JP2020012115A - Green pigment coloring resin composition, color filter, liquid crystal display device and organic EL display device - Google Patents

Abstract

To provide a green pigment colored resin composition, which reduces breakage of pixels when a color filter is formed; and to further provide a color filter excellent in linearity of patterns, exhibiting no light leakage, having high color purity, and exhibiting high luminance and high contrast, and to provide a liquid crystal display device and an organic EL display device comprising the color filter.SOLUTION: A green pigment colored resin composition comprises a halogenated zinc phthalocyanine green pigment, a photopolymerization initiator, and a solvent, and further comprises a blue dye.SELECTED DRAWING: None

Description

  The present invention resides in a green pigmented resin composition, a color filter, a liquid crystal display, and an organic EL display.

  Conventionally, as a method of manufacturing a color filter used in a liquid crystal display device or the like, a coating film of a colored radiation-sensitive composition is formed on a substrate or on a substrate on which a light-shielding layer of a desired pattern is formed in advance, A method of obtaining pixels of each color by irradiating radiation (hereinafter referred to as “exposure”) through a photomask having a pattern, developing and dissolving and removing unexposed portions, and then post-baking is known. I have.

In recent years, the flow of technological innovation has been rapid, and liquid crystal display devices equipped with color filters are required to have higher brightness and an expanded color reproduction range. It is required to have color purity.
Under these circumstances, in recent years, for increasing the luminance of a green pixel, for example, Patent Literatures 1 and 2 disclose a zinc phthalocyanine green pigment having a specific hue.

However, a pixel formed using the zinc phthalocyanine green pigment has problems that light leakage easily occurs and display unevenness of a display device easily occurs. Further, there has been a demand for further increasing the luminance and contrast of the obtained pixels.
Patent Literatures 3 to 5 disclose that a colored radiation-sensitive composition using a zinc phthalocyanine green pigment is liable to cause chipping of pixels when forming a coating film, and that linearity is hardly obtained. It describes the problem that chipping is further increasing.

JP 2008-122478 A JP 2009-052020A JP 2009-053652A JP 2010-014961 A JP 2010-097172 A

In view of the above-described conventional problems, an object of the present invention is to provide a green pigment coloring resin composition that reduces chipping of a pixel when a color filter is formed.
Further, the present invention provides a color filter having excellent pattern linearity, high light purity without light leakage, high brightness and high contrast, and a liquid crystal display device and an organic EL display device including the color filter. As an issue.

As a result of intensive studies, the present inventors have found that, when pixels are formed using zinc phthalocyanine green pigment, chipping of the pixels is the cause of the problem.
As a result of further study, it has been found that the first cause of the chipping of the pixel is due to an insufficient amount of the curable component caused by the following reason.
(1) The halogenated zinc phthalocyanine green pigment has a lower coloring power than pigments of other colors such as blue. Therefore, the content of the pigment contained in the green pigment coloring resin composition is larger than that of the blue pigment coloring resin composition.
(2) Since the halogenated zinc phthalocyanine green pigment has low dispersion stability, the dispersant and the dispersed resin contained in the green pigment coloring resin composition are increased.

That is, when the content of the pigment, the dispersant, and the dispersion resin increases, the amount of the curing component decreases, and the possibility of insufficient curing increases.
Furthermore, the second cause is that the halogenated zinc phthalocyanine green pigment blocks wavelengths of around 400 nm or less. By this blocking, it was found that one of the factors was that the photopolymerization initiator contained in the green pigment-colored resin composition was not functioning sufficiently.

That is, it has been found that the insufficient amount of the curable component and the insufficient function of the photopolymerization initiator are the causes of chipping of pixels.
The present inventors have conducted further studies based on these findings, and as a result, have found that the above problems can be solved by including a blue pigment in the green pigment-colored resin composition, and reached the present invention. did.

  That is, the present invention provides a green pigment comprising (A) a halogenated zinc phthalocyanine green pigment, (B) a photopolymerization initiator and (H) a solvent, and (D) a blue dye. The present invention resides in a colored resin composition, a color filter, a liquid crystal display device, and an organic EL display device.

When a pixel is formed using the green pigment-colored resin composition of the present invention, chipping of the pixel is small.
Further, the present invention provides a color filter having excellent pattern linearity, high light purity without light leakage, high brightness and high contrast, and a liquid crystal display device and an organic EL display device including the color filter. Becomes possible.

FIG. 1 is a schematic cross-sectional view illustrating an example of an organic EL device including a green color filter of the present invention. It is a microscope picture of a typical example of the pattern (pixel) used for the halftone measurement. In FIG. 2, (a) a pattern without a number, (b) a pattern with a number of 57, and (c) a pattern with a number of 100 or more.

Hereinafter, embodiments of the present invention will be described in detail. However, the following description is an example of embodiments of the present invention, and the present invention is not limited to these contents.
In the present invention, “(meth) acryl”, “(meth) acrylate” and the like mean “acryl and / or methacryl”, “acrylate and / or methacrylate” and the like, and for example, “(meth) acrylic acid” "Means" acrylic acid and / or methacrylic acid ".

The term "total solids" means all components of the green pigment-colored resin composition for a color filter of the present invention other than the solvent components described below.
In the present invention, the term “amine value” means an amine value in terms of effective solid content unless otherwise specified, and is a value represented by the weight of KOH equivalent to the amount of base per 1 g of solid content of a dispersant. is there. The measuring method will be described later.

Terms such as “CI Pigment Green” mean a color index (CI).
The green pigment coloring resin composition of the present invention contains (A) a halogenated zinc phthalocyanine green pigment, (B) a photopolymerization initiator and (H) a solvent, and further (D) a green pigment containing a blue dye. It is a resin composition.

First, the zinc halide phthalocyanine green pigment (A) will be described.
[(A) Halogenated zinc phthalocyanine green pigment]
The green pigment coloring resin composition of the present invention contains (A) a zinc halide phthalocyanine green pigment.
Ordinary zinc phthalocyanine has 16 hydrogen atoms in one molecule, and halogenated zinc phthalocyanine green pigment is obtained by replacing these hydrogen atoms with bromine atoms or chlorine atoms, and is preferably used in the present invention. Is a brominated zinc phthalocyanine green pigment.

  Above all, brominated zinc phthalocyanine containing an average of 13 or more bromine atoms in one molecule is preferable because it exhibits extremely high transmittance and is suitable for forming a green pixel of a color filter. Further, a brominated zinc phthalocyanine having 13 to 16 bromine atoms in one molecule and containing no chlorine or having an average of 3 or less in one molecule is preferable. A brominated zinc phthalocyanine having from 16 to 16 chlorine atoms in one molecule or having an average of 2 or less is preferred. Particularly preferably, C.I. I. Pigment Green 58.

  Among such halogenated zinc phthalocyanine green pigments, for example, brominated zinc phthalocyanine green pigments can be produced by a known production method disclosed in JP-A-50-130816. For example, a method of synthesizing a pigment by using phthalic acid or phthalonitrile, in which some or all of the hydrogen atoms of the aromatic ring are substituted with a halogen atom such as chlorine, as well as bromine as appropriate starting materials, may be mentioned. In this case, a catalyst such as ammonium molybdate may be used as necessary.

  As another method, there is a method in which zinc phthalocyanine is brominated with a bromine gas in a melt at about 110 to 170 ° C. which is a mixture of aluminum chloride, sodium chloride, sodium bromide and the like. In this method, the ratio of various brominated zinc phthalocyanines having different bromine contents is adjusted by adjusting the ratio of chloride and bromide in the molten salt or changing the amount of chlorine gas introduced or the reaction time. It can be arbitrarily controlled.

After completion of the reaction, when the obtained mixture is poured into an acidic aqueous solution such as hydrochloric acid, the generated brominated zinc phthalocyanine precipitates. Thereafter, post-treatments such as filtration, washing, and drying are performed to obtain brominated zinc phthalocyanine.
The brominated zinc phthalocyanine thus obtained may be used alone, or a brominated zinc phthalocyanine having a different bromination rate or chlorination rate, or a metal having a central metal of another metal as long as the effects of the present invention are not impaired. And a mixture thereof with a brominated phthalocyanine or the like. By changing the chlorination rate and bromination rate, and by changing the center metal, the color tone of the pigment changes, and the variation in the hue that can be reproduced increases.

Further, even with the same green pigment, C.I. I. Pigment Green (PG) 36 or 7 and the like may be mixed with a copper halide phthalocyanine.
The average primary particle size of the green pigment containing a halogenated zinc phthalocyanine is generally 0.1 μm or less, preferably 0.04 μm or less, more preferably 0.03 μm or less, further preferably 0.025 μm or less, and usually 0.1 μm or less. 005 μm or more. The average primary particle size of the other pigments is the same as described above.

By setting the average primary particle size to the upper limit or less, it is possible to form a pixel having less foreign matter in the composition, low depolarization, sufficient contrast and light transmittance, and a lower limit. By doing so, a green pigment-colored resin composition having good dispersion stability and sufficient heat and light resistance can be obtained.
The average primary particle size of the pigment can be determined by the following method. That is, the pigment is ultrasonically dispersed in chloroform, dropped on a mesh attached with a collodion film, dried, and a primary particle image of the pigment is obtained by observation with a transmission electron microscope (TEM). The primary particle size is measured from this image, and the number average value is calculated according to the following formula to determine the average particle size.

  In the case of an organic pigment, the particle diameter of each pigment particle was determined as the area circle equivalent diameter converted to the diameter of a circle having the same area, and the particle diameter was determined for each of a plurality, usually about 200 to 300 pigment particles. Thereafter, the number average value is calculated according to the following formula to determine the average particle size.

  The thus obtained brominated zinc phthalocyanine green pigment is dry-milled in a pulverizer such as an attritor, a ball mill, a vibration mill, a vibration ball mill, if necessary, and then pigmented by a solvent salt milling method or a solvent boiling method. By doing so, a brominated zinc phthalocyanine green pigment that emits green with high transmittance and contrast can be obtained. Although there is no particular limitation on the pigmentation method, it is preferable to employ a solvent salt milling method in that crystal growth can be easily suppressed and pigment particles having a large specific surface area can be obtained.

  The solvent salt milling method means kneading and milling a crude pigment immediately after synthesis, an inorganic salt, and an organic solvent. Specifically, a crude pigment, an inorganic salt, and an organic solvent that does not dissolve it are charged into a kneader, and kneading and milling are performed therein. The kneading machine at this time has, for example, a kneader or a mix muller, or a pulverizing space in which a gap between a circular fixed disk and a concentric rotating disk is formed as described in JP-A-2006-77062. A continuous kneader or the like is preferably used.

As the inorganic salt, a water-soluble inorganic salt can be suitably used, and for example, an inorganic salt such as sodium chloride, potassium chloride, and sodium sulfate is preferably used. Further, the particle diameter of these inorganic salts is more preferably 0.5 to 50 μm. Such an inorganic salt can be easily obtained by pulverizing a usual inorganic salt.
The content of the zinc halide phthalocyanine green pigment contained in the green pigment coloring resin composition of the present invention is usually 30 to 99.95% by weight, preferably 35 to 99.92% by weight, more preferably all pigments. Is 38 to 99.9% by weight.

It is preferable that the content is within the above-mentioned range since a satisfactory color filter with sufficient luminance, little chipping of the obtained pixels, excellent pattern linearity and few defects can be obtained.
In addition, the green pigment-colored resin composition of the present invention includes, as a pigment containing a pigment and a dye, in addition to the halogenated zinc phthalocyanine green pigment, a blue pigment described later, and a yellow pigment, if necessary, and other pigments. It may be appropriately contained.

The ratio of the coloring material to the total solid content in the colored resin composition of the present invention is usually 10 to 90% by weight, preferably 25 to 90% by weight.
When the content is within the above range, the film thickness is appropriate for the color density, and the gap control when forming a liquid crystal cell is easy. Furthermore, it is preferable because the dispersion stability is high and reagglomeration and thickening are difficult to set.
[(B) Photopolymerization initiator]
The green pigment coloring resin composition of the present invention contains (B) a photopolymerization initiator. The photopolymerization initiator is usually a mixture of (B) a photopolymerization initiator and, if necessary, (B1) a polymerization accelerator, and (B2) an additive such as a sensitizing dye (photopolymerization initiation system). Is a component having a function of directly absorbing light or being photosensitized to cause a decomposition reaction or a hydrogen abstraction reaction to generate a polymerization active radical.

  Examples of the photopolymerization initiator (B) constituting the photopolymerization initiation system include titanocene derivatives described in JP-A-59-152396 and JP-A-61-151197; JP-A-10-300922. Hexaarylbiimidazole derivatives described in JP-A-11-174224 and JP-A-2000-56118; halomethylated oxadiazole derivatives described in JP-A-10-39503 and the like; halomethyl-s -Triazine derivatives, N-aryl-α-amino acids such as N-phenylglycine, radical activators such as N-aryl-α-amino acid salts, N-aryl-α-amino acid esters, α-aminoalkylphenone derivatives And the like: Oxime ester derivatives described in JP-A-2000-80068 and the like.

  Specifically, for example, as biimidazole derivatives, 2- (2'-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (2'-chlorophenyl) -4,5-bis (3 ' -Methoxyphenyl) imidazole dimer, 2- (2′-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (2′-methoxyphenyl) -4,5-diphenylimidazole dimer, (4'-methoxyphenyl) -4,5-diphenylimidazole dimer and the like.

  Or, as the romethyl-s-triazine derivatives, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloro Methyl) -s-triazine, 2- (4-ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl)- s-triazine and the like.

  Examples of the α-aminoalkylphenone derivatives include 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one and 2-benzyl-2-dimethylamino-1- (4- Morpholinophenyl) -butanone-1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzoate , 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4 -Diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone and the like. It is.

Examples of the oxime ester derivatives include 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (o-benzoyloxime), ethanone, and 1- [9-ethyl-6- ( 2-methylbenzoyl) -9H-carbazol-3-yl], 1- (o-acetyloxime), and the like.
In addition, benzoin alkyl ethers, anthraquinone derivatives; acetophenone derivatives such as 2-methyl- (4′-methylthiophenyl) -2-morpholino-1-propanone, 2-ethylthioxanthone, and 2,4-diethylthioxanthone Thioxanthone derivatives, benzoic acid ester derivatives, acridine derivatives, phenazine derivatives, anthrone derivatives and the like are also included.

Among these photopolymerization initiators, α-aminoalkylphenone derivatives, thioxanthone derivatives, and oxime ester derivatives are more preferable. In particular, oxime ester derivatives are preferred.
Examples of the (B1) polymerization accelerator used if necessary include N, N-dialkylaminobenzoic acid alkyl esters such as N, N-dimethylaminobenzoic acid ethyl ester; 2-mercaptobenzothiazole, 2-mercapto Mercapto compounds having a heterocyclic ring such as benzoxazole and 2-mercaptobenzimidazole; and mercapto compounds such as aliphatic polyfunctional mercapto compounds.

As the photopolymerization initiator (B) and the polymerization accelerator (B1), one kind may be used alone, or two or more kinds may be used in combination.
A sensitizing dye (B2) is used for the purpose of increasing the sensitivity as required. As the sensitizing dye, an appropriate one is used depending on the wavelength of the image exposure light source. For example, xanthene dyes described in JP-A-4-221958 and JP-A-4-219756; Coumarin dyes having a heterocyclic ring described in JP-A-239703 and JP-A-5-289335; 3-ketocoumarin dyes described in JP-A-3-239703 and JP-A-5-289335; Pyrromethene dyes described in JP-A-6-19240 and the like; JP-A-47-2528, JP-A-54-155292, JP-B-45-37377, JP-A-48-84183, JP-A-52-112681. JP-A-58-15503, JP-A-60-88005, JP-A-59-56403, JP-A-2-69, JP-A-57-168088, and JP-A-5-10 761 No., JP-A-5-210240, dyes having a dialkyl aminobenzene skeleton described in JP-A 4-288818 Patent JP-like.

As the sensitizing dye (B2), one type may be used alone, or two or more types may be used in combination.
In the green pigment-colored resin composition of the present invention, the content of the photopolymerization initiation system is usually 0.1 to 40% by weight, preferably 0.2 to 30% by weight, more preferably 0 to 30% by weight based on the total solid content. The range is from 0.5 to 20% by weight. It is preferable for it to be within the above range because the sensitivity to exposure light is good and the unexposed part has good solubility in a developing solution.

[(H) solvent]
The green pigment coloring resin composition of the present invention contains (H) a solvent.
The (H) solvent in the present invention is not particularly limited as long as it dissolves or disperses the components constituting the green pigment-colored resin composition and has an appropriate viscosity, but preferably has a boiling point of 100 to 200 ° C. And more preferably a solvent having a boiling point of 120 to 170 ° C.

Examples of such a solvent include the following.
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol mono-t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, methoxymethyl pentanol, propylene Glycol monoalkyl ethers such as glycol monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, and tripropylene glycol monomethyl ether;
Glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether;
Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monoethyl Glycol alkyl ether acetates such as ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, and 3-methyl-3-methoxybutyl acetate;
Ethers such as diethyl ether, dipropyl ether, diisopropyl ether, diamyl ether, ethyl isobutyl ether, dihexyl ether;
Ketones such as acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone;
Mono- or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerin;
aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane;
Alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexyl;
Aromatic hydrocarbons such as benzene, toluene, xylene, cumene;
Amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl Caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxypropionic acid Linear or cyclic esters such as butyl, γ-butyrolactone;
Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;
Halogenated hydrocarbons such as butyl chloride and amyl chloride;
Ether ketones such as methoxymethylpentanone;
Nitriles such as acetonitrile and benzonitrile:
Commercially available solvents corresponding to the above include Mineral Spirit, Valsol # 2, Apco # 18 Solvent, Apco Thinner, Socal Solvent No. 1 and No. 1 2, Solvesso # 150, Shell TS28 Solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, diglyme (all of which are trade names).

One of these solvents may be used alone, or two or more thereof may be used in combination.
Among the above solvents, glycol alkyl ether acetates (glycol alkyl ether acetate-based solvents) are preferred from the viewpoint of good dispersibility in solvents such as the zinc halide phthalocyanine green pigment of the present invention described above. Further, propylene glycol monomethyl ether acetate is particularly preferred from the viewpoint of the solubility of various components in the green pigment coloring resin composition.

In addition, it is more preferable to use a mixture of glycol monoalkyl ethers as a solvent from the viewpoint that the coatability, the surface tension and the like are well balanced and the solubility of the components in the composition is relatively high.
(H) The proportion of glycol monoalkyl ethers in the solvent is preferably from 5 to 50% by weight, more preferably from 5 to 30% by weight, from the viewpoint of good storage stability.

When used in the slit coating method, it is also preferable to use a solvent having a boiling point of 150 ° C. or more. In this case, the content of the solvent having a boiling point of 150 ° C. or higher is preferably 1 to 50% by weight, more preferably 2 to 40% by weight, and particularly preferably 3 to 30% by weight, based on the whole solvent (H).
When it is within the above range, the drying speed is appropriate, so that the coloring material components and the like hardly precipitate and solidify at the tip of the slit nozzle, and the tact defect of the vacuum drying process in the color filter manufacturing process, pin marks of prebaking, etc. Is difficult to occur.

Examples of the solvent having a boiling point of 150 ° C. or higher include glycol alkyl ether acetates, glycol alkyl ethers, and chain or cyclic esters.
In addition, when used in the ink jet method, it is preferable to use a high boiling point solvent. This is because the ink ejected from the nozzle is very small, several to several tens of pL, and the solvent evaporates before the ink lands around the nozzle opening or in the pixel bank. This is to prevent drying.

As the high boiling point solvent, specifically, the boiling point of the solvent (H) is preferably 180 ° C. or higher, more preferably 200 ° C. or higher, and particularly preferably 220 ° C. or higher.
The content of the solvent at 180 ° C. or higher is preferably 50% by weight or more based on the whole solvent (H). It is preferable that the content is within the above range, since the effect of preventing the solvent from evaporating from the ink droplets is sufficient.

In the green pigment-colored resin composition of the present invention, the content of the solvent (H) is not particularly limited as long as the effects of the present invention are not impaired, but is usually 75% by weight or more, preferably 80% by weight or more, and more preferably Is 82% by weight or more, and usually 99% by weight or less.
Within the above range, the green pigment-colored resin composition has a viscosity suitable for application, and is preferable in that a good coating film can be formed.

[(D) Blue dye]
The blue pigment (D) in the present invention may be a blue pigment or a blue dye, but is preferably a blue pigment in terms of good coloring power. The blue pigment is not particularly limited as long as the effects of the present invention are not impaired, and known materials can be used.

(Specific examples of blue pigment)
As compounds corresponding to blue pigments, C.I. I. Pigment Blue 15: 6, 15: 1, 15: 2, 15: 3, 15: 4, 15: 5, 1, 1: 2, 9, 14, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79, etc. (C.I. I.) Those having numbers are given.

It is preferable to use a phthalocyanine blue pigment because it is inexpensive and easily available. More specifically, C.I. I. Pigment Blue 15: 1, 15: 2, 15: 3, 15: 4, 15: 5, 15: 6, 16, 17: 1 and the like.
In particular, a copper phthalocyanine blue pigment having a transmission region in a short wavelength region is preferable. More specifically, the blue dye in the present invention is preferably a compound represented by the following formula (1-I).

(In the above formula (1-I), each R independently represents a hydrogen atom or a halogen atom.)
Rs each independently represent a hydrogen atom or a halogen atom, and it is particularly preferable that all of them be hydrogen atoms from the viewpoint of easily transmitting the wavelength excited by the photopolymerization initiator (B).
Among them, C.I. I. Pigment Blue 15: 6 is most preferred. The phthalocyanine blue pigment used in the green pigment coloring resin composition of the present invention may be used alone or in combination of two or more.
The average primary particle size of the blue pigment is the same as in the above-described embodiment of <Halogenated zinc phthalocyanine green pigment>. The same applies to the preferred embodiment.

(Content)
The content of the blue pigment contained in the green pigment-colored resin composition of the present invention is usually 0.05 to 2.0% by weight, preferably 0.08 to 1.5% by weight, more preferably all pigments. Is 0.1 to 1.0% by weight.
It is preferable that the content is within the above-mentioned range since a satisfactory color filter with sufficient luminance, little chipping of the obtained pixels, excellent pattern linearity and few defects can be obtained.

[Yellow pigment]
The green pigment-colored resin composition of the present invention preferably contains (E) a yellow pigment in order to exhibit a better green color tone.
Further, the yellow pigment (E) in the present invention may be a yellow pigment or a yellow dye, but is preferably a yellow pigment in terms of good coloring power.

Examples of yellow pigments include monoazo, diazo, condensed diazo, benzimidazolone, azo metal complexes, azomethine, pyrazolone, quinophthalone, isoindoline, isoindolinone, and flavatron. An azo type, a quinophthalone type, and an isoindoline type are preferable in terms of excellent transmittance and contrast.
Preferred specific examples of the yellow pigment are shown below, but the present invention is not limited thereto.

(Specific examples of yellow pigment)
As a yellow pigment, a nickel azo complex, C.I. I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 86, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 125, 126, 127, 127: 1, 128, 129, 133, 134, 136, 137, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 69, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208. Among these, nickel azo complex, C.I. I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, more preferably a nickel azo complex, C.I. I. Pigment Yellow 83, 138, 139, 150, and 180.

Incidentally, the average primary particle size of the yellow pigment is the same as in the above-described embodiment of <Halogenated zinc phthalocyanine green pigment>. The same applies to the preferred embodiment.
(Content)
The content of the yellow pigment in all the pigments contained in the green pigment coloring resin composition of the present invention is usually 0.05 to 70% by weight, preferably 0.08 to 65% by weight, and more preferably 0.1 to 65% by weight. 62% by weight.

It is preferable that it is within the above range, since color adjustment can be performed well.
<Reason for effect>
As described above, when a pixel is formed using a zinc halide phthalocyanine green pigment, the cause of the chipping of the pixel is that the amount of the curable component is small and the initiator does not function sufficiently. The reason why the initiator does not function sufficiently is assumed as follows.

The photopolymerization initiator preferably has an absorption wavelength of 380 nm or less in order to maintain good transparency in the visible light region. However, a high-pressure mercury lamp, which is a general-purpose exposure light source, emits h-line and g-line, and an initiator having an absorption wavelength in a wavelength region exceeding 400 nm is used for high sensitivity.
However, the halogenated zinc phthalocyanine green pigment has a low transmittance near 400 nm. For this reason, a photopolymerization initiator or the like having increased sensitivity is unlikely to be radicalized by absorbing light.

On the other hand, the blue dye has a high transmittance near 400 nm, and easily generates photopolymerization initiator radicals. In other words, the photopolymerization initiator functions sufficiently by including the blue dye in the composition, and even if the curable component is small, the pixels to be formed can be sufficiently cured, and the resulting pixels are less chipped. .
Further, by containing a yellow pigment, it becomes possible to exhibit green chromaticity, and the content of the zinc halide phthalocyanine green pigment can be reduced to such an extent that chipping of the obtained pixels can be reduced.

[(F) Dispersant]
The type of the dispersant (F) in the present invention is not particularly limited as long as the pigment can be dispersed and stability can be maintained. For example, a dispersant such as a cationic dispersant, an anionic dispersant, a nonionic dispersant or an amphoteric dispersant can be used, but a polymer dispersant is preferable. Specific examples include modified acrylic copolymers, acrylic copolymers, polyurethanes, polyesters, alkylammonium salts or phosphate esters of high molecular weight copolymers, and cationic comb-type graft polymers. Among these dispersants, modified acrylic copolymers, polyurethanes, and cationic comb graft polymers are preferred. In particular, a modified acrylic copolymer is preferable. Among them, it is a block copolymer composed of an A block having a solvent affinity and a B block having a functional group containing a nitrogen atom, and has an amine value of 80 mgKOH / g or more and 150 mgKOH / g. What is the following (effective solid content conversion) is especially preferable. More preferably, it is 100 to 140 mgKOH / g.

When it is within the above range, the adsorbing power to the pigment surface is sufficient, and the dispersion stability is good.
Among them, (meth) acrylic block copolymers described in JP-A-2009-025813 are preferable.
The acrylic block copolymer can very efficiently disperse the pigment (A). This is presumed to be due to the fact that the molecular arrangement is controlled so that there are few structures that hinder the adsorption of the dispersant to the pigment.

Further, in the present invention, the acrylic block copolymer is preferably an AB block composed of an A block and a B block and / or an ABA block copolymer.
B blocks constituting the acrylic block copolymer has an amino group, an amino group is preferably -NR ⁴¹ R ⁴² (where, R ⁴¹ and R ⁴² each independently have a substituent And an optionally substituted cyclic or chain alkyl group, an optionally substituted aryl group, or an optionally substituted aralkyl group.) Is preferably represented by the following formula, for example.

(However, R ⁴¹ and R ⁴² have the same meanings as R ⁴¹ and R ⁴² described above, R ⁴³ is an alkylene group having 1 or more carbon atoms, and R ⁴⁴ represents a hydrogen atom or a methyl group.) ⁴¹ and R ⁴² is preferably a methyl group, R ⁴³ is preferably a methylene group or an ethylene group,, R ⁴⁴ is preferably methyl. Such a compound includes a partial structure represented by the following formula.

  As described above, two or more kinds of amino group-containing partial structures may be contained in one B block. In this case, two or more amino group-containing partial structures may be contained in the B block in any mode of random copolymerization or block copolymerization. Further, a partial structure not containing an amino group may be partially contained in the B block as long as the effects of the present invention are not impaired. Examples of such a partial structure include (meth) acrylic acid esters And a partial structure derived from a system monomer.

On the other hand, in the present invention, the A block of the dispersant (F) is not particularly limited as long as it is a solvent-philic and is composed of a monomer copolymerizable with the monomer constituting the B block described above.
Examples of the A block include a polymer structure obtained by copolymerizing a comonomer such as a styrene monomer, a (meth) acrylate monomer, a (meth) acrylate monomer, a vinyl acetate monomer, and a glycidyl ether monomer. Can be

The (F) dispersant contained in the green pigment-colored resin composition of the present invention is an AB block or ABA block copolymer type polymer compound composed of the A block and the B block as described above. Above all, an AB block copolymer is preferable. Such a block copolymer is prepared, for example, by a living polymerization method.
Living polymerization includes anionic living polymerization, cationic living polymerization, and radical living polymerization. Specifically, for example, a method described in JP-A-2007-270147 is exemplified.

The amine value (in terms of effective solid content) of the dispersant is represented by the weight of KOH equivalent to the amount of base per 1 g of solid content excluding the solvent in the dispersant sample, and is measured by the following method. 0.5-1.5 g of the dispersant sample is precisely weighed in a 100 mL beaker, and dissolved with 50 mL of acetic acid. This solution is neutralized and titrated with a 0.1 mol / L HClO ₄ acetic acid solution using an automatic titrator equipped with a pH electrode. The amine value is determined by the following equation using the inflection point of the titration pH curve as the end point of the titration.

Amine value [mgKOH / g] = (561 × V) / (W × S)
(W: W: weighed amount of dispersant sample [g], V: titer at the end of titration [mL], S: solid content concentration of dispersant sample [wt%].)
Further, the acid value of this block copolymer depends on the presence or absence and the type of the acidic group from which the acid value is derived, but is preferably low, usually 50 mgKOH / g or less, preferably 40 or less, more preferably 30 or less. It is as follows.

When the average primary particle size of the pigment is small, the specific surface area increases and the adsorbed amount of the dispersant per unit area decreases. In this case, the dispersant comprising the copolymer has a greater effect than other dispersants and is preferably used.
The dispersant used in the present invention is preferably used in an amount of about 5 to 200% by weight, more preferably about 10 to 100% by weight, based on the total amount of the pigment in the green pigmented resin composition.

The green pigment-colored resin composition of the present invention may contain other dispersants as long as the effects of the present invention are not impaired. Examples of other dispersants include, for example, those described in JP-A-2006-343648.
[Dispersion aid]
The green pigment coloring resin composition of the present invention may contain a dispersing aid. The dispersion aid referred to herein may be a pigment derivative. Examples of the pigment derivative include, for example, JP-A-2001-220520, JP-A-2001-271004, JP-A-2002-179976, and JP-A-2007-2007. Various compounds described in JP-A-113000 and JP-A-2007-186681 can be used.

  Incidentally, the content of the dispersing aid in the green pigment-colored resin composition of the present invention is usually 0.1% by weight or more, and usually 30% by weight or less, preferably 20% by weight or less based on the total solid content of the pigment. , More preferably 10% by weight or less, still more preferably 5% by weight or less. By controlling the addition amount in the above range, the effect as a dispersing aid is exhibited, and the dispersibility and the dispersion stability are more preferable.

Further, when other dispersing aids are contained, the total amount of the dispersing aids is adjusted to be within the above range.
[Dispersion resin]
The green pigment-colored resin composition of the present invention may contain a part or all of a resin selected from the binder resin (C) and other binder resins described below as the following dispersion resin.

  Specifically, in the dispersion treatment step described below, by adding the (C) binder resin together with the above-mentioned component (F) such as the dispersant, the (C) binder resin is mixed with the (F) dispersant. The synergistic effect contributes to the dispersion stability of (A) the halogenated zinc phthalocyanine green pigment and other pigments. As a result, the amount of the dispersant (F) may be reduced, which is preferable. In addition, it is preferable because the developing property is improved, undissolved matter does not remain in the non-pixel portion of the substrate, and the adhesion of the pixel to the substrate is improved.

As described above, the binder resin (C) used in the dispersion process may be referred to as a dispersion resin. The dispersing resin is preferably used in an amount of about 0 to 200% by weight, more preferably about 10 to 100% by weight, based on the total amount of the pigment in the pigment dispersion.
Various (C) binder resins described below can be used as the dispersion resin.
The acid value of the dispersion resin is preferably 0.5 mg KOH / g or more, more preferably 1 mg KOH / g or more, most preferably 5 mg KOH / g or more, and preferably 300 mg KOH / g or less, more preferably 200 mg KOH / g or less, and 150 mg KOH / g. The following are most preferred. By controlling the acid value in the above range, alkali developability is improved, and handling becomes easy even in synthesis.

  The weight average molecular weight of the dispersion resin in terms of polystyrene measured by GPC is preferably 1,000 or more, more preferably 1500 or more, most preferably 2,000 or more, and preferably 200,000 or less, more preferably 50,000 or less, and 30,000 or less. Most preferred. By controlling the molecular weight in the above range, the alkali developability is improved and the dispersion stability can be prevented from lowering.

[(C) Binder resin]
(C) The preferred resin differs depending on the curing means.
When the colored resin composition of the present invention is a photopolymerizable resin composition, examples of the binder resin (C) include JP-A-7-207211, JP-A-8-259876, JP-A-10-300922, and JP-A-10-300922. Polymer compounds described in JP-A-11-140144, JP-A-11-174224, JP-A-2000-56118, JP-A-2003-233179, and the like can be used. C-1) to (C-5) resins and the like.

(C-1): For a copolymer of an epoxy group-containing (meth) acrylate and another radically polymerizable monomer, an unsaturated monobasic acid is used for at least a part of the epoxy group of the copolymer. An alkali-soluble resin obtained by adding a polybasic acid anhydride to at least a part of a hydroxyl group generated by the addition reaction or a hydroxyl group generated by the addition reaction (hereinafter, may be referred to as “resin (C-1)”) .)
(C-2): Carboxyl group-containing linear alkali-soluble resin (C-2) (hereinafter sometimes referred to as “resin (C-2)”).
(C-3): a resin in which an epoxy group-containing unsaturated compound is added to the carboxyl group of the resin (C-2) (hereinafter sometimes referred to as “resin (C-3)”).
(C-4): (meth) acrylic resin (hereinafter sometimes referred to as “resin (C-4)”)
(C-5): epoxy acrylate resin having a carboxyl group (hereinafter sometimes referred to as “resin (C-5)”)
Of these, resin (C-1) is particularly preferred, and the resin will be described below.

The resins (C-2) to (C-5) may be any resin as long as it is dissolved by an alkaline developer and has a solubility to the extent that the intended development processing is performed. It is the same as that described as the same item in 2009-025813. The same applies to the preferred embodiment.
(C-1): For a copolymer of an epoxy group-containing (meth) acrylate and another radically polymerizable monomer, an unsaturated monobasic acid is used for at least a part of the epoxy group of the copolymer. An alkali-soluble resin obtained by adding a polybasic anhydride to at least a part of a hydroxyl group generated by the addition reaction or a hydroxyl group generated by the addition reaction is one of particularly preferred resins (C-1). 10 to 100 mol% of epoxy groups contained in the copolymer of 5 to 90 mol% of the contained (meth) acrylate and 10 to 95 mol% of another radically polymerizable monomer are unsaturated. Examples thereof include a resin obtained by adding a monobasic acid, and an alkali-soluble resin obtained by adding a polybasic acid anhydride to 10 to 100 mol% of hydroxyl groups generated by the addition reaction.

  Examples of the epoxy group-containing (meth) acrylate include glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. ) Acrylate glycidyl ether and the like. Among them, glycidyl (meth) acrylate is preferred. One of these epoxy group-containing (meth) acrylates may be used alone, or two or more thereof may be used in combination.

  The other radical polymerizable monomer copolymerized with the epoxy group-containing (meth) acrylate is not particularly limited as long as the effects of the present invention are not impaired. For example, vinyl aromatics, dienes, (meth) Acrylic esters, (meth) acrylic amides, vinyl compounds, unsaturated dicarboxylic diesters, monomaleimides, etc., are particularly preferred. Mono (meth) having a structure represented by the following formula (7) Acrylates are preferred.

  The repeating unit derived from a mono (meth) acrylate having a structure represented by the following formula (7) is a repeating unit derived from “another radically polymerizable monomer” that has a content of 5 to 90 mol%. Preferably, those containing 10 to 70 mol% are more preferable, and those containing 15 to 50 mol% are particularly preferable.

In the above formula (7), R ⁸⁹ represents a hydrogen atom or a methyl group, and R ⁹⁰ represents a structure represented by the following formula (8).

In the above formula (8), R ^{91 to} R ⁹⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Incidentally, R ⁹⁶ and R ⁹⁸ may be linked to each other to form a ring.
The ring formed by linking R ⁹⁶ and R ⁹⁸ is preferably an aliphatic ring, which may be saturated or unsaturated, and more preferably 5 to 6 carbon atoms.
Above all, among the structures represented by the formula (8), those represented by the following structural formulas (8a), (8b) or (8c) are preferable.

The mono (meth) acrylate having the structure represented by the formula (8) may be used alone or in combination of two or more.
As the “other radically polymerizable monomer” other than the mono (meth) acrylate having the structure represented by the formula (8), the colored resin composition can have excellent heat resistance and strength. , Styrene, n-butyl (meth) acrylate, -tert-butyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, benzyl (meth) acrylate , 2-hydroxyethyl (meth) acrylate, N-phenylmaleimide, N-cyclohexylmaleimide.

The content of the repeating unit derived from at least one selected from the above monomer group is preferably from 1 to 70 mol%, more preferably from 3 to 50 mol%.
A known solution polymerization method is applied to the copolymerization reaction between the epoxy group-containing (meth) acrylate and the other radical polymerizable monomer.
In the present invention, the copolymer of the epoxy group-containing (meth) acrylate and the other radically polymerizable monomer includes 5-90 mol% of a repeating unit derived from the epoxy group-containing (meth) acrylate; Of a repeating unit derived from a radical polymerizable monomer of 10 to 95 mol%, more preferably 20 to 80 mol% of the former and 80 to 20 mol% of the latter, and more preferably 30 to 95 mol% of the former. Those comprising 70 mol% and the latter 70 to 30 mol% are particularly preferred.

It is preferable for the amount to be in the above range because the amounts of the polymerizable component and the alkali-soluble component described later are sufficient and the heat resistance and strength are sufficient.
The unsaturated monobasic acid (polymerizable component) and the polybasic acid anhydride (alkali-soluble component) are reacted with the epoxy group portion of the epoxy group-containing copolymer synthesized as described above.
Here, as the unsaturated monobasic acid to be added to the epoxy group, known ones can be used, and examples thereof include an unsaturated carboxylic acid having an ethylenically unsaturated double bond.

  Specific examples include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, and the α-position substituted with a haloalkyl group, an alkoxyl group, a halogen atom, a nitro group, or a cyano group. Monocarboxylic acids such as (meth) acrylic acid are exemplified. Among them, (meth) acrylic acid is preferable. These may be used alone or in combination of two or more.

By adding such components, polymerizability can be imparted to the binder resin used in the present invention.
These unsaturated monobasic acids are usually added to 10 to 100 mol% of the epoxy groups of the copolymer, preferably 30 to 100 mol%, more preferably 50 to 100 mol%. It is preferable for it to be in the above-mentioned range because the colored resin composition has excellent stability over time. In addition, as a method of adding an unsaturated monobasic acid to the epoxy group of the copolymer, a known method can be adopted.

Further, as the polybasic acid anhydride to be added to the hydroxyl group generated when an unsaturated monobasic acid is added to the epoxy group of the copolymer, known ones can be used.
For example, dibasic anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride; trimellitic anhydride, pyromellitic anhydride, benzophenone An anhydride of an acid having three or more bases such as tetracarboxylic anhydride, biphenyltetracarboxylic anhydride and the like can be mentioned. Among them, succinic anhydride and tetrahydrophthalic anhydride are preferred. One of these polybasic acid anhydrides may be used alone, or two or more may be used in combination.

By adding such components, alkali solubility can be imparted to the binder resin used in the present invention.
These polybasic acid anhydrides are usually added to the epoxy groups of the copolymer in an amount of 10 to 100 mol% of the hydroxyl groups generated by adding an unsaturated monobasic acid, preferably 20 to 90 mol. %, More preferably 30 to 80 mol%.

It is preferable that the content is in the above range because the residual film ratio and the solubility at the time of development are sufficient.
In addition, as a method of adding a polybasic acid anhydride to the hydroxyl group, a known method can be adopted.
Furthermore, in order to improve the photosensitivity, after adding the above-mentioned polybasic acid anhydride, glycidyl (meth) acrylate or a glycidyl ether compound having a polymerizable unsaturated group is added to a part of the generated carboxyl group. You may. Such a resin structure is described in, for example, JP-A-8-297366 and JP-A-2001-89533.

  The weight average molecular weight (Mw) of the above-mentioned binder resin (C-1) in terms of polystyrene measured by GPC (gel permeation chromatography) is preferably from 3,000 to 100,000, particularly preferably from 5,000 to 50,000. If the molecular weight is less than 3,000, heat resistance and film strength may be poor, and if it exceeds 100,000, the solubility in a developer tends to be insufficient. As a standard of the molecular weight distribution, the ratio of weight average molecular weight (Mw) / number average molecular weight (Mn) is preferably 2.0 to 5.0.

The acid value of the binder resin (C-1) is usually 10 to 200 mg-KOH / g, preferably 15 to 150 mg-KOH / g, and more preferably 25 to 100 mg-KOH / g.
It is preferable for it to be within the above range, since the solubility in a developing solution is good and the film is hardly roughened.

The content of the binder resin (C) is usually 0.1 to 80% by weight, preferably 1 to 60% by weight, based on the total solid content.
It is preferable if it is in the above range, because the adhesion to the substrate is good, the permeability of the developing solution to the exposed portion is appropriate, and the surface smoothness and sensitivity of the pixel are good.
[(G) Polymerizable monomer]
The green pigment coloring resin composition of the present invention preferably contains (G) a polymerizable monomer. (G) The polymerizable monomer is not particularly limited as long as it is a polymerizable low-molecular compound, but an addition-polymerizable compound having at least one ethylenic double bond (hereinafter sometimes referred to as an “ethylenic compound”). Is preferred).

The ethylenic compound is a compound having an ethylenic double bond such that when the green pigment-colored resin composition of the present invention is irradiated with actinic rays, it undergoes addition polymerization by the action of the photopolymerization initiation system and cures. . The polymerizable monomer (G) in the present invention means a concept corresponding to a so-called polymer substance, and includes dimers, trimers and oligomers in addition to monomers in a narrow sense.
(G) Examples of the ethylenic compound in the polymerizable monomer include unsaturated carboxylic acids such as (meth) acrylic acid; esters of monohydroxy compounds and unsaturated carboxylic acids; aliphatic polyhydroxy compounds and unsaturated carboxylic acids. Ester of an aromatic polyhydroxy compound with an unsaturated carboxylic acid; esterification of an unsaturated carboxylic acid with a polyvalent carboxylic acid and the aforementioned polyvalent hydroxy compound such as the aliphatic polyhydroxy compound and the aromatic polyhydroxy compound Ester obtained by the reaction; an ethylenic compound having a urethane skeleton obtained by reacting a polyisocyanate compound with a (meth) acryloyl group-containing hydroxy compound; and the like.

  Examples of the ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid include ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and trimethylolethane tri (meth) acrylate. Pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) (Meth) acrylic acid esters such as acrylate and glycerol (meth) acrylate. In addition, itaconic acid ester in which the (meth) acrylic acid portion of the (meth) acrylic acid ester is replaced with the itaconic acid portion, crotonic acid ester in which the crotonic acid portion is replaced, or maleic acid ester in which the maleic acid portion is replaced. Is mentioned.

Examples of the ester of the aromatic polyhydroxy compound with the unsaturated carboxylic acid include hydroquinone di (meth) acrylate, resorcinol di (meth) acrylate, and pyrogallol tri (meth) acrylate.
The ester obtained by the esterification reaction of the unsaturated carboxylic acid with the polyvalent carboxylic acid and the polyvalent hydroxy compound is not necessarily a single substance, but may be a mixture. Representative examples include condensates of (meth) acrylic acid, phthalic acid, and ethylene glycol; condensates of (meth) acrylic acid, maleic acid, and diethylene glycol; condensation of (meth) acrylic acid, terephthalic acid, and pentaerythritol Products; condensates of (meth) acrylic acid, adipic acid, butanediol, and glycerin.

  Examples of the ethylenic compound having a urethane skeleton obtained by reacting a polyisocyanate compound with a (meth) acryloyl group-containing hydroxy compound include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; alicyclic rings such as cyclohexane diisocyanate and isophorone diisocyanate. Formula diisocyanate; aromatic diisocyanate such as tolylene diisocyanate, diphenylmethane diisocyanate, and (meth) acryloyl such as 2-hydroxyethyl (meth) acrylate and 3-hydroxy [1,1,1-tri (meth) acryloyloxymethyl] propane A reaction product with a group-containing hydroxy compound is exemplified.

In addition, examples of the ethylenic compound used in the present invention include (meth) acrylamides such as ethylenebis (meth) acrylamide; allyl esters such as diallyl phthalate; and vinyl group-containing compounds such as divinyl phthalate. .
Among these, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid is preferred, a (meth) acrylate of pentaerythritol or dipentaerythritol is more preferred, and dipentaerythritol hexa (meth) acrylate is particularly preferred.

  Further, the ethylenic compound may be a monomer having an acid value. The monomer having an acid value is, for example, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and the non-aromatic carboxylic anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound to obtain an acid. A polyfunctional monomer having a group is preferable, and particularly preferably, in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol.

One of these monomers may be used alone, but a mixture of two or more may be used because it is difficult to obtain a single compound in production.
If necessary, (G) a polymerizable monomer having no acid group and a polyfunctional monomer having an acid group may be used in combination.
The preferred acid value of the polyfunctional monomer having an acid group is 0.1 to 40 mg-KOH / g, and particularly preferably 5 to 30 mg-KOH / g.

When the content is within the above range, the development dissolution characteristics are not easily reduced, and the production and handling are easy. Further, it is preferable because the photopolymerization performance is hard to decrease and the curability such as the surface smoothness of the pixel is good.
In the present invention, a more preferred polyfunctional monomer having an acid group is, for example, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, or a mixture mainly containing a succinic ester of dipentaerythritol pentaacrylate. This polyfunctional monomer can be used in combination with another polyfunctional monomer.

In the green pigment-colored resin composition of the present invention, the content of the polymerizable monomer (G) in the total solid content is usually 1% by weight or more, preferably 5% by weight or more, more preferably 10% by weight or more. Yes, it is usually at most 80% by weight, preferably at most 70% by weight, more preferably at most 50% by weight, particularly preferably at most 40% by weight.
The ratio of (G) the total amount of the polymerizable monomer to the total colorants, that is, (A) the zinc phthalocyanine green pigment, (D) the blue pigment, (E) the yellow pigment, and the other pigments is usually 1% by weight. It is preferably at least 5% by weight, more preferably at least 10% by weight, particularly preferably at least 20% by weight, and usually at most 200% by weight, preferably at most 150% by weight, more preferably at most 110% by weight. is there.

When the content is within the above range, photocuring is moderate, poor adhesion during development is difficult to place, and the cross section after development is unlikely to have an inverse tapered shape, and further, peeling phenomenon and poor defect due to reduced solubility are difficult to place. preferable.
[Method for Preparing Green Pigment Colored Resin Composition]
In the present invention, the green pigment-colored resin composition can be prepared by an appropriate method. For example, (A) a halogenated zinc phthalocyanine green pigment, (B) a photopolymerization initiator, (H) a solvent, D) It can be prepared by mixing with a blue dye and other additives.

  As a more preferable preparation method, (A) a halogenated zinc phthalocyanine green pigment and other pigments (including a blue pigment and a yellow pigment) in a solvent, (F) a dispersing agent and a dispersing agent to be added as necessary. In the presence, optionally with a part of the binder resin (C), for example, using a paint shaker, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, etc., pulverize and mix and disperse while disintegrating. Prepare liquid. A method of adding (B) a photopolymerization initiator, (C) a binder resin, and if necessary, an additive such as (G) a polymerizable monomer to the colored dispersion, and mixing the resulting mixture is followed by mixing. it can.

[Application of green pigment coloring resin composition]
The green pigment-colored resin composition of the present invention is usually in a state in which all components are dissolved or dispersed in a solvent. The green pigment-colored resin composition is supplied onto a substrate, and components such as a color filter, a liquid crystal display, and an organic EL display are formed.
Hereinafter, as an application example of the green pigment coloring resin composition of the present invention, an application as a color filter and a liquid crystal display device (panel) and an organic EL display device using the same will be described.

<Color filter>
The color filter of the present invention includes pixels formed from the green pigment-colored resin composition of the present invention.
Hereinafter, a method for forming the color filter of the present invention will be described.
The pixels of the color filter can be formed in various ways. Here, the case of forming by photolithography using a photopolymerizable green pigment coloring resin composition will be described as an example, but the manufacturing method is not limited to this.

  First, on the surface of the substrate, if necessary, a black matrix is formed so as to partition a portion for forming a pixel, and after applying the green pigment-colored resin composition of the present invention on the substrate, prebaking is performed. To evaporate the solvent to form a coating. Next, after this coating film is exposed through a photomask, it is developed using an alkaline developer to dissolve and remove the unexposed portion of the coating film, and then post-baked, so that each of the red, green, and blue colors is removed. A color filter can be manufactured by forming a pixel pattern.

The substrate used when forming the pixel is not particularly limited as long as it is transparent and has an appropriate strength.For example, a polyester resin, a polyolefin resin, a polycarbonate resin, an acrylic resin, a thermoplastic resin Sheet, epoxy resin, thermosetting resin, various types of glass, and the like.
In addition, these substrates may be appropriately subjected to a pretreatment such as a thin film formation treatment with a silane coupling agent or a urethane resin, a surface treatment such as a corona discharge treatment or an ozone treatment, if desired.

When the green pigment-colored resin composition is applied to a substrate, a spinner method, a wire bar method, a flow coating method, a slit-and-spin method, a die coating method, a roll coating method, a spray coating method and the like can be mentioned. Among them, the slit and spin method and the die coating method are preferred.
The thickness of the coating film is usually from 0.2 to 20 μm, preferably from 0.5 to 10 μm, particularly preferably from 0.8 to 5.0 μm, as the thickness after drying.

It is preferable that the content is within the above range, since the gap can be easily adjusted in the pattern development or the liquid crystal cell forming step, and the desired color can be easily expressed.
As the radiation used for forming the pixel, for example, visible light, ultraviolet light, far ultraviolet light, an electron beam, X-ray, or the like can be used, and radiation having a wavelength in the range of 190 to 450 nm is preferable.

  The light source for using radiation having a wavelength of 190 to 450 nm used for image exposure is not particularly limited. For example, a xenon lamp, a halogen lamp, a tungsten lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, Lamp light sources such as medium-pressure mercury lamps, low-pressure mercury lamps, carbon arcs, and fluorescent lamps; and laser light sources such as argon ion lasers, YAG lasers, excimer lasers, nitrogen lasers, helium cadmium lasers, and semiconductor lasers. When irradiating with light of a specific wavelength, an optical filter can be used.

The radiation exposure amount is preferably from 10 to 10,000 J / m ² . Examples of the alkali developer include, for example, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, Inorganic alkaline compounds such as potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide; mono-di- or tri-ethanolamine, mono-di- or tri- -Methylamine, mono-di- or tri-ethylamine, mono- or di-isopropylamine, n-butylamine, mono-di- or tri-isopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium Hydroxide (TMAH) Aqueous solution of an organic alkaline compound choline are preferred.

An appropriate amount of a water-soluble organic solvent such as isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol, or a surfactant may be added to the alkali developer. After the alkali development, the film is usually washed with water.
As a developing treatment method, any method such as an immersion developing method, a spray developing method, a brush developing method, and an ultrasonic developing method can be used. The development condition is preferably room temperature (23 ° C.) for 5 to 300 seconds.

The conditions for the development treatment are not particularly limited, but the development temperature is usually 10 ° C. or higher, especially 15 ° C. or higher, further 20 ° C. or higher, and usually 50 ° C. or lower, particularly 45 ° C. or lower, and more preferably 40 ° C. or lower. Is preferred.
The developing method can be based on any method such as an immersion developing method, a spray developing method, a brush developing method, and an ultrasonic developing method.

  When the color filter manufactured in this way is used for a liquid crystal display device, a transparent electrode such as ITO is formed on an image in this state, and the color filter is used as a part of a component of a color display, a liquid crystal display device, or the like. Although used, a top coat layer of polyamide, polyimide, or the like can be provided on the image as needed to enhance surface smoothness and durability. In some applications, such as a planar orientation type driving method (IPS mode), the transparent electrode may not be formed. In the vertical alignment type driving method (MVA mode), a rib may be formed. In addition, a pillar structure (photo spacer) by photolithography may be formed instead of the bead scattering spacer.

<Liquid crystal display device>
The liquid crystal display of the present invention uses the above-described color filter of the present invention. There is no particular limitation on the type and structure of the liquid crystal display device of the present invention, and the liquid crystal display device can be assembled according to an ordinary method using the color filter of the present invention.
For example, the liquid crystal display device of the present invention can be formed by the method described in “Liquid Crystal Device Handbook” (Nikkan Kogyo Shimbun, published on September 29, 1989, by the 142nd Committee of the Japan Society for the Promotion of Science).

<Organic EL display device>
When producing an organic EL display device including the color filter of the present invention, for example, as shown in FIG. 1, a blue color filter in which pixels 20 are formed on a transparent support substrate 10 with the green pigment-colored resin composition of the present invention. A multicolor organic EL element is manufactured by laminating an organic light emitting body 500 on the organic protective layer 30 and the inorganic oxide film 40 via the inorganic oxide film 40.

  As a method of laminating the organic light emitting body 500, a method of sequentially forming a transparent anode 50, a hole injection layer 51, a hole transport layer 52, a light emitting layer 53, an electron injection layer 54, and a cathode 55 on the upper surface of the color filter, And a method of bonding the organic light emitting body 500 formed on another substrate to the inorganic oxide film 40. The organic EL element 100 manufactured as described above can be applied to a passive drive type organic EL display device and an active drive type organic EL display device.

Next, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples as long as the gist of the present invention is not exceeded.
In the following examples, "parts" means "parts by weight".
[1] Synthesis of resin
<Synthesis Example 1: Synthesis of binder resin A>
Prepare a separable flask equipped with a cooling tube as a reaction tank, charge 400 parts by weight of propylene glycol monomethyl ether acetate, replace with nitrogen, and then heat the mixture in an oil bath with stirring to raise the temperature of the reaction tank to 90 ° C. did.

  On the other hand, 30 parts by weight of dimethyl-2,2 '-[oxybis (methylene)] bis-2-propenoate, 60 parts by weight of methacrylic acid, 110 parts by weight of cyclohexyl methacrylate, t-butylperoxy-2-ethyl 5.2 parts by weight of hexanoate and 40 parts by weight of propylene glycol monomethyl ether acetate are charged, and 5.2 parts by weight of n-dodecyl mercaptan and 27 parts by weight of propylene glycol monomethyl ether acetate are charged into a chain transfer agent tank. After the temperature was stabilized at 90 ° C., dropping was started from the monomer tank and the chain transfer agent tank, and polymerization was started. While the temperature was maintained at 90 ° C., the dropwise addition was performed over 135 minutes, and 60 minutes after the completion of the dropwise addition, the temperature was raised to 110 ° C. in the reaction vessel.

  After maintaining at 110 ° C. for 3 hours, a gas introducing tube was attached to the separable flask, and bubbling of a mixed gas of oxygen / nitrogen = 5/95 (v / v) was started. Next, 39.6 parts by weight of glycidyl methacrylate, 0.4 part by weight of 2,2′-methylenebis (4-methyl-6-t-butylphenol), and 0.8 part by weight of triethylamine were charged into the reaction vessel, and the mixture was kept at 110 ° C. For 9 hours. The resin A thus obtained had a weight average molecular weight Mw measured by GPC of 8,000 and an acid value of 101 mgKOH / g.

<Synthesis Example 2: Synthesis of binder resin B>
114.0 g of propylene glycol monomethyl ether acetate was placed in a 500 ml four-necked flask, and heated to 85 ° C. while performing nitrogen bubbling. 100.1 g (0.55 mol) of cyclohexyl methacrylate, 33.3 g (0.45 also 1) of methacrylic acid, and 4.925 g (0.03 mol) of 2.2′-azobis (isobutyronitrile) were added to propylene glycol. It was dissolved in 96.45 g of monomethyl ether acetate and added dropwise over 4 hours. After the dropwise addition, the mixture was further stirred for 2 hours while maintaining the reaction solution at 85 ° C., and then the temperature was raised to 100 ° C. for 1 hour with nitrogen bubbling stopped. The resin B thus obtained had a weight average molecular weight Mw measured by GPC of about 15,000 and an acid value of 190 mgKOH / g.

<Synthesis Example 3: Synthesis of binder resin C>
The mixture was stirred while replacing 145 parts by weight of propylene glycol monomethyl ether acetate with nitrogen, and heated to 120 ° C. 10 parts by weight of styrene, 85.2 parts by weight of glycidyl methacrylate and 66 parts by weight of a monoacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) were added dropwise thereto, and 2.2′-azobis-2-methyl was added. 8.47 parts by weight of butyronitrile were added dropwise over 3 hours, and the mixture was further stirred at 90 ° C. for 2 hours. Next, the inside of the reaction vessel was replaced with air, and 0.7 parts by weight of trisdimethylaminomethylphenol and 0.12 parts by weight of hydroquinone were added to 43.2 parts by weight of acrylic acid, and the reaction was continued at 100 ° C. for 12 hours. Thereafter, 56.2 parts by weight of tetrahydrophthalic anhydride (THPA) and 0.7 parts by weight of triethylamine were added and reacted at 100 ° C. for 3.5 hours. The resin C thus obtained had a weight average molecular weight Mw measured by GPC of about 8400 and an acid value of 80 mgKOH / g.

[2] Preparation of pigment dispersion
[2-1] Preparation of green pigment dispersion C.I. I. Pigment Green 58 (manufactured by DIC; hereinafter, abbreviated as "G58") is 37.88 parts by weight, and "BYK-LPN6919" manufactured by BYK-Chemie (methacrylic acid-based AB block copolymer, amine value 121 mgKOH / g, (Acid value: 1 mgKOH / g or less) 9.48 parts by weight in terms of solids, 12.64 parts by weight in terms of solids of binder resin A of Synthesis Example 1 as a binder resin, and 240.00 parts by weight of propylene glycol monomethyl ether acetate as a solvent Parts, 225 parts by weight of zirconia beads having a diameter of 0.5 mm were filled in a stainless steel container and dispersed with a paint shaker for 6 hours to prepare a green pigment dispersion.

[2-2] Preparation of Yellow Pigment Dispersion 18.4 parts by weight of E4GN-GT (manufactured by LANXESS; hereinafter, abbreviated as “NiAzo-Y”) as a pigment and BYK-LPN6919 (manufactured by BYK-Chemie) as a dispersant. 4.74 parts by weight in terms of solids, 6.32 parts by weight in terms of solids of binder resin A of Synthesis Example 1 as a resin, 120.00 parts by weight of propylene glycol monomethyl ether acetate as a solvent, zirconia beads having a diameter of 0.5 mm 225 parts by weight were filled in a stainless steel container, and dispersed in a paint shaker for 6 hours to prepare a yellow pigment dispersion.

[2-3] Preparation of blue dye dispersion C.I. I. Pigment Blue 15: 6 (hereinafter abbreviated as "B15: 6"), 9.26 parts by weight, Disperbyk2000 (manufactured by BYK-Chemie) as a dispersant (acrylic block copolymer, quaternary ammonium base (dimethylbenzylammonium base)) An AB block copolymer consisting of a B block having the following formula and an A block having no, an amine value of 10 mg KOH / g, and an acid value of 0 mg KOH / g) were produced in an amount of 2.65 parts by weight in terms of the solid content of the dispersant and further prepared in Synthesis 2. A stainless steel container was charged with 3.09 parts by weight of the binder resin B in terms of solid content, 60.00 parts by weight of propylene glycol monomethyl ether acetate as a solvent, and 225 parts by weight of zirconia beads having a diameter of 0.5 mm. The mixture was dispersed for a time to prepare a blue dye dispersion.

[3] Preparation of coloring composition Dispersion prepared in [2-1] to [2-3], propylene glycol monomethyl ether acetate and ethyl 3-ethoxypropionate as solvents, resin C as binder resin, photopolymerizable monomer As dipentaerythritol hexaacrylate as a photopolymerization initiation system component “IRGACURE 907” (2-methyl-1- [4- (
Methylthio) phenyl] -2-morpholinopropan-1-one) and "IRGACURE OXE02" (Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl) manufactured by Ciba Japan. -, 1- (O-acetyl oxime) and F-475 (fluorine surfactant) manufactured by DIC as a surfactant were mixed at the ratio shown in Table 1, and the coloring compositions of Examples and Comparative Examples were mixed. The numerical values in Table 1 are contents (parts by weight).

[3] Production of Pattern (Pixel) Each of the coloring compositions was spin-coated on a chromium-deposited glass substrate, and prebaked on a hot plate at 80 ° C. for 3 minutes. The number of coating revolutions was adjusted so that color coordinates y = 0.599 after post-baking.
Next, the sample was exposed at 30 mj / cm ² through a linear mask pattern having a width of 50 μm and a length of 3 mm using a high-pressure mercury lamp, and then a 0.04% by weight aqueous solution of potassium hydroxide was used. Spray development was performed at a pressure of 25 MPa. The development time was twice the dissolution time of the colored composition measured in advance. The measurement of the dissolution time will be described later. After development, the substrate was rinsed with sufficient water and then dried with clean air. Thereafter, post-baking was performed in an oven at 230 ° C. for 30 minutes. The dry film thickness was as shown in Table 2.

[4] Measurement of chromaticity and luminance of coloring composition As in [3], after applying the coloring composition on a glass substrate AN100 (manufactured by Asahi Glass Co., Ltd.), drying, exposing, developing, and post-baking, the spectrophotometer U Chromaticity and luminance with a C light source were measured using -3310 (manufactured by Hitachi Ltd.).
[5] Measurement of dissolution time of coloring composition As in [3], the coloring composition is applied to a glass substrate, dried, exposed, and then developed with a 0.04% by weight aqueous solution of potassium hydroxide. When spray-developed at a temperature of 23 ° C. and a pressure of 0.25 MPa, the time during which the unexposed portion of the coloring composition completely dissolved in the developer and the substrate was exposed was defined as the dissolving time of the coloring composition.

[6] Measurement of cross-over of a linear pattern The pattern was developed for 40 seconds according to the method described in [3], and the obtained 10 linear patterns having a line width of 50 μm were observed with an optical microscope at a magnification of 10 times, and a dent at a line edge was obtained. Was counted as a multiple. This was repeated twice to confirm reproducibility. FIG. 12 shows a micrograph of a representative example of the pattern (pixel).

The same evaluation was performed by changing the exposure amount from 30 mj / cm ² to 40 mj / cm ² . Table 2 shows the chromaticity, dissolution time, and number of chips.

As shown in Table 2, it can be seen that the pixels formed using the green pigment coloring resin composition of the present invention have reduced chipping of the pixels while maintaining the characteristics of the pixels, that is, the characteristics such as luminance and contrast. . That is, a good linear pattern is obtained as a pixel.
Thus, the color filter formed using the green pigment-colored resin composition of the present invention has no color leakage, high color purity, high luminance and high contrast.

  Further, as the luminance, in particular, a value larger than 56.0% is useful as a practical level, and the embodiments 1 to 8 satisfy the characteristics at the practical level of luminance. It is particularly preferable because the number of chips is reduced.

Claims (8)

(A) a halogenated zinc phthalocyanine green pigment, (B) a photopolymerization initiator and (H) a solvent,
Further, (D) contains a blue dye and a fluorine-based surfactant,
The (D) blue dye is a copper phthalocyanine pigment represented by the following formula (1-I),
A green pigment-colored resin composition for forming a green pixel, wherein the solvent (H) contains propylene glycol monomethyl ether acetate and a solvent having a boiling point of 150 ° C. or higher.

(In the above formula (1-I), each R independently represents a hydrogen atom.)   2. The green pigment-colored resin composition according to claim 1, wherein the content of the solvent having a boiling point of 150 ° C. or higher with respect to the entire solvent (H) is 1 to 50% by weight. 3.   The green pigment-colored resin composition according to claim 1, further comprising (E) a yellow pigment.   The green pigment-colored resin composition according to any one of claims 1 to 3, further comprising (F) a dispersant.   The green pigment-colored resin composition according to any one of claims 1 to 4, wherein the (A) halogenated zinc phthalocyanine green pigment is a brominated zinc phthalocyanine green pigment.   The green pigment coloring according to any one of claims 1 to 5, wherein the (D) blue pigment is contained in an amount of 0.05% by weight or more and 2.0% by weight or less in all the pigments. Resin composition.   The green pigment-colored resin composition according to any one of claims 1 to 6, wherein the (H) solvent contains a glycol alkyl ether acetate-based solvent.   The green pigment coloring resin composition according to any one of claims 1 to 7, further comprising (G) a polymerizable monomer.

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