JP5817099B2 - Green pigment colored resin composition, color filter, liquid crystal display device, and organic EL display device - Google Patents

Description

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

  Conventionally, as a method for producing 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 a substrate on which a light-shielding layer having a desired pattern has been previously formed. There is known a method of obtaining pixels of each color by irradiating radiation through a photomask having a pattern (hereinafter referred to as “exposure”), developing and dissolving and removing unexposed portions, and then post-baking. Yes.

In recent years, the trend of technological innovation has been rapid, and liquid crystal display elements equipped with color filters have been required to have higher brightness and expanded color reproduction area. For this reason, color filters also have higher light transmittance and higher recently. It is required to have color purity.
Under such circumstances, recently, for example, Patent Documents 1 and 2 disclose zinc phthalocyanine green pigments having a specific hue with regard to increasing the brightness of green pixels.

However, a pixel formed using the zinc phthalocyanine green pigment has a problem that light leakage easily occurs and display unevenness of the display device easily occurs. Further, there has been a demand for further increasing the brightness and contrast of the obtained pixels.
In Patent Documents 3 to 5, a colored radiation-sensitive composition using a zinc phthalocyanine green pigment is liable to cause pixel chipping when formed into a coating film, and it is difficult to obtain linearity. It describes the problem that the number of bits increases.

JP 2008-122478 A JP 2009-052020 A JP 2009-036552 A JP 2010-014961 A JP 2010-097172 A

In view of the above conventional problems, an object of the present invention is to provide a green pigment-colored resin composition that reduces chipping of pixels when a color filter is formed.
Furthermore, the present invention provides a color filter having excellent pattern linearity, no light leakage, high color purity, high luminance and high contrast, and a liquid crystal display device and an organic EL display device including the color filter. Is an issue.

As a result of intensive studies, the present inventors have found that when a pixel is formed using a zinc phthalocyanine green pigment, the lack of the pixel is the cause of the problem.
As a result of further studies, it has been found that the first cause of the lack of pixels is that the amount of the curable component produced due to the following reason is insufficient.
(1) A zinc halide phthalocyanine green pigment has a weak coloring power compared to other color pigments such as blue. Therefore, the content of the pigment contained in the green pigment colored resin composition is larger than that of the blue pigment colored resin composition.
(2) Moreover, since the halogenated zinc phthalocyanine green pigment has low dispersion stability, the dispersant and the dispersion resin contained in the green pigment colored resin composition are increased.

That is, when the content of the pigment, the dispersant, and the dispersion resin is increased, the curing component is decreased, and there is a high possibility that the curing is not sufficient.
Furthermore, the second cause is that the halogenated zinc phthalocyanine green pigment blocks a wavelength of about 400 nm or less. It has been found that due to this blocking, the photopolymerization initiator contained in the green pigment colored resin composition does not function sufficiently.

In other words, it has been found that the fact that the photopolymerization initiator does not function sufficiently in addition to the small amount of the curable component is the cause of the lack of pixels.
As a result of further studies based on these findings, the present inventors have found that the above problem can be solved by including a blue pigment in the green pigment-colored resin composition, and have reached the present invention. did.

That is, the present invention contains (A) a zinc halide phthalocyanine green pigment, (B) a photopolymerization initiator and (H) a solvent, and further contains (D) a blue dye and (F) a dispersant, (D) a blue dye, a copper phthalocyanine pigment represented by the formula (1-I), wherein (F) dispersing agent, Ri modified acrylic copolymer der, wherein (H) solvent, propylene glycol A green color for forming a green pixel , comprising monomethyl ether acetate and a solvent having a boiling point of 150 ° C. or higher, wherein the content of the solvent having a boiling point of 150 ° C. or higher with respect to the total amount of the solvent (H) is 1 to 50% by weight. It exists in a pigment coloring resin composition, a color filter, a liquid crystal display device, and an organic EL display device.

When pixels are formed using the green pigment colored resin composition of the present invention, there are few missing pixels.
Furthermore, the present invention provides a color filter having excellent pattern linearity, no light leakage, high color purity, high luminance and high contrast, and a liquid crystal display device and an organic EL display device including the color filter. Is possible.

It is a cross-sectional schematic diagram which shows an example of the organic EL element provided with the green color filter of this invention. It is a microscope picture of the representative example of the pattern (pixel) used for the measurement. In FIG. 2, (a) a pattern with no multiplication, (b) a pattern with 57 multiplications, and (c) a pattern with 100 or more multiplications.

Embodiments of the present invention will be described in detail below, but 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, for example, “(meth) acrylic acid” "Means" acrylic acid and / or methacrylic acid ".

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

Moreover, 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 (D) a green pigment coloring containing a blue dye. It is a resin composition.

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

  Of these, 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. Furthermore, brominated zinc phthalocyanine having 13 to 16 bromine atoms in one molecule and not containing chlorine or having an average of 3 or less in one molecule is preferable, and in particular, an average of 14 bromine atoms in one molecule is 14 Brominated zinc phthalocyanine having ˜16 and not containing 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 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 in addition to bromine as an appropriate starting material. In this case, a catalyst such as ammonium molybdate may be used as necessary.

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

When the obtained mixture is put into an acidic aqueous solution such as hydrochloric acid after the reaction is completed, the produced brominated zinc phthalocyanine is precipitated. Thereafter, post-treatment such as filtration, washing and drying is performed to obtain brominated zinc phthalocyanine.
The brominated zinc phthalocyanine thus obtained may be used singly, but the brominated zinc phthalocyanine having a different bromination rate or chlorination rate and other metals as long as the effect of the present invention is not impaired. It can be used by mixing with brominated phthalocyanine or the like substituted. Changing the chlorination rate and bromination rate, or changing the central metal changes the color tone of the pigment and increases the number of hues that can be reproduced.

Even with the same green pigment, C.I. I. You may mix with halogenated copper phthalocyanines, such as pigment green (PG) 36 or 7.
The average primary particle size of the green pigment containing zinc halide phthalocyanine is usually 0.1 μm or less, preferably 0.04 μm or less, more preferably 0.03 μm or less, and even more preferably 0.025 μm or less. 005 μm or more. The average primary particle size of other pigments is the same as described above.

By setting the average primary particle size to be equal to or less than the above upper limit value, it is difficult to generate foreign matters in the composition, the depolarization is low, and a pixel having sufficient contrast and light transmittance can be formed. By setting it as the above, the dispersion stability is favorable and the green pigment coloring resin composition which ensured sufficient heat resistance and light resistance can be obtained.
In addition, the average primary particle diameter of a pigment can be calculated | required with the following method. That is, the pigment is ultrasonically dispersed in chloroform, dropped onto a collodion film-attached mesh, dried, and a primary particle image of the pigment is obtained by observation with a transmission electron microscope (TEM). The primary particle diameter is measured from this image, the number average value is calculated according to the following formula, and the average particle diameter is obtained.

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

  The brominated zinc phthalocyanine green pigment obtained in this way is dry-ground in a grinder such as an attritor, ball mill, vibration mill, vibration ball mill, etc. if necessary, and then pigmented by the solvent salt milling method or solvent boiling method. By doing so, a brominated zinc phthalocyanine green pigment that develops a green color with high transmittance and contrast can be obtained. There is no particular limitation on the pigmentation method, but it is preferable to employ the solvent salt milling method in that pigment 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 grinding 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 grinding are performed therein. The kneading machine at this time has, for example, a kneader, a mix muller, or a pulverizing space in which a gap portion of a rotating disk concentric with an annular fixed disk as described in JP-A 2006-77062 is formed A continuous kneader or the like is preferably used.

As the inorganic salt, a water-soluble inorganic salt can be preferably used. For example, an inorganic salt such as sodium chloride, potassium chloride, 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 normal inorganic salt.
The content of the halogenated zinc phthalocyanine green pigment contained in the green pigment-colored resin composition of the present invention is generally 30 to 99.95% by weight, preferably 35 to 99.92% by weight, more preferably in all pigments. Is 38-99.9% by weight.

Within the above-mentioned range, it is preferable in terms of obtaining a good color filter with sufficient luminance, few missing pixels, excellent pattern linearity and few defects.
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 aforementioned halogenated zinc phthalocyanine green pigment, a blue pigment described later, and a yellow pigment and other pigments as necessary. You may contain suitably.

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 it is within the above range, the film thickness is appropriate with respect to the color density, and it is easy to control the gap when forming a liquid crystal cell. Furthermore, the dispersion stability is high, and reaggregation and thickening are difficult to place, which is preferable.
[(B) Photopolymerization initiator]
The green pigment colored 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, (B2) an additive such as a sensitizing dye (photopolymerization initiation system). And is a component having a function of generating a polymerization active radical by directly absorbing light or being photosensitized to cause a decomposition reaction or a hydrogen abstraction reaction.

  Examples of the (B) photopolymerization initiator constituting the photopolymerization initiation system include titanocene derivatives described in JP-A Nos. 59-152396 and 61-151197, etc .; Hexaarylbiimidazole derivatives described in JP-A-11-174224, JP-A-2000-56118, etc .; halomethylated oxadiazole derivatives described in JP-A-10-39503, etc., halomethyl-s -Radical activators such as triazine derivatives, N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acid salts, N-aryl-α-amino acid esters, α-aminoalkylphenone derivatives And oxime ester derivatives described in JP-A No. 2000-80068 and the like.

  Specifically, for example, biimidazole derivatives include 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, And (4′-methoxyphenyl) -4,5-diphenylimidazole dimer.

  Alternatively, the romethyl-s-triazine derivatives include 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)- Examples thereof include s-triazine.

Examples of α-aminoalkylphenone derivatives include 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4- Morpholinophenyl) -butanone-1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzoe -To, 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.

The oxime ester derivatives include 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (o-benzoyloxime), ethanone, 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, 2,4-diethylthioxanthone, etc. Examples also include thioxanthone derivatives, benzoate derivatives, acridine derivatives, phenazine derivatives, anthrone derivatives and the like.

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

One of these (B) photopolymerization initiator and (B1) polymerization accelerator may be used alone, or two or more thereof may be used in combination.
Further, (B2) sensitizing dye is used for the purpose of increasing the sensitivity as required. As the sensitizing dye, an appropriate one is used according to the wavelength of the image exposure light source. For example, xanthene dyes described in JP-A-4-221958 and JP-A-4-219756; No. 239703, JP-A-5-289335, etc. Coumarin dyes having a heterocyclic ring; JP-A-3-239703, JP-A-5-289335, etc .; 3-ketocoumarin dyes; 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, 58-15503, JP 60-88005, JP 59-56403, JP 2-69, JP 57-168088, JP 5-10. 761 No., JP-A-5-210240, dyes having a dialkyl aminobenzene skeleton described in JP-A 4-288818 Patent JP-like.

(B2) A sensitizing dye may also be used individually by 1 type, and may use 2 or more types together.
In the green pigment colored resin composition of the present invention, the content of these photopolymerization initiation systems is usually 0.1 to 40% by weight, preferably 0.2 to 30% by weight, more preferably 0, based on the total solid content. The range is from 5 to 20% by weight. Within the above range, the sensitivity to exposure light is good, and the solubility of the unexposed portion in the developer is good, which is preferable.

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

Examples of such solvents 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, methoxymethylpentanol, propylene Glycol monoalkyl ethers such as glycol monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, 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, 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;
Cycloaliphatic 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, Barsol # 2, Apco # 18 Solvent, Apco thinner, Soal Solvent No. 1 and no. 2, Solvesso # 150, Shell TS28 Solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, diglyme (all trade names) and the like.

These solvents may be used alone or in combination of two or more.
Of the above solvents, glycol alkyl ether acetates (glycol alkyl ether acetate solvents) are preferred because of their good dispersibility in solvents such as the aforementioned halogenated zinc phthalocyanine green pigment in the present invention. Furthermore, propylene glycol monomethyl ether acetate is particularly preferable from the viewpoint of the solubility of various components in the green pigment colored resin composition.

In addition, it is more preferable to use a glycol monoalkyl ether as a solvent by mixing from the viewpoints of good balance such as applicability and surface tension and relatively high solubility of the components in the composition.
(H) The proportion of glycol monoalkyl ethers in the solvent is preferably 5 to 50% by weight and more preferably 5 to 30% by weight in terms of good storage stability.

Moreover, when using for a slit coat system, it is also preferable to use together the solvent with a boiling point of 150 degreeC 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 total amount of the solvent (H).
If it is within the above range, the drying speed is appropriate, so it is difficult for colorant components to precipitate and solidify at the tip of the slit nozzle, tact failure in the vacuum drying process in the color filter manufacturing process, pre-baking pin marks, etc. Is preferable because

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.
Moreover, when using for the inkjet method, it is preferable to use a high boiling-point solvent. This is because the ink emitted from the nozzle is very small, from several to several tens of pL, and the solvent evaporates before landing on the periphery of the nozzle opening or in the pixel bank. This is to prevent drying out.

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 higher with respect to the whole (H) solvent. Within the above range, the effect of preventing the solvent from evaporating from the ink droplets is sufficient, which is preferable.

In the green pigment coloring resin composition of the present invention, the content ratio of the (H) solvent 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 is preferred in that it has a viscosity suitable for coating and can form a coating film satisfactorily.

[(D) Blue dye]
The (D) blue pigment 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 a known material can be used.

(Specific examples of blue pigments)
As a compound corresponding to a blue pigment, 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. I.) Numbers can be mentioned.

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 pigment in the present invention is preferably a compound represented by the following formula (1-I).

(In the formula (1-I), each R independently represents a hydrogen atom or a halogen atom.)
R each independently represents a hydrogen atom or a halogen atom, and (B) it is particularly preferable that all are hydrogen atoms from the viewpoint of favorably easily transmitting the wavelength excited by the photopolymerization initiator.
Among them, C.I. I. Pigment Blue 15: 6 is most preferable. Moreover, the phthalocyanine blue pigment used for the green pigment coloring resin composition of this invention may be used individually by 1 type, or may use multiple types together. The average primary particle size of the blue pigment is the same as that described in the section <Zinc halide phthalocyanine green pigment>. The preferred embodiment is also the same.

(Content)
The content of the blue dye contained in the green pigment-colored resin composition of the present invention is generally 0.05 to 2.0% by weight, preferably 0.08 to 1.5% by weight, more preferably in all the dyes. Is 0.1 to 1.0% by weight.
Within the above-mentioned range, it is preferable in terms of obtaining a good color filter with sufficient luminance, few missing pixels, excellent pattern linearity and few defects.

[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.
Furthermore, the yellow pigment (E) in the present invention may be a yellow pigment or a yellow dye, but is preferably a yellow pigment from the viewpoint of good coloring power.

Examples of yellow pigments include monoazo, diazo, condensed diazo, benzimidazolone, azo metal complexes, azomethine, pyrazolone, quinophthalone, isoindoline, isoindolinone, and flavatron. From the viewpoint of excellent transparency and contrast, azo, quinophthalone and isoindoline are preferred.
Although the preferable specific example as a yellow pigment is shown below, this invention is not limited to these.

(Specific examples of yellow pigment)
Examples of yellow pigments include nickel azo complexes, 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, 169, 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, 180.

The average primary particle size of the yellow pigment is the same as that described in the above section <Zinc halide phthalocyanine green pigment>. The preferred embodiment is also the same.
(Content)
The content of the yellow pigment in the total pigment of the green pigment coloring resin composition of the present invention is usually 0.05 to 70 wt%, preferably 0.08 to 65 wt%, more preferably 0.1 to 0.1 wt%. 62% by weight.

Within the above range, it is preferable in that the color adjustment can be performed satisfactorily.
<Reason for effect>
As described above, when a pixel is formed using a zinc halide phthalocyanine green pigment, the cause of the lack of the pixel is that there are few curable components and the initiator does not function sufficiently. The reason why the initiator does not function sufficiently is estimated 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-rays and g-rays, and an initiator having an absorption wavelength in a wavelength region exceeding 400 nm is used for high sensitivity.
However, the zinc halide phthalocyanine green pigment has a low transmittance around 400 nm. For this reason, a photopolymerization initiator or the like having increased sensitivity is difficult to be radicalized by absorbing light.

On the other hand, the blue pigment has a high transmittance around 400 nm, and easily generates photopolymerization initiator radicals. In other words, by including a blue pigment in the composition, the photopolymerization initiator functions sufficiently, so that even if there are few curable components, the pixels to be formed can be sufficiently cured, and the number of obtained pixels is reduced. .
Furthermore, by including 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 (F) dispersant in the present invention is not particularly limited as long as the pigment is dispersed and can maintain stability. For example, cationic, anionic, nonionic or amphoteric dispersants can be used, but polymer dispersants are preferred. Specifically, a modified acrylic copolymer, an acrylic copolymer, polyurethane, polyester, a polymer copolymer alkylammonium salt or phosphate ester salt, a cationic comb graft polymer, and the like can be given. Among these dispersants, modified acrylic copolymers, polyurethane, and cationic comb graft polymers are preferable. In particular, a modified acrylic copolymer is preferable. Among these, a block copolymer composed of an A block having a solvophilic property and a B block having a functional group containing a nitrogen atom has an amine value of 80 mgKOH / g or more and 150 mgKOH / g. The following (in terms of effective solid content) is particularly preferable. More preferably, it is 100-140 mgKOH / g.

Within the above range, the adsorptive power to the pigment surface is sufficient and the dispersion stability is good.
Of these, the (meth) acrylic block copolymer described in JP-A-2009-025813 is preferable. The acrylic block copolymer can disperse the pigment (A) very efficiently. This is presumably because the molecular arrangement is controlled, so that there are few structures that obstruct the dispersant when adsorbing to the pigment.

In the present invention, the acrylic block copolymer is preferably an AB block comprising an A block and a B block and / or an ABA block copolymer.
The B block constituting the acrylic block copolymer has an amino group, and the amino group is preferably —NR ⁴¹ R ⁴² (provided that R ⁴¹ and R ⁴² each independently have a substituent). A cyclic or chain alkyl group which may be substituted, an aryl group which may have a substituent, or an aralkyl group which may have a substituent. A preferable example is represented by the following formula, for example.

^{(However, R 41} and ^{R 42} has the same meaning as above ^{R 41} and ^{R 42, R 43} is one or more alkylene groups having a carbon ^{number, R 44} represents a hydrogen atom or a methyl group.)
Among them, R ⁴¹ and R ⁴² are preferably methyl groups, R ⁴³ is preferably a methylene group or an ethylene group, and R ⁴⁴ is preferably a methyl group. Examples of such a compound include a partial structure represented by the following formula.

Two or more kinds of the partial structure containing an amino group as described above may be contained in one B block. In that case, two or more amino group-containing partial structures may be contained in the B block in any form of random copolymerization or block copolymerization. In addition, a partial structure not containing an amino group may be partially contained in the B block within a range not impairing the effects of the present invention. Examples of such a partial structure include (meth) acrylic acid esters. And a partial structure derived from a monomer.

On the other hand, in the present invention, the A block of the (F) dispersant is not particularly limited as long as it is solvophilic and is composed of a monomer copolymerizable with the monomer constituting the B block described above.
Examples of the A block include polymer structures obtained by copolymerizing comonomers such as styrene monomers, (meth) acrylate monomers, (meth) acrylate monomers, vinyl acetate monomers, glycidyl ether monomers, and the like. It is done.

The dispersant (F) contained in the green pigment-colored resin composition of the present invention is an AB block or ABA block copolymeric polymer compound composed of an A block and a B block as described above. Of these, AB block copolymers are preferred. Such a block copolymer is prepared, for example, by a living polymerization method.
The living polymerization method includes an anion living polymerization method, a cation living polymerization method, and a radical living polymerization method. Specifically, for example, a method described in JP-A-2007-270147 can be mentioned.

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

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

When the average primary particle size of the pigment is small, the specific surface area increases and the amount of adsorbing dispersant per unit area decreases. In this case, the dispersant made of the copolymer is preferably used because it is more effective than the other dispersants.
The dispersant 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 pigment colored 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 those described in JP-A-2006-343648, for example.
[Dispersion aid]
The green pigment coloring resin composition of the present invention may contain a dispersion aid. The dispersion aid here may be a pigment derivative. Examples of the pigment derivative include JP-A Nos. 2001-220520, 2001-271004, 2002-179976, and 2007-. Various compounds described in Japanese Patent Application Publication No. 113000 and Japanese Patent Application Publication No. 2007-186681 can be used.

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

Further, when other dispersion aids are contained, the total amount of the dispersion aids is set within the above range.
[Dispersion resin]
The green pigment coloring resin composition of the present invention may contain a part or all of a resin selected from (C) binder resin or other binder resin described later as the following dispersion resin.

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

Thus, the (C) binder resin used in the dispersion treatment step may be referred to as a dispersion resin. The dispersion 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 pigment in the pigment dispersion.
As the dispersion resin, various (C) binder resins described later can be used.
The acid value of the dispersion resin is preferably 0.5 mgKOH / g or more, more preferably 1 mgKOH / g or more, most preferably 5 mgKOH / g or more, more preferably 300 mgKOH / g or less, more preferably 200 mgKOH / g or less, and 150 mgKOH / g. The following are most preferred. By controlling the acid value within the above range, the alkali developability is improved, and the handling becomes easy in synthesis and the like.

  The weight average molecular weight in terms of polystyrene measured by GPC of the dispersion resin is preferably 1000 or more, more preferably 1500 or more, most preferably 2000 or more, more preferably 200000 or less, more preferably 50000 or less, and 30000 or less. Most preferred. By controlling the molecular weight within the above range, the alkali developability can be improved and the dispersion stability can be prevented from being lowered.

[(C) Binder resin]
(C) The preferred resin for the binder resin differs depending on the curing means.
When the colored resin composition of the present invention is a photopolymerizable resin composition, examples of the (C) binder resin include JP-A-7-207211, JP-A-8-259876, JP-A-10-300922, 11-14144, JP-A No. 11-174224, JP-A No. 2000-56118, JP-A No. 2003-233179, and the like can be used. C-1) to (C-5) resins and the like.

(C-1): With respect to a copolymer of an epoxy group-containing (meth) acrylate and another radical polymerizable monomer, an unsaturated monobasic acid is added to at least a part of the epoxy group of the copolymer. Resin to be added, or an alkali-soluble resin (hereinafter referred to as “resin (C-1)”) obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl group generated by the addition reaction. .)
(C-2): Carboxyl group-containing linear alkali-soluble resin (C-2) (hereinafter sometimes referred to as “resin (C-2)”)
(C-3): a resin obtained by adding an epoxy group-containing unsaturated compound to the carboxyl group portion 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, the resin (C-1) is particularly preferable, and the resin will be described below.

The resins (C-2) to (C-5) may be anything as long as they are dissolved in an alkaline developer and are soluble to the extent that the desired development processing is performed. It is the same as that described as the same item in 2009-025813. The preferred embodiment is also the same.
(C-1): With respect to a copolymer of an epoxy group-containing (meth) acrylate and another radical polymerizable monomer, an unsaturated monobasic acid is added to at least a part of the epoxy group of the copolymer. As one of particularly preferable resins of the alkali-soluble resin resin (C-1) obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl group generated by the addition reaction, or an epoxy group, Unsaturated in 10 to 100 mol% of the epoxy group of the copolymer with respect to the copolymer of 5 to 90 mol% of (meth) acrylate and 10 to 95 mol% of other radical polymerizable monomer Examples thereof include a resin obtained by adding a monobasic acid, or an alkali-soluble resin obtained by adding a polybasic acid anhydride to 10 to 100 mol% of a hydroxyl group 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. Of these, glycidyl (meth) acrylate is preferred. These epoxy group-containing (meth) acrylates may be used alone or in combination of two or more.

  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) Examples include acrylic acid esters, (meth) acrylic acid amides, vinyl compounds, unsaturated dicarboxylic acid diesters, monomaleimides, and the like, and in particular, mono (meth) having a structure represented by the following formula (7) Acrylate is preferred.

  The repeating unit derived from the mono (meth) acrylate having the structure represented by the following formula (7) contains 5 to 90 mol% among the repeating units derived from “other radical polymerizable monomers”. The content is preferably 10 to 70 mol%, more preferably 15 to 50 mol%.

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).

The formula ^{(8), R} 91 ~R ⁹⁸ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ⁹⁶ and R ⁹⁸ may be connected to each other to form a ring.
The ring formed by connecting R ⁹⁶ and R ⁹⁸ is preferably an aliphatic ring, may be saturated or unsaturated, and preferably has 5 to 6 carbon atoms.
Among these, among the structures represented by the formula (8), those represented by the following structural formulas (8a), (8b), or (8c) are particularly preferable.

In addition, the mono (meth) acrylate which has a structure represented by the said Formula (8) may be used individually by 1 type, and may use 2 or more types together.
As "other radical polymerizable monomers" other than the mono (meth) acrylate having the structure represented by the formula (8), the heat resistance and strength excellent in the colored resin composition can be improved. , Styrene, (n-butyl) (meth) acrylate, tert-butyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, benzyl (meth) acrylate , (Meth) acrylic acid-2-hydroxyethyl, N-phenylmaleimide, N-cyclohexylmaleimide.

The content ratio of repeating units derived from at least one selected from the above monomer group is preferably 1 to 70 mol%, more preferably 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, as a copolymer of the epoxy group-containing (meth) acrylate and the other radical polymerizable monomer, 5 to 90 mol% of repeating units derived from the epoxy group-containing (meth) acrylate, and others Is preferably composed of 10 to 95 mol% of repeating units derived from the radically polymerizable monomer, more preferably composed of 20 to 80 mol% of the former and 80 to 20 mol% of the latter. What consists of 70 mol% and the latter 70-30 mol% is especially preferable.

Within the above range, the addition amount of the polymerizable component and alkali-soluble component described later is sufficient, and the heat resistance and strength are sufficient, which is preferable.
The epoxy group portion of the epoxy group-containing copolymer synthesized as described above is reacted with an unsaturated monobasic acid (polymerizable component) and a polybasic acid anhydride (alkali-soluble component).
Here, as an unsaturated monobasic acid added to an epoxy group, a well-known thing can be used, For example, unsaturated carboxylic acid which has an ethylenically unsaturated double bond is mentioned.

  Specific examples include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position substituted with a haloalkyl group, an alkoxyl group, a halogen atom, a nitro group, or a cyano group. And monocarboxylic acids such as (meth) acrylic acid. Of these, (meth) acrylic acid is preferred. 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 group of the copolymer, preferably 30 to 100 mol%, more preferably 50 to 100 mol%. It is preferable for it to be in the above range since the colored resin composition is excellent in stability over time. In addition, a well-known method is employable as a method of adding unsaturated monobasic acid to the epoxy group of a copolymer.

Furthermore, a well-known thing can be used as a polybasic acid anhydride added to the hydroxyl group produced when an unsaturated monobasic acid is added to the epoxy group of a copolymer.
For example, dibasic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride; trimellitic anhydride, pyromellitic anhydride, benzophenone Examples thereof include anhydrides of three or more bases such as tetracarboxylic acid anhydride and biphenyltetracarboxylic acid anhydride. Of these, succinic anhydride and tetrahydrophthalic anhydride are preferred. These polybasic acid anhydrides may be used individually by 1 type, and may use 2 or more types together.

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

Within the above range, the remaining film ratio and solubility during development are sufficient, which is preferable.
In addition, a well-known method is employable as a method of adding a polybasic acid anhydride to the said hydroxyl group.
Furthermore, in order to improve 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. May be. Such a resin structure is described in, for example, Japanese Patent Application Laid-Open Nos. 8-297366 and 2001-89533.

  The polystyrene-reduced weight average molecular weight (Mw) of the above-described binder resin (C-1) measured by GPC (gel permeation chromatography) is preferably 3000 to 100,000, and particularly preferably 5000 to 50000. If the molecular weight is less than 3000, heat resistance and film strength may be inferior, and if it exceeds 100,000, the solubility in a developer tends to be insufficient. Moreover, as a standard of molecular weight distribution, the ratio of weight average molecular weight (Mw) / number average molecular weight (Mn) is preferably 2.0 to 5.0.

In addition, the acid value of binder resin (C-1) is 10-200 mg-KOH / g normally, Preferably it is 15-150 mg-KOH / g, More preferably, it is 25-100 mg-KOH / g.
Within the above range, the solubility in a developer is good and film roughness is not likely to occur, which is preferable.

Moreover, the content rate of (C) binder resin is 0.1-80 weight% normally in a total solid, Preferably it is 1-60 weight%.
Within the above range, the adhesion to the substrate is good, the permeability of the developer to the exposed area is moderate, and the surface smoothness and sensitivity of the pixels are good.
[(G) polymerizable monomer]
The green pigment colored 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 it may be an addition-polymerizable compound having at least one ethylenic double bond (hereinafter referred to as “ethylenic compound”). Is preferred).

The ethylenic compound is a compound having an ethylenic double bond that undergoes addition polymerization and cures by the action of the photopolymerization initiation system when the green pigment colored resin composition of the present invention is irradiated with actinic rays. . In addition, the (G) polymerizable monomer in this invention means the concept opposite to what is called a polymeric substance, and also includes a dimer, a trimer, and an oligomer other than a monomer 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; Esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; Esterification of unsaturated carboxylic acids with polyvalent carboxylic acids and polyhydric hydroxy compounds such as aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds described above An ester obtained by the reaction; an ethylenic compound having a urethane skeleton obtained by reacting a polyisocyanate compound and a (meth) acryloyl group-containing hydroxy compound;

Esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, 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) Examples include (meth) acrylic acid esters such as acrylate and glycerol (meth) acrylate. In addition, the (meth) acrylic acid portion of these (meth) acrylic acid esters is replaced with an itaconic acid portion, a crotonic acid portion replaced with a crotonic acid portion, or a maleic acid ester replaced with a maleic acid portion, etc. Is mentioned.

Examples of the ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include hydroquinone di (meth) acrylate, resorcin di (meth) acrylate, pyrogallol tri (meth) acrylate, and the like.
The ester obtained by the esterification reaction of an unsaturated carboxylic acid with a polyvalent carboxylic acid and a polyvalent hydroxy compound is not necessarily a single substance but may be a mixture. Representative examples are 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 A condensate of (meth) acrylic acid, adipic acid, butanediol, and glycerin.

  Examples of the ethylenic compound having a urethane skeleton obtained by reacting a polyisocyanate compound and 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 diisocyanates; aromatic diisocyanates such as tolylene diisocyanate and 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 ethylene bis (meth) acrylamide; allyl esters such as diallyl phthalate; vinyl group-containing compounds such as divinyl phthalate. .
Among these, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids are preferred, pentaerythritol or (meth) acrylic acid esters of dipentaerythritol are more preferred, and dipentaerythritol hexa (meth) acrylate is particularly preferred.

  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 a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound. A polyfunctional monomer having a group is preferable, and in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol.

These monomers may be used alone, but since it is difficult to obtain a single compound in production, a mixture of two or more kinds may be used.
Moreover, you may use together the polyfunctional monomer which does not have an acid group, and the polyfunctional monomer which has an acid group as (G) polymeric monomer as needed.
A preferable 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 it is within the above range, the development and dissolution characteristics are hardly deteriorated, and the production and handling are easy. Furthermore, it is preferable because the photopolymerization performance is hardly lowered 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, a mixture containing succinic acid ester of dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentaacrylate as a main component. It is also possible to use this polyfunctional monomer in combination with another polyfunctional monomer.

In the green pigment coloring resin composition of the present invention, the content ratio of these (G) polymerizable monomers is usually 1% by weight or more, preferably 5% by weight or more, and more preferably 10% by weight or more in the total solid content. In addition, it is usually 80% by weight or less, preferably 70% by weight or less, more preferably 50% by weight or less, and particularly preferably 40% by weight or less.
The ratio of (G) polymerizable monomers to the total amount of all coloring materials, that is, (A) zinc halide phthalocyanine green pigment, (D) blue dye, (E) yellow dye, and other dyes is usually 1% by weight. Or more, preferably 5% by weight or more, more preferably 10% by weight or more, particularly preferably 20% by weight or more, and usually 200% by weight or less, preferably 150% by weight or less, more preferably 110% by weight or less. is there.

Within the above range, photocuring is appropriate, poor adhesion during development is difficult to place, the cross-section after development is difficult to reverse taper, and further, peeling phenomenon and omission failure due to lower 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 zinc halide phthalocyanine green pigment, (B) a photopolymerization initiator, (H) a solvent, ( D) It can be prepared by mixing with a blue pigment 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) are added in a solvent, (F) a dispersing agent and a dispersing aid to be added as necessary. In the presence, optionally with (C) a part of the binder resin, for example, paint shaker, sand grinder, ball mill, roll mill, stone mill, jet mill, homogenizer, etc. Prepare the solution. Examples of the color dispersion include (B) a photopolymerization initiator, (C) a binder resin, and, if necessary, (G) an additive such as a polymerizable monomer, and a method of preparing the mixture by mixing. it can.

[Application of green pigment colored resin composition]
The green pigment colored resin composition of the present invention is usually in a state where all of the constituent components are dissolved or dispersed in a solvent. This green pigment-colored resin composition is supplied onto the substrate to form components such as a color filter, a liquid crystal display device, and an organic EL display device.
Hereinafter, as an application example of the green pigment colored 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 them will be described.

<Color filter>
The color filter of this invention is provided with the pixel formed from the green pigment coloring resin composition of this invention.
The method for forming the color filter of the present invention will be described below.
The pixel of the color filter can be formed by various methods. Here, although the case where it forms by the photolithographic method using a photopolymerizable green pigment coloring resin composition is demonstrated to an example, a manufacturing method is not limited to this.

First, on the surface of the substrate, if necessary, a black matrix is formed so as to define a portion for forming pixels, and after applying the green pigment coloring resin composition of the present invention on this substrate, pre-baking is performed. To evaporate the solvent and form a coating. Then, after exposing this coating film through a photomask, developing with an alkali developer, dissolving and removing the unexposed portion of the coating film, and then post-baking, each of red, green, and blue A color filter can be manufactured by forming a pixel pattern.

The substrate used for 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, or a thermoplastic resin is used. A sheet, an epoxy resin, a thermosetting resin, various glass, etc. are mentioned.
In addition, these substrates may be appropriately subjected to pretreatment as desired, such as thin film formation treatment with a silane coupling agent or urethane resin, surface treatment such as corona discharge treatment or ozone treatment, if desired.

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

Within the above range, it is preferable in that the gap can be easily adjusted in the pattern development or liquid crystal cell forming step, and a desired color can be easily expressed.
For example, visible rays, ultraviolet rays, far ultraviolet rays, electron beams, X-rays, and the like can be used as the radiation used when forming the pixels, but radiation having a wavelength in the range of 190 to 450 nm is preferable.

  The light source used for image exposure for using radiation having a wavelength of 190 to 450 nm is not particularly limited. Lamp light sources such as medium pressure mercury lamp, low pressure mercury lamp, carbon arc, fluorescent lamp; laser light sources such as argon ion laser, YAG laser, excimer laser, nitrogen laser, helium cadmium laser, semiconductor laser, and the like. An optical filter can also be used when used by irradiating light of a specific wavelength.

Exposure of radiation, 10~10,000J / ^{m 2} is preferred.
Examples of the alkaline developer include 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 the like can be added to the alkali developer. In addition, it is usually washed with water after alkali development.
As the development processing method, any method such as an immersion development method, a spray development method, a brush development method, and an ultrasonic development method can be used. The development conditions are preferably 5 to 300 seconds at room temperature (23 ° C.).

There are no particular restrictions on the conditions of the development processing, but the development temperature is usually 10 ° C. or higher, especially 15 ° C. or higher, more preferably 20 ° C. or higher, and usually 50 ° C. or lower, especially 45 ° C. or lower, more preferably 40 ° C. or lower. Is preferred.
The developing method can be any one of immersion developing method, spray developing method, brush developing method, ultrasonic developing method and the like.

  When the color filter thus produced is used in a liquid crystal display device, a transparent electrode such as ITO is formed on the image as it is, and is used as a part of a color display, a liquid crystal display device, or the like. Although used, in order to improve surface smoothness and durability, a top coat layer such as polyamide or polyimide can be provided on the image as necessary. Further, in some applications such as a planar alignment type drive system (IPS mode), the transparent electrode may not be formed. In the vertical alignment type driving method (MVA mode), ribs may be formed. Also, a column structure (photo spacer) made of photolithography may be formed instead of the bead dispersion type spacer.

<Liquid crystal display device>
The liquid crystal display device of the present invention uses the above-described color filter of the present invention. There is no restriction | limiting in particular about the model and structure of the liquid crystal display device of this invention, It can assemble in accordance with a conventional method using the color filter of this 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, September 29, 1989, Japan Society for the Promotion of Science 142nd Committee).

<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 by the green pigment-colored resin composition of the present invention. A multicolor organic EL element is produced by laminating an organic light-emitting body 500 on the organic protective layer 30 and the inorganic oxide film 40 thereon.

  As a method for laminating the organic light emitter 500, 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 are sequentially formed on the upper surface of the color filter. For example, a method of adhering the organic light-emitting body 500 formed on another substrate onto the inorganic oxide film 40 can be used. The organic EL element 100 manufactured as described above can be applied to both a passive drive type organic EL display device and an active drive type organic EL display device.

EXAMPLES Next, although an Example and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to a following example, unless the summary is exceeded.
In the following examples, “part” represents “part by weight”.
[1] Resin synthesis
<Synthesis Example 1: Synthesis of Binder Resin A>
Prepare a separable flask with a cooling tube as a reaction tank, charge 400 parts by weight of propylene glycol monomethyl ether acetate, purge with nitrogen, and heat in an oil bath while 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, cyclohexyl methacrylate 110 in the monomer tank
Parts by weight, 5.2 parts by weight of t-butylperoxy-2-ethylhexanoate, 40 parts by weight of propylene glycol monomethyl ether acetate, 5.2 parts by weight of n-dodecyl mercaptan, propylene glycol monomethyl in a chain transfer agent tank 27 parts by weight of ether acetate was charged, and after the temperature of the reaction vessel was stabilized at 90 ° C., dropping was started from the monomer tank and the chain transfer agent tank to initiate polymerization. While maintaining the temperature at 90 ° C., dropping was carried out over 135 minutes each, and 60 minutes after the dropping was finished, the temperature was raised and the reaction vessel was brought to 110 ° C.

  After maintaining at 110 ° C. for 3 hours, a gas introduction tube was attached to the separable flask and bubbling of oxygen / nitrogen = 5/95 (v / v) mixed gas was started. Next, 39.6 parts by weight of glycidyl methacrylate, 0.4 parts by weight of 2,2′-methylenebis (4-methyl-6-tert-butylphenol), and 0.8 parts by weight of triethylamine were charged into the reaction vessel at 110 ° C. as it was. For 9 hours. The weight average molecular weight Mw measured by GPC of the resin A thus obtained was 8000, and the acid value was 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. To this was added 100.1 g (0.55 mol) of cyclohexyl methacrylate, 33.3 g (0.45 also) of methacrylic acid, and 4.925 g (0.03 mol) of 2.2′-azobis (isobutyronitrile) in propylene glycol. It melt | dissolved in 96.45g of monomethyl ether acetate, and was dripped over 4 hours. After the dropwise addition, the reaction solution was further stirred for 2 hours while maintaining the temperature at 85 ° C., and thereafter the nitrogen bubbling was stopped and the temperature was raised to 100 ° C. for 1 hour. The weight average molecular weight Mw measured by GPC of the resin B thus obtained was about 15000, and the acid value was 190 mgKOH / g.

<Synthesis Example 3: Synthesis of Binder Resin C>
145 parts by weight of propylene glycol monomethyl ether acetate was stirred while purging with nitrogen, and the temperature was raised to 120 ° C. 10 parts by weight of styrene, 85.2 parts by weight of glycidyl methacrylate, and 66 parts by weight of monoacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) were added dropwise thereto, and 2.2'-azobis-2-methyl 8.47 parts by weight of butyronitrile was added dropwise over 3 hours, and stirring was continued at 90 ° C. for 2 hours. Next, the inside of the reaction vessel was changed to air substitution, 0.7 part by weight of trisdimethylaminomethylphenol and 0.12 part 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 weight average molecular weight Mw measured by GPC of the resin C thus obtained was about 8400, and the acid value was 80 mgKOH / g.

[2] Preparation of pigment dispersion
[2-1] Preparation of green pigment dispersion
As a pigment, C.I. I. Pigment Green 58 (manufactured by DIC; hereinafter abbreviated as “G58”), 37.88 parts by weight, as a dispersant, “BYK-LPN6919” (methacrylic acid AB block copolymer, amine value 121 mgKOH / g, Acid value 1 mg KOH / g or less) 9.48 parts by weight in terms of solids, binder resin A of Synthesis Example 1 as binder resin 12.64 parts by weight in terms of solids, and 240.00 parts by weight of propylene glycol monomethyl ether acetate as solvent A 0.25 part by weight zirconia bead having a diameter of 0.5 mm was filled in a stainless steel container, and dispersed in a paint shaker for 6 hours to prepare a green pigment dispersion.

[2-2] Preparation of yellow pigment dispersion
E4GN-GT (manufactured by LANXESS; hereinafter abbreviated as “NiAzo-Y”) as a pigment, 18.94 parts by weight, BYK-LPN6919 (manufactured by BYK Chemie) as a dispersant, 4.74 parts by weight in terms of solid content, resin In a stainless steel container, 6.32 parts by weight of the binder resin A of Synthesis Example 1 in terms of solid content, 120.00 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 are filled in a stainless steel container. A yellow pigment dispersion was prepared by dispersing for 6 hours with a shaker.

[2-3] Preparation of blue pigment dispersion C.I. I. Pigment Blue 15: 6 (hereinafter abbreviated as “B15: 6”) 9.26 parts by weight, Dispersbyk 2000 (manufactured by Big Chemie) as a dispersant (acrylic block copolymer, quaternary ammonium base (dimethylbenzylammonium base) AB block copolymer composed of B block having and A block not having an amine value of 10 mgKOH / g, acid value of 0 mgKOH / g) was 2.65 parts by weight in terms of dispersant solid content, and further prepared in Synthesis 2. The stainless steel container was filled 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. A blue pigment dispersion was prepared by time dispersion.

[3] Preparation of coloring composition
[2-1] to [2-3] dispersion, propylene glycol monomethyl ether acetate and ethyl 3-ethoxypropionate as solvent, resin C as binder resin, dipentaerythritol hexaacrylate as photopolymerizable monomer, light As a polymerization 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-acetyloxime) and F-475 (fluorine-based surfactant) manufactured by DIC as a surfactant are mixed at a ratio shown in Table 1, and the colored compositions of Examples and Comparative Examples are mixed. The numerical values in Table 1 are the contents (parts by weight).

[3] Manufacture of patterns (pixels)
Each of the colored compositions was spin-coated on a glass substrate on which chromium was deposited, and prebaked for 3 minutes on a hot plate at 80 ° C. The coating rotation speed was adjusted so that the color coordinate y = 0.599 after post-baking.
Next, after exposing the sample at 30 mj / cm ² through a linear mask pattern having a width of 50 μm and a length of 3 mm with a high-pressure mercury lamp, a 0.04 wt% potassium hydroxide aqueous solution was used,
Spray development was performed at a developer temperature of 23 ° C. and a pressure of 0.25 MPa. The development time was set to twice the dissolution time of the colored composition measured in advance. The dissolution time measurement 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. Table 2 shows the dry film thickness.

[4] Measurement of chromaticity and brightness of colored composition As in [3], the colored composition is applied on a glass substrate AN100 (Asahi Glass Co., Ltd.), dried, exposed, developed, post-baked, and then the spectrophotometer U -3310 (manufactured by Hitachi, Ltd.), chromaticity and luminance with a C light source were measured.
[5] Measurement of dissolution time of coloring composition
As in [3], a colored composition is applied on a glass substrate, dried, exposed, and spray-developed using a 0.04 wt% aqueous potassium hydroxide solution at a developer temperature of 23 ° C. and a pressure of 0.25 MPa. The time when the colored composition in the unexposed area was completely dissolved in the developer and the substrate was exposed was taken as the dissolution time of the colored composition.

[6] Measurement of linear pattern overhang
[10] Ten linear patterns having a line width of 50 μm, which were developed for 40 seconds by the method described in [3], were observed with an optical microscope at a magnification of 10 times, and the number of the dents at the edge of the line was counted. This was repeated twice to confirm reproducibility. A photomicrograph of a representative example of the pattern (pixel) is shown in FIG.

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-colored resin composition of the present invention have reduced pixel defects while maintaining the characteristics of the pixels, that is, characteristics such as luminance and contrast. . That is, a good linear pattern is obtained as a pixel.
Accordingly, the color filter formed using the green pigment colored resin composition of the present invention has no light leakage, high color purity, high luminance, and high contrast.

  In addition, as the luminance, in particular, a value greater than 56.0% is useful as a practical level, so that the forms of Examples 1 to 8 satisfy the characteristics at the practical level of luminance, Moreover, it is particularly preferable because the number of chips is reduced.

Claims (8)

(A) a zinc halide phthalocyanine green pigment, (B) a photopolymerization initiator and (H) a solvent,
And (D) a blue pigment and (F) a dispersant,
The (D) blue pigment is a copper phthalocyanine pigment represented by the following formula (1-I):
Wherein (F) dispersing agent, Ri modified acrylic copolymer der,
The (H) solvent includes propylene glycol monomethyl ether acetate and a solvent having a boiling point of 150 ° C. or higher,
The green pigment colored resin composition for forming a green pixel, wherein the content of the solvent having a boiling point of 150 ° C. or higher with respect to the total amount of the (H) solvent is 1 to 50% by weight .
(In the formula (1-I), each R independently represents a hydrogen atom.)   Furthermore, the green pigment coloring resin composition of Claim 1 characterized by including a yellow pigment | dye (E).   The green pigment-colored resin composition according to claim 1 or 2, wherein the (A) halogenated zinc phthalocyanine green pigment is a brominated zinc phthalocyanine green pigment.   The said (D) blue pigment | dye is 0.05 weight% or more and 2.0 weight% or less in all the pigments, The green pigment coloring as described in any one of Claims 1-3 characterized by the above-mentioned. Resin composition. (G) The green pigment coloring resin composition as described in any one of Claims 1-4 characterized by containing a polymerizable monomer. Characterized in that it comprises a pixel formed by using a green pigmented resin composition according to any one of claims 1 to 5 color filter. A liquid crystal display device comprising the color filter according to claim 6 . An organic EL display device comprising the color filter according to claim 6 .