In the present invention, polyhalogenated zinc phthalocyanine and C.I. are combined by using a copolymer containing the repeating unit represented by the general formula (I) and the repeating unit derived from (meth) acrylic acid. I. The developability of the color filter coloring composition containing an organic pigment composed of CI Pigment Yellow 150 can be improved.
Although this effect is not clear, the use of the copolymer having the above specific structure reduces the aggregation of the pigment in the coloring composition for color filters, and the repetition represented by the general formula (I) It is presumed that the alkyleneoxy site in the unit attracts the developer and lowers the adhesion at the substrate interface of the non-exposed part, and as a result, the development residue hardly remains.
Further, for the reasons described above, it is considered that pixel defects derived from the development residue are reduced in the color filter produced using the color filter coloring composition of the present invention.

ADVANTAGE OF THE INVENTION According to this invention, while being excellent in developability, the coloring composition for color filters which can form the pixel part excellent in contrast and the brightness | luminance can be provided.
According to the present invention, it is possible to provide a color filter that is excellent in contrast and brightness, and further has reduced pixel defects, and a method for manufacturing the color filter.

  Hereinafter, the coloring composition for color filter of the present invention, the color filter, and the production method thereof will be described in detail.

<Coloring composition for color filter>
The coloring composition for a color filter of the present invention comprises polyhalogenated zinc phthalocyanine having an average primary particle diameter of 10 nm to 40 nm and C.I. I. Pigment Yellow 150, an organic pigment (A), a copolymer (B) containing a repeating unit represented by the general formula (I) and a repeating unit derived from (meth) acrylic acid, a bifunctional monomer A polymerizable compound (C) containing at least one monomer selected from a pentafunctional monomer and a hexafunctional monomer , a photopolymerization initiator (D), an organic solvent (E), In addition, it is characterized by containing a pigment derivative (G) which is a compound in which a basic or acidic substituent is introduced into an organic pigment.
Hereinafter, each component which comprises the coloring composition for color filters of this invention is demonstrated in detail.

[Organic pigment (A)]
The coloring composition for a color filter of the present invention contains an organic pigment, which is substantially composed of polyhalogenated zinc phthalocyanine and C.I. I. It consists of a mixture with CI Pigment Yellow 150.
In the coloring composition for a color filter of the present invention, polyhalogenated zinc phthalocyanine and C.I. I. The total amount of the organic pigment containing CI Pigment Yellow 150 is preferably 5% by mass to 60% by mass with respect to the total amount excluding the solvent in the coloring composition for a color filter of the present invention, and is 10% by mass to 50% by mass. More preferably, it is 15 mass%-45 mass% optimally. By setting the addition amount within this range, a color filter having excellent color characteristics, high contrast, and high luminance can be obtained.

  In addition, in the range which does not impair the effect of this invention, polyhalogenated zinc phthalocyanine and C.I. I. Organic pigments other than CI Pigment Yellow 150 (other organic pigments) may be included, but in this case, the content ratio of the other organic pigments may be polyhalogenated zinc phthalocyanine and C.I. I. 10 mass% or less is preferable with respect to the total mass of the pigment yellow 150, More preferably, it is 5 mass% or less.

(Polyhalogenated zinc phthalocyanine)
First, the polyhalogenated zinc phthalocyanine used in the present invention will be described.
In general, zinc phthalocyanine has 16 hydrogen atoms in the phthalocyanine ring. Therefore, up to 16 of these hydrogen atoms can be replaced with halogen atoms. For example, when these hydrogen atoms are replaced with bromine and chlorine atoms, the number of bromine atoms is 0 to 16, the number of chlorine atoms is 0 to 16, and the number of hydrogen atoms is 0 to 16, and the total is theoretically 136 kinds of substitution products can be produced.
The polyhalogenated zinc phthalocyanine in the present invention is obtained by substituting 2 to 16 hydrogen atoms with halogen atoms in the phthalocyanine ring. As the halogen atom, a bromine atom or a chlorine atom is preferable. Moreover, all the halogen atoms to be substituted may be the same or different.
When the number of substituents on the phthalocyanine ring is constant, the green color increases in the order of bromine atom> chlorine atom.

  A preferred example of such a polyhalogenated zinc phthalocyanine is a compound represented by the following general formula (1).

In the general formula (1), X ^{1 to} X ¹⁶ are each independently a chlorine atom, a bromine atom, or a hydrogen atom. However, at least 8 out of all X ^{1 to} X ¹⁶ are chlorine atoms or bromine atoms.

Here, polyhalogenated zinc phthalocyanine is optimal because it contains 8 or more bromine atoms, which produces a yellowish, light green color and is optimal for use in the green pixel portion of a color filter. is there.
In the present invention, polyhalogenated zinc phthalocyanine containing 8 or more bromine atoms is particularly referred to as “polybrominated zinc phthalocyanine”. This polybrominated zinc phthalocyanine is preferred as the polyhalogenated zinc phthalocyanine of the present invention.

  The average composition of the polyhalogenated zinc phthalocyanine can be easily obtained from mass spectrometry based on mass spectroscopy and halogen content analysis by flask combustion ion chromatography.

  The polyhalogenated zinc phthalocyanine can be produced by a known production method such as a chlorosulfonic acid method, a halogenated phthalonitrile method, or a melting method. More specific production methods are described in detail in Japanese Patent Application Laid-Open No. 2008-19383, Japanese Patent Application Laid-Open No. 2007-320986, Japanese Patent Application Laid-Open No. 2004-70342, and the like. It can also be applied to.

The polyhalogenated zinc phthalocyanine of the present invention needs to have an average primary particle diameter of 10 nm to 40 nm.
By using a polyhalogenated zinc phthalocyanine having an average primary particle diameter in this range, a colored composition for a color filter having excellent dispersibility stability and coloring power can be obtained. A pixel portion with high contrast can be formed.

  In the present invention, the average primary particle diameter means that 100 particles of polyhalogenated zinc phthalocyanine constituting aggregates on a two-dimensional image obtained by photographing particles in the field of view with a transmission electron microscope. The average value of the longer diameter (major axis) and the shorter diameter (minor axis) is obtained and averaged.

  In obtaining the polyhalogenated zinc phthalocyanine of the present invention having an average primary particle diameter of 10 nm to 40 nm, fine particles can be obtained by any method, but crystal growth can be easily suppressed and comparison of average particle diameters is possible. It is preferable to employ a solvent salt milling treatment in that small pigment particles can be obtained.

The solvent salt milling process means kneading and grinding a mixture of polyhalogenated zinc phthalocyanine, an inorganic salt, and an organic solvent. The polyhalogenated zinc phthalocyanine having a large particle size may be subjected to a solvent salt milling treatment after dry-grinding in advance.
More specifically, a polyhalogenated zinc phthalocyanine, an inorganic salt, and an organic solvent that does not dissolve the inorganic salt are charged into a kneader and kneaded and ground therein. As a kneader at this time, for example, a kneader, a mix muller, or the like can be used.

As the inorganic salt used in the solvent salt milling treatment, a water-soluble inorganic salt is suitable, and examples thereof include inorganic salts such as sodium chloride, potassium chloride, sodium sulfate and the like.
Moreover, it is more preferable to use an inorganic salt having an average particle size of 0.5 to 50 μm. An inorganic salt having such a particle size can be easily obtained by pulverizing a normal inorganic salt.

  In obtaining a polyhalogenated zinc phthalocyanine having an average primary particle diameter of 10 nm to 40 nm used in the present invention, the amount of inorganic salt used is increased with respect to the amount of polyhalogenated zinc phthalocyanine used in the solvent salt milling treatment. preferable. That is, the amount of the inorganic salt used is preferably 5 to 20 parts, more preferably 7 to 15 parts with respect to 1 part of the polyhalogenated zinc phthalocyanine in terms of mass.

  As the organic solvent used for the solvent salt milling treatment, an organic solvent capable of suppressing crystal growth is preferably used, and as such an organic solvent, a water-soluble organic solvent is suitable, for example, diethylene glycol, glycerin, ethylene Glycol, propylene glycol, liquid polyethylene glycol, liquid polypropylene glycol, 2- (methoxymethoxy) ethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol monomethyl ether, diethylene glycol Coal monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, 1-methoxy-2-propanol, 1-ethoxy 2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol, and the like.

  The amount of the water-soluble organic solvent used in the solvent salt milling treatment is not particularly limited, but is 0.01 to 5 parts and 0.8 to 2 parts per 1 part of the polyhalogenated zinc phthalocyanine in terms of mass. Part is preferred.

  The temperature during the solvent salt milling treatment is preferably 30 ° C to 150 ° C, and more preferably 80 ° C to 100 ° C. The time for the solvent salt milling treatment is preferably 5 hours to 20 hours, more preferably 8 hours to 18 hours.

  In this way, a mixture containing polyhalogenated zinc phthalocyanine, an inorganic salt, and an organic solvent as main components is obtained. The organic solvent and the inorganic salt are removed from the mixture, and if necessary, the main component is polyhalogenated zinc phthalocyanine. Fine polyhalogenated zinc phthalocyanine powder can be obtained by washing, filtering, drying, pulverizing, and the like.

As the washing, either water washing or hot water washing can be employed.
The number of washings can be repeated in the range of 1 to 5 times.
In the case of the mixture using a water-soluble inorganic salt and a water-soluble organic solvent, the organic solvent and the inorganic salt can be easily removed by washing with water.

In addition, as the drying after the filtration and washing, for example, batch or continuous drying in which the pigment is dehydrated and / or desolvated by heating at 80 ° C. to 120 ° C. by a heating source installed in a dryer. Etc. Here, as a drier, there are generally a box drier, a band drier, a spray drier, etc., and these are used.
In addition, pulverization after drying is not an operation for increasing the specific surface area or reducing the average particle size of the primary particles, for example, in the case of drying using a box dryer or a band dryer, When the pigment is in the form of a lamp or the like, the treatment is performed to break the pigment into powder, and examples thereof include mortar, hammer mill, disk mill, pin mill, jet mill and the like.

In this way, a powder of polyhalogenated zinc phthalocyanine is obtained.
The polyhalogenated zinc phthalocyanine used in the present invention is a pigment, but has a property that the cohesion of the primary particles is weaker than that of the conventional copper halide phthalocyanine, and it is easier to unravel. Therefore, the coloring composition for a color filter of the present invention containing this polyhalogenated zinc phthalocyanine can form a high-contrast green pixel portion.

  When the aspect ratio of the length and breadth of the primary particles of the polyhalogenated zinc phthalocyanine of the present invention is 1 to 3, the viscosity characteristics are improved in the colored composition for a color filter of the present invention, and the fluidity is further increased. In order to obtain the aspect ratio, as in the case of obtaining the average particle diameter of the primary particles as described above, the particles in the field of view are photographed with a transmission electron microscope or a scanning electron microscope. Then, an average value of the longer diameter (major diameter) and the shorter diameter (minor diameter) is obtained for 100 primary particles constituting the aggregate on the two-dimensional image, and the average value is calculated using these values. .

  In addition, the polyhalogenated zinc phthalocyanine having an average primary particle size of 10 nm to 40 nm can be obtained by, for example, the above-described method, but a commercial product of Dainippon Ink & Chemicals, Inc. can also be used. is there.

  In the coloring composition for a color filter of the present invention, polyhalogenated zinc phthalocyanine and C.I. I. Pigment Yellow 150 is used in combination. C. used in combination I. The average primary particle size of CI Pigment Yellow 150 is also preferably 10 nm to 40 nm. C. having such an average primary particle size. I. The pigment yellow 150 can be easily obtained by performing salt milling with a conventionally known method, for example, a kneader or a continuous atomizer.

  In the present invention, polyhalogenated zinc phthalocyanine and C.I. I. The combined use ratio with CI Pigment Yellow 150 is C.I. per 100 parts of the polyhalogenated zinc phthalocyanine in terms of mass. I. Pigment Yellow 150 is preferably 10 to 100 parts, more preferably 15 to 90 parts, and most preferably 20 to 80 parts.

[Copolymer (B)]
The colored composition for a color filter of the present invention contains a copolymer (B) containing a repeating unit represented by the following general formula (I) and a repeating unit derived from (meth) acrylic acid.
Since this copolymer (B) exhibits an excellent pigment dispersion effect, the copolymer (B) functions to prevent aggregation of the pigment in the colored composition of the present invention and to maintain a finely dispersed state of the pigment. This anti-aggregation effect is also exhibited in the dried coating film, contributing to the reduction of residues during development. Further, the alkyleneoxy moiety has a high affinity with the developer, and contributes to further reduction of residues during development by lowering the adhesion with the substrate interface of the non-exposed area.
The content of the copolymer (B) in the colored composition for a color filter of the present invention is preferably 10 parts by mass to 200 parts by mass, more preferably 20 parts by mass to 100 parts by mass with respect to 100 parts by mass in total of the organic pigment. Part by mass.

In the general formula (I), R ¹ represents a hydrogen atom or a methyl group, R ² represents a C 2 or C ³ alkylene group, R ³ represents a hydrogen atom or a C 1-20 alkyl group, n represents an integer of 1 to 15.

The repeating unit represented by the general formula (I) has good adsorption and / or orientation on the pigment surface due to the effect of π electrons of the benzene ring present in the side chain. In particular, when this side chain portion has an ethylene oxide or propylene oxide structure of paracumylphenol, its steric effect is added, and a better adsorption and / or orientation plane can be formed on the pigment. Therefore, it is more effective and preferable.
R ³ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and is preferably an alkyl group having 1 to 20 carbon atoms. In addition, when R ³ is an alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable. This is because when R ³ is an alkyl group having 1 to 10 carbon atoms, this alkyl group becomes an obstacle and suppresses the approach between resins to promote adsorption and / or orientation to the pigment. This is because the steric hindrance effect of the alkyl group is increased and the adsorption and / or orientation of the benzene ring on the pigment surface may be hindered. This phenomenon becomes more prominent as the chain length of the alkyl group of R ³ becomes longer. When the carbon number exceeds 20, the adsorption and / or orientation of the benzene ring is extremely lowered. Therefore, the alkyl group represented by R ³ has a range of 1 to 20 carbon atoms.
The alkyl group represented by R ³ is preferably an unsubstituted alkyl group or an alkyl group substituted with a phenyl group.

R ² in general formula (I) is preferably an alkylene group having 2 carbon atoms from the viewpoint of developability.
Furthermore, n in the general formula (I) is preferably in the range of 1 to 12 from the viewpoint of developability.

  The repeating unit represented by the general formula (I) in the present invention is introduced into the copolymer (B) using an ethylenically unsaturated monomer represented by the following general formula (i).

In the general formula ^{(i), R 1, R} 2, R 3, and ^{n, R 1, R 2, R} 3 in Formula (I), and have the same meanings as n, it is preferable examples .

  Examples of the ethylenically unsaturated monomer represented by the general formula (i) include phenol ethylene oxide modified (meth) acrylate, paracumylphenol ethylene oxide modified (meth) acrylate, nonylphenol ethylene oxide modified (meth) acrylate, and nonylphenol propylene. An oxide modified (meth) acrylate etc. are mentioned.

0.1-50 mass parts is preferable and, as for the content rate of the repeating unit represented by general formula (I) in a copolymer (B), it is more preferable that it is 10-35 mass parts.
Within this range, a sufficient developability improving effect can be obtained, and sufficient compatibility with other components in the color filter coloring composition of the present invention can be obtained.

The copolymer (B) in the present invention contains a repeating unit derived from (meth) acrylic acid in addition to the repeating unit represented by the general formula (I).
The content ratio of the repeating unit derived from (meth) acrylic acid in the copolymer (B) is preferably 15 parts by mass to 50 parts by mass, and more preferably 20 parts by mass to 40 parts by mass.
Within this range, solubility in an alkali developer can be obtained, and the occurrence of dropout of the pixel portion from the substrate and film roughness on the pixel portion surface during development can be suppressed.

The copolymer (B) in the present invention may contain other repeating units in addition to the repeating unit represented by the general formula (I) and the repeating unit derived from (meth) acrylic acid.
Other monomers that can form repeating units include methyl (meth) acrylate, ethyl (meth) acrylate, (iso) propyl (meth) acrylate, (iso) butyl (meth) acrylate, n-butyl (meth) ) Acrylate, (iso) pentyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, glycidyl (meth) acrylate, isobonyl ( (Meth) acrylate acid phosphooxyethyl (meth) acrylate, acid phosphooxypropyl (meth) acrylate, 3 chloro 2-acid phosphooxyethyl (meth) acrylate, acid phosphooxypolyethylene glycol mono ( Data) acrylate.

Among these, it is preferable that a copolymer (B) contains the repeating unit derived from n-butyl (meth) acrylate and / or hydroxyethyl (meth) acrylate.
The content ratio of the repeating unit derived from n-butyl (meth) acrylate and / or hydroxyethyl (meth) acrylate in the copolymer (B) is preferably 5 parts by mass to 70 parts by mass, and 10 parts by mass to 60 parts by mass. More preferably, it is part by mass.

The copolymer (B) is derived from benzyl (meth) acrylate, in addition to the repeating unit derived from n-butyl (meth) acrylate and / or hydroxyethyl (meth) acrylate. It is also preferable to include a repeating unit.
The content ratio of the repeating unit derived from benzyl (meth) acrylate in the copolymer (B) is preferably 5 parts by mass to 60 parts by mass, and more preferably 10 parts by mass to 50 parts by mass.

  The weight average molecular weight (Mw) of the copolymer (B) in this invention becomes like this. Preferably it is 3,000-100,000, Preferably it is 5,000-40,000, More preferably, it is 7,000-30. , 000.

[Other resins]
In the color filter coloring composition of the present invention, a thermoplastic resin other than the above-mentioned copolymer (B), a thermosetting resin, and an active energy ray curable resin are used in combination as long as the effects of the present invention are not impaired. Also good.
Examples of the thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, and polyester resin. Acrylic resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, polyimide resins, and the like. Examples of the thermosetting resin include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenol resins.
In addition, as the active energy ray-curable resin, a linear polymer having a reactive substituent such as a hydroxyl group, a carboxyl group, or an amino group has a reactive substituent such as an isocyanate group, an aldehyde group, or an epoxy group (meta ) A resin obtained by reacting an acrylic compound or cinnamic acid to introduce a photocrosslinkable group such as a (meth) acryloyl group or a styryl group into the linear polymer is used. Further, a linear polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is converted into a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. Half-esterified products are also used.

[Polymerizable compound (C)]
The coloring composition for a color filter of the present invention contains a polymerizable compound (C) such as a monomer or an oligomer.
The usage-amount of the polymeric compound in this invention becomes like this. Preferably it is 5 mass parts-500 mass parts with respect to 100 mass parts of the above-mentioned copolymers (B), More preferably, they are 20 mass parts-300 mass parts. Within this range, sufficient strength and surface smoothness of the pixel area can be obtained, and alkali developability is improved, so that the occurrence of background stains, film residue, etc. on the substrate and the light shielding layer in the unexposed area is suppressed. Is done.

Monomers and oligomers used in the present invention include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, and β-carboxy. Ethyl (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, 1,6-hexanediol diglycidyl ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) a Relate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, (meth) acrylic acid ester of methylolated melamine, epoxy (meth) Acrylic esters and methacrylic esters such as acrylate and urethane acrylate, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (Meth) acrylamide, N-vinylformamide, acrylonitrile and the like can be mentioned.
These may be used alone or in combination of two or more.

In the present invention, polymerizable compound (C), combination of a bifunctional monomer, and at least one monomer selected 5 functional monomers and hexafunctional monomers or et al., It is particularly preferable from the viewpoint of developability.
Examples of bifunctional monomers include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,3-butylene glycol di (Meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (Meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 2-hydroxy-1,3-diaacryloxypropane, 2,2-bis [4- (acryloxyate) B) Phenyl] propane, 2,2-bis [4- (acryloxydiethoxy) phenyl] propane, bis (acryloyloxyethyl) ether of bisphenol A, (meth) acrylic acid modified product of bisphenol A type epoxy resin, Examples include 3-methylpentanediol di (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, dimethylol-tricyclodecanedi (meth) acrylate, and preferably dimethylol-tricyclodecanedi (meth) acrylate. , Neopentyl glycol di (meth) acrylate, ethoxylated bisphenol A diacrylate, and (meth) acrylic acid modified products of bisphenol A type epoxy resin.
Among these, ethoxylated bisphenol A diacrylate is more preferable from the viewpoint of maintaining good developability and the cross-sectional shape of the pattern. Of the ethoxylated bisphenol A diacrylates, the total number of ethoxy repeats is preferably 10 to 30 in terms of developability, and most preferably 15 to 25.

Examples of pentafunctional monomers or hexafunctional monomers include dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and UA-306H manufactured by Kyoeisha Chemical Co., Ltd. Examples thereof include urethane acrylates such as UA-306T and UA-306I.
Among these, dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate are preferable from the viewpoint of solvent resistance, and a 3 to 7 (mass ratio) mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate is a viewpoint of solvent resistance. And most preferred.

  Moreover, the ratio of the combined use of the bifunctional monomer and the pentafunctional monomer and / or the hexafunctional monomer is a pentafunctional monomer with respect to 100 parts by mass of the bifunctional monomer. And it is preferable from a viewpoint of developability and solvent resistance that the ratio of a hexafunctional monomer is 20 mass parts-500 mass parts.

[Photopolymerization initiator (D)]
The colored composition for a color filter of the present invention contains a photopolymerization initiator (D).
The photopolymerization initiator can be used in an amount of preferably 5 parts by mass to 200 parts by mass, more preferably 10 parts by mass to 150 parts by mass with respect to a total of 100 parts by mass of the organic pigment.

As photopolymerization initiator (D), 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2- Acetophenone photopolymerization initiators such as morpholinopropan-1-one;
Benzoin photopolymerization initiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzyldimethyl ketal;
Benzophenone-based photopolymerization initiators such as benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide;
Thioxanthone photopolymerization initiators such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone;

2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s -Triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloromethyl) -s-triazine, 2,4-bis (trichloro) Methyl) -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, 2,4-trichloromethyl (4′-methoxystyryl) -6-tri Triazine photopolymerization initiators such as azine;
Borate photopolymerization initiator;
A carbazole photoinitiator;
Imidazole-based photopolymerization initiators; etc. are used.

These photopolymerization initiators can be used alone or in admixture of two or more.
These photopolymerization initiators include α-acyloxy ester, acylphosphine oxide, methylphenylglyoxylate, benzyl-9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone as sensitizers. 4,4′-diethylisophthalophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 4,4′-diethylaminobenzophenone, and the like can be used in combination.
The sensitizer can be used preferably in an amount of 0.1 to 60 parts by mass with respect to 100 parts by mass of the photopolymerization initiator.

[Organic solvent (E)]
The coloring composition for a color filter of the present invention contains an organic solvent (E).
The organic solvent can be used in an amount of preferably 800 parts by weight to 4000 parts by weight, more preferably 1000 parts by weight to 2500 parts by weight with respect to 100 parts by weight of the organic pigment.

Examples of the organic solvent include 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, ethyl 3-ethoxypropionate, 3-methyl-1,3-butane Diol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-di Chlorobenzene, N, N-dimethylacetamide, N, N-dimethylformamide, n-butyl Lucol, n-butylbenzene, n-propyl acetate, N-methylpyrrolidone, 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 monopropylene 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, benzyl alcohol, methyl isobutyl Ketone, methyl cyclohexanol, acetic acid n- amyl acetate n- butyl, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters.
These organic solvents may be used alone or in combination.

[Dispersant (F)]
In addition to the copolymer (B) described above, the coloring composition for a color filter of the present invention is excellent in pigment dispersibility as a dispersant (F) and has a large effect of preventing reaggregation of the pigment after dispersion. It is preferable to add a resin-type dispersant.
The resin-type dispersant can be used in an amount of preferably 0.1 to 60 parts by mass, more preferably 0.1 to 40 parts by mass with respect to 100 parts by mass of the organic pigment.

The resin-type dispersant has an acidic group or a basic group because it adsorbs to the surface of the pigment using an acidic group or a basic group as an anchor, and the repulsive effect of the polymer effectively acts to maintain dispersion stability. A polymer is preferred.
As the acidic group, a carboxylic acid group or a sulfone group is preferable from the viewpoint of excellent adsorption characteristics, and as the basic group, an amino group is preferable from the viewpoint of excellent adsorption characteristics.
In addition, the combined use of a dye derivative having an acidic group and a resin-type dispersant having a basic group, or the combined use of a dye derivative having a basic group and a resin-type dispersant having an acidic group is an adsorption property to the pigment. Is more preferable because it is further improved.

As a polymer having an acidic group or a basic group used as a resin type dispersant, a comb polymer having a structure in which a branch polymer part is graft-bonded to a trunk polymer part having an acidic group or a basic group is excellent in a branch polymer part. Since it has more organic solvent solubility from the steric repulsion effect, it is preferable.
Furthermore, a comb polymer having a molecular structure in which two or more branch polymers are graft-bonded to one molecule of the trunk polymer is more preferable for the above reason.

  Moreover, as a commercially available resin-type dispersant, Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170 manufactured by Big Chemie 171 174 181 182 183 184 185 190 190 2000 Bykumen et al., SOLPERSE-3000, 9000, 13240, 13650, 13940, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, manufactured by Abyssia 2500, 32600, 34750, 36600, 38500, 41000, 41090, 53095, etc., EFKA-46, 47, 48, 452, LP4008, 4009, LP4010, LP4050, LP4055, 400, 401, 402, 403 manufactured by Efka Chemicals 450, 451, 453, 4540, 4550, LP4560, 120, 150, 1501, 1502, 1503, and the like.

[Dye derivative (G)]
A color filter for coloring composition of the invention, it added dye derivative having the effect of preventing reaggregation of the pigment after dispersion (G).
The content of the pigment derivative (G) is preferably 0.001 to 40 parts by mass, and more preferably 1 to 30 parts by mass with respect to 100 parts by mass of the organic pigment.

  A pigment derivative is a compound in which a basic or acidic substituent is introduced into an organic pigment. Organic dyes include light yellow aromatic polycyclic compounds that are not generally called dyes, such as naphthalene, anthraquinone, and acridone. Examples of the dye derivative include JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, JP-A-9-176511. What is described in the gazette etc. can be used, These can be used individually or in mixture of 2 or more types.

  Specific examples of the basic group possessed by the dye derivative include substituents represented by the following general formula (2), (3), (4), or (5). In particular, a dye derivative having a basic group containing a triazine ring represented by the following general formula (5) is preferably used because of a large pigment dispersion effect.

X, n, R ^{01 to} R ⁰⁹ , and Y in the general formulas (2) to (5) are as follows.
X _{is, -SO 2 -, - CO -} , - CH 2 NHCOCH 2 -, - CH 2 -, or a single bond.
n represents an integer of 1 to 10 R ⁰¹ and R ⁰² each independently represents an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted phenyl group. . Here, as for carbon number of an alkyl group and an alkenyl group, 1-10 are preferable. R ⁰¹ and R ⁰² may be bonded to each other to form a heterocyclic ring containing a further nitrogen atom, oxygen atom, or sulfur atom. This heterocyclic ring may further have a substituent.

R ⁰³ represents an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted phenyl group. Here, as for carbon number of an alkyl group and an alkenyl group, 1-10 are preferable.
R ⁰⁴ , R ⁰⁵ , R ⁰⁶ , and R ⁰⁷ each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted phenyl group. . Here, as for carbon number of an alkyl group and an alkenyl group, 1-5 are preferable.

Y represents -NR-Z-NR'- or a single bond. R and R ′ in —NR—Z—NR′— are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted group. Represents a phenyl group. Here, as for carbon number of an alkyl group and an alkenyl group, 1-5 are preferable. Z represents an alkylene group that may be substituted, an alkenylene group that may be substituted, or a phenylene group that may be substituted. Here, as for carbon number of an alkylene group and an alkenylene group, 1-8 are preferable.
R ⁰⁸ represents a substituent represented by the following general formula (6) or a substituent represented by the following general formula (7).
R ⁰⁹ represents a hydroxyl group, an alkoxyl group, a substituent represented by the following general formula (6), or a substituent represented by the following general formula (7).

In the general formula (6) and ^(7), R 01 ^{to R 07,} and n are as defined ^R 01 ^{to R 07} and, n mentioned above, and preferred examples are also the same.

Specific examples of the acidic group possessed by the dye derivative include a sulfonic acid group and a terephthalic acid monoamidomethyl group.
The sulfonic acid group may form a salt with a metal such as aluminum, potassium, sodium, calcium, or an amine.
In particular, an aluminum salt of a pigment derivative having an acidic group is preferably used because of a large dispersion effect of the treated pigment.

  Examples of the organic dye constituting the dye derivative include, for example, diketopyrrolopyrrole dyes, azo dyes such as azo, disazo, polyazo, phthalocyanine dyes, diaminodianthraquinone, anthrapyrimidine, flavantron, anthanthrone, indanthrone, Anthraquinone dyes such as pyranthrone, violanthrone, quinacridone dyes, dioxazine dyes, perinone dyes, perylene dyes, thioindigo dyes, isoindoline dyes, isoindolinone dyes, quinophthalone dyes, selenium dyes, metal complexes And system dyes.

[Other additives]
(Dispersing aid)
In the coloring composition for a color filter of the present invention, a dispersion aid such as a surfactant can be appropriately used.
Since the dispersion aid is excellent in pigment dispersion and has a great effect of preventing re-aggregation of the pigment after dispersion, when a coloring composition obtained by dispersing the pigment in a resin using the dispersion aid is used, A color filter having excellent transparency can be obtained.
The dispersion aid can be used in the range of preferably 0.1 to 40 parts by mass, more preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the organic pigment.

Surfactants include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate, lauryl sulfate monoethanolamine, lauryl Anionic surfactants such as triethanolamine sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer; polyoxyethylene oleyl ether, polyoxyethylene Lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene sorbitan monostearate, polyethylene glycol Nonionic surfactants such as laurate;
Chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts;
Examples include alkylbetaines such as alkyldimethylaminoacetic acid betaine and amphoteric surfactants such as alkylimidazoline, and these can be used alone or in admixture of two or more.

(Storage stabilizer)
The coloring composition for a color filter of the present invention can contain a storage stabilizer in order to stabilize the viscosity with time.
The storage stabilizer can be used preferably in the range of 0.1 to 10 parts by mass with respect to 100 parts by mass in total of the pigment.

  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 coloring composition for a color filter of the present invention is obtained by performing a process of kneading a mixture of the above-described components (organic pigment, dye derivative, copolymer, etc.) with a two-roll mill into a sheet, a plurality of times, You may prepare using the chip | tip obtained by grind | pulverizing. As the mixture used here, it is particularly preferable to use a mixture in which each component is sufficiently mixed and homogeneously dispersed before being mixed with a two-roll mill.

  The kneader used to knead the mixture is a two-roll mill, which itself has a roll rotation speed ratio of 1: 1.1 to 1: 1.3, and a roll gap of 0.5 mm to 3 mm. It is preferable to use it by adjusting to a range of 0.0 mm. When the rotational speed ratio is within this range, a shearing force is applied, and the dispersion of the pigment proceeds sufficiently. In addition, when the gap between the rolls is within this range, a shearing force is applied, the dispersion of the pigment proceeds sufficiently, the mixture easily passes between the two rolls, and the impact on the obtained sheet-like material is suppressed. The risk of ignition caused by the pigment used is also reduced.

  In the step of kneading into a sheet, the mixture is passed through two rotating rolls of the two-roll mill to form a sheet. The material is folded into several sheets and passed through a roll mill a plurality of times. Further, instead of the above-described method of passing the mixture through the roll gap and kneading, a method of winding the mixture around two rolls and kneading can also be adopted, and this method also has the same effect as the above method. can get.

The chip manufacturing process can be performed in the presence of a solvent, if necessary.
Examples of the solvent include alcohols such as methyl alcohol and ethyl alcohol, esters such as ethyl acetate, propyl acetate, and propylene glycol methyl ether acetate, ketones such as acetone, methyl ethyl ketone, and cyclohexanone, and aromatic hydrocarbons such as benzene, toluene, and xylene. Etc. can be used.
Furthermore, the solvent is not limited to one type, and two or more types can be mixed and used, and the above components may be mixed to form the mixture.

  A process is normally performed in the temperature range of 20 to 120 degreeC. The rotational speed of the roll of the two roll mill is usually 10 r. p. m. ~ 50r. p. m. The rotational speed ratio of the two rolls is adjusted to the above value within this range.

The pigment dispersion used in the color composition for color filter of the present invention can be obtained, for example, by stirring and dissolving the above chip in an organic solvent and dispersing with a media dispersing machine such as a bead mill. It can also be obtained by dispersing the above mixture and organic solvent with a media dispersing machine such as a bead mill without using a chip.
When preparing a pigment dispersion using a bead mill, for example, glass beads having a diameter of about 0.01 mm to 1 mm, titania beads or zirconia beads are used, and the pigment mixture is preferably cooled with cooling water or the like. However, it can be carried out by mixing and dispersing.
In this case, the filling rate of beads is preferably 50% to 90% of the mill capacity. The treatment time is preferably 2 hours to 50 hours, more preferably 2 hours to 25 hours.

  In addition, the coloring composition for color filters of this invention is polyhalogenated zinc phthalocyanine and C.I. I. Pigment Yellow 150 is contained, but each pigment may be dispersed as a separate pigment dispersion or may be co-dispersed.

  The coloring composition for a color filter of the present invention can be prepared by blending the above-described pigment dispersion with a polymerizable compound, a photopolymerization initiator, a solvent, and other components as necessary.

  The coloring composition for a color filter of the present invention is a coarse particle of 5 μm or more, preferably a coarse particle of 1 μm or more, more preferably a coarse particle of 0.5 μm or more by means of centrifugation, sintered filter, membrane filter or the like. It is preferable to remove the mixed dust.

<Color filter and manufacturing method thereof>
Next, the color filter of the present invention will be described.
The color filter of this invention is a color filter which has a pixel part formed using the coloring composition for color filters of this invention.
The color filter includes an additive color mixing type and a subtractive color mixing type including at least one red pixel portion, at least one green pixel portion, and at least one blue pixel portion. It is formed using a color filter coloring composition.

As the color filter coloring composition used when forming pixel portions other than the green pixel portion, each color coloring composition containing each color pigment, the copolymer (B), the polymerizable compound (C), etc. It can be formed using an object.
Examples of the red coloring composition include C.I. I. Pigment Red 7, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2, 81: 3, 81: 4, 146, 168, 177, 178, 184 Red pigments such as 185, 187, 200, 202, 208, 210, 246, 254, 255, 264, 270, 272, and 279 are used.
The red coloring composition includes C.I. I. Pigment Orange 43, 71, 73 and other orange pigments, C.I. I. Pigment Yellow 83, 110, 138, 139, 150, 180, 185 and the like can be used in combination.

Examples of the blue coloring composition include C.I. I. Blue pigments such as Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64 are used.
Blue coloring compositions include C.I. I. Purple violet pigments such as Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, and 50 can be used in combination.

The color filter of the present invention can be manufactured by forming a pixel portion of each color on a substrate using the coloring composition for a color filter of the present invention and each normal color coloring composition by applying a photolithography method. it can.
As the substrate, a glass plate having a high transmittance with respect to visible light, or a resin plate such as polycarbonate, polymethyl methacrylate, or polyethylene terephthalate is used.

The formation of each color pixel portion by photolithography is performed by the following method.
First, a colored composition prepared as a solvent developing type or alkali developing type colored resist material that is cured by light irradiation (the colored composition for a color filter of the present invention or each colored coloring composition of the present invention) on a transparent substrate, By a coating method such as spray coating, spin coating, slit coating, or roll coating, the coating is applied so that the dry film thickness is 0.2 μm to 5 μm. Thereafter, if necessary, the dried film is exposed to ultraviolet rays through a mask having a predetermined pattern provided in contact or non-contact with the film. After exposure, the film is immersed in a solvent or an alkali developer, or sprayed with a developer or the like to remove uncured portions of the film and form a desired pattern. A color filter can be manufactured by repeating the same operation for other colors.
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 printing method can be manufactured.

In the development, an aqueous solution of sodium carbonate, sodium hydroxide, potassium hydroxide or the like 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 exposure sensitivity to ultraviolet rays, after applying and drying the colored resist material, a water-soluble or alkali-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied and dried on the film to inhibit polymerization by oxygen. After forming a film for preventing the exposure, ultraviolet exposure can also be performed.

Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In Examples and Comparative Examples, “parts” and “%” mean “parts by mass” and “% by mass”. The molecular weight of the resin is a weight average molecular weight in terms of polystyrene measured by GPC (gel permeation chromatography).
In addition, in the Example shown below, all the things outside the range of Claim 1 are reference examples.

[Synthesis Example 1: Synthesis of copolymer (1)]
70.0 parts of cyclohexanone 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. N-butyl methacrylate 10.2 parts, 2-hydroxyethyl methacrylate 4.6 parts, methacrylic acid 7.4 parts, benzyl methacrylate 3.7 parts, paracumylphenol ethylene oxide modified acrylate ("Aronix M110" manufactured by Toagosei Co., Ltd.) ") 3.7 parts of a mixture of 2,2'-azobisisobutyronitrile 0.8 parts was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for another 3 hours to obtain a solution of copolymer (1) having a solid content of 30%. The weight average molecular weight of this copolymer (1) was 19,000.

[Synthesis Example 2: Synthesis of Comparative Copolymer (2)]
70.0 parts of cyclohexanone 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. 13.3 parts of n-butyl methacrylate, 4.0 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, 8.0 parts of benzyl methacrylate, and 0.4 of 2,2′-azobisisobutyronitrile. Part of the mixture was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a copolymer (2) solution having a solid content of 30%. The comparative copolymer (2) had a weight average molecular weight of 23,000.

[Synthesis Example 3: Synthesis of Aluminum Salt of Sulfonated Dye Derivative]
Quinophthalone yellow pigment C.I. I. 30 parts of Pigment Yellow 138 (“Pariotol Yellow K0960-HD” manufactured by BASF) was dissolved in 300 parts of 101% sulfuric acid prepared from fuming sulfuric acid (25% SO ₃ ) and sulfuric acid, and stirred at 70 ° C. for 8 hours. Then, sulfonation reaction was performed. The end point of the reaction was defined as the point at which no change in the spectrum was observed by measuring the spectrum of the sulfuric acid solution. Next, this reaction solution was poured into 3000 parts of ice water, and the precipitated sulfonated dye derivative was separated by filtration and washed with water to obtain a sulfonated dye derivative paste.
The obtained sulfonated dye derivative was subjected to LC-MASS analysis. In HPLC (column: “ODS-100S” manufactured by Tosoh Corporation), the molecular weight of the main peak occupying an area ratio of 80% is Mw = 774 (electron spray method, minus mode). I. Consistent with the molecular weight of the monosulfonated derivative of Pigment Yellow 138. Further, it was identified by 1H-NMR as a sulfonated dye derivative having the following structure.

The obtained sulfonated pigment derivative paste was redispersed in 10,000 parts of water (pH 2.5). Next, the solution was adjusted to pH 11 with an aqueous sodium hydroxide solution and dissolved to give a red solution. To this solution, 278 parts of an aqueous aluminum sulfate solution (liquid sulfuric acid band) was gradually added. Precipitates appeared one after another from the dropped portions, and the pH decreased with the addition. At the end of the addition, pH 3.6 and bleed were not observed. The slurry containing this precipitate was filtered off and washed with water. I. An aluminum salt of a sulfonated derivative of Pigment Yellow 138 was obtained.
The yield after drying was 334 parts, and the yield was 99%. The resulting aluminum salt of the sulfonated dye derivative is presumed to have the following structure.

[Example 1]
(Chip manufacturing method)
A mixture of the following composition A was sufficiently mixed in advance, and then kneaded with a two-roll mill to obtain a sheet. The sheet was folded into several sheets and passed through a two-roll mill again. After repeating this process 10 to 40 times, a green chip was produced by pulverizing with a pulverizer.

-Composition A-
Polybrominated zinc phthalocyanine (average primary particle size 25 nm) 7.3 parts I. Pigment Yellow 150 (average primary particle size 25 nm) 3.7 parts ・ Basic pigment derivative containing triazine ring (the following structure) 1.0 part ・ Copolymer (1) solution obtained in Synthesis Example 1 14.0 parts

(Method for producing pigment dispersion)
A mixture of the following composition B was uniformly stirred and mixed, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 3 hours using zirconia beads having a diameter of 0.3 mm, and then a 5 μm filter. To prepare a pigment dispersion.

-Composition B-
-16.0 parts of the green chip obtained as described above-2.0 parts of the copolymer (1) solution obtained in Synthesis Example 1-2.4 parts of resin-type dispersant having an acidic group (Bic Chemie) "Disperbyk-111")
・ 79.6 parts of propylene glycol monomethyl ether acetate

(Method for producing green coloring composition)
Next, the mixture of the following composition C was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to obtain a green colored composition having photosensitivity.

-Composition C-
Pigment dispersion obtained as described above 67.0 parts Copolymer (1) solution obtained in Synthesis Example 1 5.0 parts Dipentaerythritol hexaacrylate 4.0 parts Photopolymerization initiator 1.4 parts ("Irgacure 907" manufactured by Ciba Specialty Chemicals)
・ Sensitizer (“EAB-F” manufactured by Hodogaya Chemical Co., Ltd.) 0.2 part ・ Propylene glycol monomethyl ether acetate 22.4 parts

  Two pieces of the obtained green coloring composition were applied on a 100 mm × 100 mm glass substrate (1737, manufactured by Corning) using a spin coater so that the y value serving as an index of color density was 0.595. Thereafter, pre-baking was performed for 2 minutes in a clean oven at 90 ° C. to form a coating film.

Next, after cooling the substrate to room temperature, one of the two coated substrates was prepared, and a high pressure mercury lamp was used for the coated film of this substrate, and a film of 365 nm, 405 nm, and 436 nm was passed through a photomask. Radiation including each wavelength was exposed at an exposure amount of 1,000 J / m ² . Thereafter, the substrate was immersed in a developer composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. for 1 minute, developed, washed with ultrapure water, and air-dried. Thereafter, post-baking was performed at 230 ° C. for 30 minutes to form a green stripe pixel pattern on the substrate.
This substrate was used as a substrate for evaluating foreign matter, chromaticity, and developability described later.

In addition, a high-pressure mercury lamp is used for the coating film of the other coating film substrate, and radiation including wavelengths of 365 nm, 405 nm, and 436 nm is exposed at an exposure amount of 1,000 J / m ² without using a photomask. did. Thereafter, post-baking was performed at 230 ° C. for 30 minutes to form a solid green cured film on the substrate.
This substrate was used as a contrast ratio evaluation substrate described later.

-Evaluation of foreign matter and chromaticity-
When the formed pixel pattern was observed with an optical microscope, no foreign matter was observed on the pixel.
Further, when the chromaticity of the pixel was evaluated with a color analyzer MCPD2000 (manufactured by Otsuka Electronics Co., Ltd.), it was (x, y, Y) = (0.299, 0.595, 59.5).

-Evaluation of developability-
In the exposure process, the presence or absence of residues in the areas not exposed to light (unexposed areas) was observed with an optical microscope, and the developability was evaluated. It was not a level to become.

-Evaluation of contrast ratio-
The obtained substrate is sandwiched between two polarizing plates, the front side polarizing plate is rotated while irradiating with a fluorescent lamp (wavelength range of 380 to 780 nm) from the back side, and the transmitted light intensity is measured with a luminance meter LS-100 (MINOLTA). When the maximum value and the minimum value were measured by the company, and the contrast ratio was evaluated as a value obtained by dividing the maximum value by the minimum value, it was 11,100.
In addition, it can be said that it is favorable if the contrast value exceeds 10,000.

[Example 2]
In Example 1, the “basic pigment derivative containing a triazine ring (the above structure)” was replaced with the “aluminum salt of a sulfonated dye derivative” obtained in Synthesis Example 3, and “resin-type dispersion having an acidic group” Green colored composition in the same manner as in Example 1 except that the agent (Bicchemy, “Disperbyk-111”) was replaced with “resin-type dispersant having a basic group (Avisia,“ Solsperse 24000 ”). Got.
Thereafter, using the obtained green coloring composition, in the same manner as in Example 1, a foreign substance, chromaticity and developability evaluation substrate and a contrast ratio evaluation substrate were prepared. And evaluation similar to Example 1 was performed using these board | substrates for evaluation.
As a result of the evaluation, no foreign matter was found on the pixel, and the chromaticity of the pixel was (x, y, Y) = (0.300, 0.595, 59.7). Further, although a slight amount of residue was observed in the unexposed area, it was not at a level causing a practical problem. The contrast ratio was 10,900.

[Example 3]
In Example 1, the “basic pigment derivative containing a triazine ring (the above structure)” was replaced with the “aluminum salt of a sulfonated dye derivative” obtained in Synthesis Example 3, and “resin-type dispersion having an acidic group” 3. “Dipentaerythritol hexaacrylate” in the composition C is used in place of the agent (manufactured by Big Chemie, “Disperbyk-111”) with “resin-type dispersant having a basic group (Avisia,“ Solsperse 24000 ”). “0 parts” was changed to “3.0 parts of dipentaerythritol hexaacrylate and 1.0 part of A-BPE-20 (manufactured by Shin-Nakamura Chemical Co., Ltd.)” in the same manner as in Example 1. A green colored composition was obtained.
The structure of A-BPE-20 is as follows.

Thereafter, using the obtained green coloring composition, in the same manner as in Example 1, a foreign substance, chromaticity and developability evaluation substrate and a contrast ratio evaluation substrate were prepared. And evaluation similar to Example 1 was performed using these board | substrates for evaluation.
As a result of the evaluation, no foreign matter was recognized on the pixel, and the chromaticity of the pixel was (x, y, Y) = (0.300, 0.595, 59.6). Further, no residue was observed in the unexposed area. The contrast ratio was 11,100.

[Comparative Example 1]
In Example 1, except that “Copolymer (1) solution obtained in Synthesis Example 1” was replaced with “Copolymer (2) solution obtained in Synthesis Example 2”, the same as Example 1. Thus, a green coloring composition was obtained.
Thereafter, using the obtained green coloring composition, in the same manner as in Example 1, a foreign substance, chromaticity and developability evaluation substrate and a contrast ratio evaluation substrate were prepared. And evaluation similar to Example 1 was performed using these board | substrates for evaluation.
As a result of the evaluation, no foreign matter was found on the pixel and the chromaticity of the pixel was (x, y, Y) = (0.299, 0.595, 59.4), but it was practically used in the unexposed area. A problematic level of residue was observed. The contrast ratio was 10,800.

[Comparative Example 2]
Example 2 was the same as Example 2 except that “the copolymer (1) solution obtained in Synthesis Example 1” was replaced with “the copolymer (2) solution obtained in Synthesis Example 2”. Thus, a green coloring composition was obtained.
Thereafter, using the obtained green coloring composition, in the same manner as in Example 1, a foreign substance, chromaticity and developability evaluation substrate and a contrast ratio evaluation substrate were prepared. And evaluation similar to Example 1 was performed using these board | substrates for evaluation.
As a result of the evaluation, no foreign matter was found on the pixel, and the chromaticity of the pixel was (x, y, Y) = (0.300, 0.595, 59.6). A problematic level of residue was observed. The contrast ratio was 10,700.

[Comparative Example 3]
(Preparation of acrylic resin solution)
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer was charged with 70.0 parts of cyclohexanone, heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen. 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, 7.4 parts of paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.), A mixture of 0.4 part of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain an acrylic resin solution having a weight average molecular weight of 26,000. After cooling this to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. In addition, the previously synthesized acrylic resin solution had a nonvolatile content of 20% by mass. Thus, cyclohexanone was added to prepare an acrylic resin solution.

Next, a method for synthesizing a crude green pigment will be described.
In addition, the measurement of the metal in the synthetic | combination crude pigment was performed with the following method.
First, 0.5 g of crude pigment, 1 ml of sulfuric acid, and 3 ml of nitric acid were placed in a 100 ml beaker, decomposed by heating for 1 hour 30 minutes on a gas stove, and then heated for 4 hours in a 600 ° C. electric furnace for decomposition. The decomposed product was dissolved in 5 ml of hydrochloric acid and 25 ml of pure water, and the dissolved product was made up to a volume of 50 ml, and the amount of metal atoms was measured by ICP atomic emission spectrometry.
The number of chlorine atoms and bromine atoms in the crude pigment (average number of chlorines and average number of bromines contained in one molecule) The filter paper of No. 6 was wrapped with 0.01 g of crude pigment, 5 drops of hydrogen peroxide were added dropwise, and burned in a combustion flask purged with oxygen. After combustion, the volume was fixed to 100 ml and measured by ion chromatography analysis.

(Synthesis of crude aluminum halide phthalocyanine pigment)
In a molten salt of 356 parts of aluminum chloride and 6 parts of sodium chloride at 200 ° C., 46 parts of aluminum phthalocyanine was dissolved, cooled to 130 ° C. and stirred for 1 hour. The reaction temperature was raised to 180 ° C., and bromine was added dropwise at 10 parts per hour for 10 hours. Thereafter, chlorine was introduced at 0.8 parts per hour for 5 hours. The reaction solution was gradually poured into 3200 parts of water, then filtered and washed with water to obtain 110.8 parts of a crude aluminum halide phthalocyanine pigment.
The average number of bromine atoms contained in one molecule of the crude aluminum halide phthalocyanine pigment was 14.0, and the average number of chlorine atoms was 2.0.

(Synthesis of crude zinc halide phthalocyanine pigment)
In a molten salt of 200 ° C. of 356 parts of aluminum chloride and 6 parts of sodium chloride, 46 parts of zinc phthalocyanine was dissolved, cooled to 130 ° C., and stirred for 1 hour. The reaction temperature was raised to 180 ° C., and bromine was added dropwise at 10 parts per hour for 10 hours. Thereafter, chlorine was introduced at 0.8 parts per hour for 5 hours. The reaction solution was gradually poured into 3200 parts of water, then filtered and washed with water to obtain 107.8 parts of a crude zinc halide phthalocyanine pigment.
The average number of bromine atoms contained in one molecule of the crude zinc halide phthalocyanine pigment was 14.1 and the average number of chlorine atoms was 1.9.

  Subsequently, the crude halogenated metal phthalocyanine pigment was pigmented by the following method to produce a phthalocyanine green pigment.

(Preparation of phthalocyanine green pigment 1)
100 parts of a crude aluminum halide phthalocyanine pigment, 100 parts of sodium chloride, and 50 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 2 hours. Next, the kneaded product is poured into 5 liters 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. overnight. As a result, a phthalocyanine green pigment 1 was obtained.

(Preparation of phthalocyanine green pigment 2)
A phthalocyanine green pigment 2 was obtained in the same manner as the phthalocyanine green pigment 1, except that a crude zinc halide phthalocyanine pigment was used instead of the crude aluminum halide phthalocyanine pigment.

(Preparation of pigment dispersion)
A mixture of the following composition D was stirred and mixed uniformly, dispersed with a pico mill for 10 hours using zirconia beads having a diameter of 0.1 mm, and then filtered with a 5 μm filter to prepare a pigment dispersion.

-Composition D-
-5.4 parts of the phthalocyanine green pigment 1-8.1 parts of the phthalocyanine green pigment 2-1.5 parts of a pigment derivative having a basic group having the following structure-Acrylic resin solution obtained by the above-mentioned method 0 parts, dipentaerythritol pentaacrylate and hexaacrylate 7.0 parts ("Aronix M400" manufactured by Toagosei Co., Ltd.)
・ 38.0 parts of cyclohexanone

(Preparation of green coloring composition)
Next, the mixture of the following composition E was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to prepare a colored composition.

-Composition E-
-53.33 parts of the pigment dispersion obtained as described above-7.75 parts of the acrylic resin solution obtained by the method described above-2.24 parts of photopolymerization initiator ("Irgacure 907" manufactured by Ciba Specialty Chemicals) )
・ Surfactant (“BYK-323” manufactured by Big Chemie) 0.03 part ・ Storage stabilizer (“TPP” manufactured by Hokuko Chemical Co., Ltd.) 0.20 part ・ Cyclohexanone 36.45 parts

  After applying the obtained green coloring composition on a 100 mm × 100 mm glass substrate (1737, manufactured by Corning) using a spin coater so that the y value serving as an index of color density is 0.595, Pre-baking was performed in a clean oven at 90 ° C. for 2 minutes to form a coating film.

Next, after cooling the substrate to room temperature, the coating film was exposed to radiation containing wavelengths of 365 nm, 405 nm, and 436 nm at a dose of 1,000 J / m ² through a photomask using a high-pressure mercury lamp. . Thereafter, the substrate is immersed in a developer comprising a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. for 1 minute, developed, washed with ultrapure water, air-dried, and further post-baked at 230 ° C. for 30 minutes. To form a green stripe pixel pattern on the substrate.

When the formed pixel pattern was observed with an optical microscope, no foreign matter was observed on the pixel.
In addition, in the exposure process, the presence or absence of residues in areas not exposed to light (unexposed areas) was observed with an optical microscope, and developability was evaluated. Residues of a level causing practical problems were found in the unexposed areas. It was.

  As described above, it can be seen that the green coloring composition of the example can form pixels with high brightness and light contrast without any foreign matter. Moreover, when the green coloring composition of an Example is used, it turns out that the image development residue in the case of image development is also suppressed compared with a comparative example.

Claims (7)

Polyhalogenated zinc phthalocyanine having an average primary particle diameter of 10 nm to 40 nm and C.I. I. An organic pigment (A) composed of CI Pigment Yellow 150, a copolymer (B) comprising a repeating unit represented by the following general formula (I) and a repeating unit derived from (meth) acrylic acid, a bifunctional monomer Polymerizable compound (C), photopolymerization initiator (D), organic solvent (E) containing a monomer and at least one monomer selected from pentafunctional monomers and hexafunctional monomers And the coloring composition for color filters characterized by containing the pigment derivative (G) which is a compound which introduce | transduced the basic or acidic substituent into the organic pigment | dye.

(In the general formula (I), R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkylene group having 2 or 3 carbon atoms, and R ³ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. , N represents an integer of 1 to 15.)   The colored composition for a color filter according to claim 1, wherein the polyhalogenated zinc phthalocyanine is polybrominated zinc phthalocyanine.   The color according to claim 1 or 2, wherein the copolymer (B) further includes a repeating unit derived from n-butyl (meth) acrylate and / or hydroxyethyl (meth) acrylate. Coloring composition for filters.   The colored composition for a color filter according to any one of claims 1 to 3, wherein the copolymer (B) further contains a repeating unit derived from benzyl (meth) acrylate.   Furthermore, a dispersing agent (F) is contained, The coloring composition for color filters of any one of Claims 1-4 characterized by the above-mentioned. Color filter and having a claim 1 pixel portion formed by using a color filter for coloring composition according to any one of claims 5. A color filter coloring composition according to any one of claims 1 to 5 is applied onto a substrate to form a coating film, and then a pixel portion is formed by applying a photolithography method to the coating film. A method for producing a color filter, comprising: forming a color filter.