JP2010102277A - Green colored composition for color filter, and color filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a green colored composition for a color filter excellent in fluidity and various resistance, and a color filter using the composition and having high brightness and contrast ratio. <P>SOLUTION: This green colored composition for the color filter contains at least: a green pigment component containing a zinc halide phthalocyanine pigment; a basic resin type dispersant having an amine number of 35-100 mgKOH/g; and a pigment carrier consisting of a resin, its precursor, or their mixture. The basic resin type dispersant is a block copolymer. The green colored composition contains a dye derivative having a basic functional group. The color filter uses the green colored composition. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a green coloring composition for a color filter used for manufacturing a color filter used for a color liquid crystal display device, a color image pickup tube element, and the like, and a color filter formed using the same.

In the liquid crystal display device, a liquid crystal layer sandwiched between two polarizing plates controls the amount of light passing through the first polarizing plate by controlling the degree of polarization of light passing through the first polarizing plate. The type using twisted nematic (TN) type liquid crystal is the mainstream. A liquid crystal display device is capable of color display by providing a color filter between two polarizing plates, and has recently been used in televisions, personal computer monitors, and the like. Increasing demands are being made.
A color filter is a surface of a transparent substrate such as glass, in which two or more kinds of fine band (striped) filter segments of different hues are arranged in parallel or crossing each other, or fine filter segments are arranged vertically and horizontally. It is made up of those arranged in The filter segments are as fine as several microns to several hundreds of microns, and are regularly arranged in a predetermined arrangement for each hue.

Generally, in a color liquid crystal display device, a transparent electrode for driving liquid crystal is formed on a color filter by vapor deposition or sputtering, and an alignment film for aligning liquid crystal in a certain direction is further formed thereon. ing. In order to sufficiently obtain the performance of these transparent electrodes and alignment films, the formation thereof must generally be performed at a high temperature of 200 ° C. or higher, preferably 230 ° C. or higher. For this reason, at present, as a method for producing a color filter, a method called a pigment dispersion method using a pigment having excellent light resistance and heat resistance as a colorant is mainly used.
However, in general, a color filter in which a pigment is dispersed has a problem that the degree of polarization controlled by the liquid crystal is disturbed due to light scattering by the pigment. That is, since light leaks when light must be blocked (OFF state) or transmitted light attenuates when light must be transmitted (ON state), display devices in the ON state and the OFF state There is a problem that the upper luminance ratio (contrast ratio) is low.

  Until now, in order to realize high brightness and high contrast of the color filter, the pigment contained in the filter segment has been refined. However, various pigments (similarly called crudes having a particle size of 10 to 100 μm produced by chemical reaction, which are made into a mixture of primary particles and aggregated secondary particles by pigmentation treatment) Even if the particles are refined by the refinement treatment method, the pigments whose primary particles or secondary particles have been refined generally tend to agglomerate. When the refinement is too advanced, a huge lump of pigment solid is formed. End up. Furthermore, even if the finely-divided pigment is dispersed in a pigment carrier containing a resin or the like, and the secondary particles of the pigment are stabilized as close as possible to the primary particles, a stable coloring composition is obtained. It is very difficult.

  Colored compositions in which pigments that have been made finer are dispersed in a pigment carrier often have a high viscosity due to aggregation of pigment particles over time and exhibit thixotropic properties. Such an increase in viscosity and poor fluidity of the colored composition causes various problems in production work and product value. For example, the filter segment of a color filter is generally formed by spin-coating a colored composition in which a pigment is dispersed in a pigment carrier containing a monomer and a resin on a glass substrate. If a poor coloring composition is used, a coating film having a uniform thickness cannot be obtained due to poor spin coatability, poor leveling, etc., which is not preferable.

  On the other hand, as described above, the color filter is required to have not only high contrast but also high brightness. In general, in order to obtain high brightness, when dispersing the pigment in the pigment carrier, the transparency of the dispersion is increased to close to the primary particles, and the spectral spectrum of the dispersion has high transmittance, thereby increasing the brightness. It has gained.

  However, green, which is one of the three primary colors (red, green, blue; RGB) of the color filter substrate, is a halogenated copper phthalocyanine pigment (for example, CI Pigment Green 36 or CI Pigment) as the main pigment. Although it is common to use green 7), it has been difficult to achieve both high contrast ratio and high brightness as long as copper halide phthalocyanine can be used.

In order to solve these problems, zinc halide phthalocyanine pigments that replace the current copper halide phthalocyanine pigment with zinc as a colorant that exhibits a clear color tone and a wide color display area and has high coloring power. Have been used.
JP-A-10-130547 JP 2001-141922 A JP 2007-204658 A

  However, the halogenated zinc phthalocyanine green pigment has higher acidity than the halogenated copper phthalocyanine green pigment. Therefore, the halogenated zinc phthalocyanine green pigment is difficult to disperse compared to the halogenated copper phthalocyanine green pigment.

  Colored compositions with poor dispersion often become thicker due to aggregation of pigment particles over time and exhibit thixotropic properties. Such an increase in viscosity and poor fluidity of the colored composition causes various problems in production work and product value. For example, the filter segment of a color filter is generally formed by spin-coating a colored composition in which a pigment is dispersed in a pigment carrier containing a monomer and a resin on a glass substrate. If a poor coloring composition is used, a coating film having a uniform thickness cannot be obtained due to poor spin coatability, poor leveling, etc., which is not preferable.

  An object of the present invention is to provide a stable green coloring composition for a color filter excellent in fluidity, and a color filter using the same and having a high brightness and contrast ratio.

  The above-mentioned problems include a green pigment component containing at least a zinc halide phthalocyanine pigment, a basic resin type dispersant having an amine value of 35 to 100 mgKOH / g, a pigment carrier comprising a resin, a precursor thereof, or a mixture thereof, It can be solved by a green coloring composition for color filters comprising

  In the preferable aspect of the green coloring composition for color filters of this invention, content of the said basic resin type dispersing agent is 0.001 to 50 weight% on the basis of the total weight of the said green pigment component.

  In a preferred embodiment of the green coloring composition for a color filter of the present invention, the basic resin type dispersant comprises a basic copolymer block (A) and a pigment carrier affinity copolymer block (B). A block copolymer resin.

  In a preferred embodiment of the green composition for a color filter of the present invention, the block copolymer resin is a block copolymer resin obtained by living radical polymerization.

  In the preferable aspect of the green composition for color filters of this invention, the pigment derivative which has a basic substituent is further included.

  In a preferred embodiment of the green coloring composition for a color filter of the present invention, the content of the pigment derivative having a basic substituent is 0.001 to 40% by weight based on the total weight of the green pigment component. .

In a preferred embodiment of the green coloring composition for a color filter of the present invention, when the resin constituting the pigment carrier has an acid value of X (mg KOH / g) and a weight average molecular weight of Y, the following formula (A ), (B), and (c) satisfying all of the conditions at the same time.
(A) Y> −750X + 51000
(A) Y> 940X-79000
(U) Y> 8000

  The present invention also relates to a color filter comprising a green filter segment formed from the green coloring composition for a color filter.

  The green coloring composition for a color filter of the present invention comprises a green pigment component containing at least a zinc halide phthalocyanine pigment, a basic resin type dispersant having an amine value of 35 to 100 mgKOH / g, a resin, a precursor thereof, or the like And a pigment carrier made of a mixture of the above, it becomes a highly fluid and stable pigment dispersion, and by using this, a color filter with high brightness and high contrast ratio can be formed. .

In particular, when the basic resin type dispersant is a block copolymer resin composed of a basic copolymer block (A) and a pigment carrier affinity copolymer block (B), it is even higher. A pigment dispersion capable of forming a color filter having a contrast ratio is obtained.
Furthermore, when a pigment derivative having a basic substituent is included, the initial contrast ratio is increased and the temporal stability is also improved.

  First, the green coloring composition for color filters of the present invention will be described in detail with reference to preferred embodiments.

  In the present application, when “(meth) acryloyl”, “(meth) acryl”, “(meth) acrylic acid”, “(meth) acrylate”, and “(meth) acryloyloxy” are particularly expressed, Unless otherwise stated, “acryloyl and / or methacryloyl”, “acrylic and / or methacrylic”, “acrylic acid and / or methacrylic acid”, “acrylate and / or methacrylate”, and “acryloyloxy and / or methacryloyloxy”, respectively. ".

  The green coloring composition for a color filter of the present invention comprises a green pigment component containing at least a zinc halide phthalocyanine pigment, a basic resin type dispersant having an amine value of 35 to 100 mgKOH / g, a resin, a precursor thereof, or the like A pigment carrier made of a mixture of

(Green pigment component)
The green coloring composition for a color filter of the present invention is characterized by using a green pigment component containing at least a zinc halide phthalocyanine pigment as a main pigment.

  A typical zinc halide phthalocyanine pigment represented by a color index (CI) number is C.I. I. Pigment Green 58 etc. can be mentioned. By using a halogenated zinc phthalocyanine pigment as the main pigment, high brightness not obtained with other green pigments can be obtained. Furthermore, what was obtained by the well-known manufacturing method can be used. In particular, the amount of acidic functional groups on the pigment surface is preferably 100 μmol when measured using n-hexylamine as a basic substance by the method described in Coloring Materials, 67 [9], 547-554 (1994). / G or more, more preferably 200 μmol / g or more can be used.

  For the pigment component, not only the halogenated zinc phthalocyanine, which is the main pigment, but also other green pigments and yellow pigments can be used in combination for color adjustment and complementary color purposes.

  Other green pigments that can be used in combination include C.I. I. And green pigments such as CI Pigment Green 7, 10, 36, and 37. Examples of yellow pigments that can be used in combination include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181 Mention may be made of the yellow pigments such as 182,185,187,188,193,194,198,199,213,214.

  The preferred concentration of the pigment component in all the non-volatile components of the colored composition according to the present invention is 10 to 90% by weight, more preferably 15 to 85% by weight, most preferably from the viewpoint of obtaining sufficient color reproducibility. Is 20 to 80% by weight. When the concentration of the pigment component is less than 10% by weight, sufficient color reproducibility cannot be obtained, and when it exceeds 90% by weight, the concentration of the pigment carrier is lowered and the stability of the coloring composition is deteriorated.

  Particularly preferred pigment ratios include, for example, 50 to 100% by weight of a halogenated zinc phthalocyanine pigment, 0 to 50% by weight of a copper halide phthalocyanine pigment, and 0 to 50% by weight of a yellow pigment, based on the total weight of the pigment component. %.

  More preferably, based on the total weight of the pigment component, the halogenated zinc phthalocyanine pigment is 50 to 90% by weight, the halogenated copper phthalocyanine pigment is 5 to 45% by weight, and the yellow pigment is 5 to 45% by weight. The chromaticity region can be expanded by such a composition ratio of the pigment.

  The green colored composition of the present invention using a halogenated zinc phthalocyanine pigment is applied to a glass substrate or the like so as to have the same chromaticity as the green colored composition using a halogenated copper phthalocyanine pigment, and the coating film is transmitted. When the rate is measured, the transmittance is higher than that of the coating film of the colored composition using the copper phthalocyanine pigment at around 530 nm from around 450 nm. In particular, the transmittance peak shows a transmittance as high as about 5% and a value of about 90%. Therefore, by combining with a backlight generally used in color liquid crystal display devices, C.I. I. Pigment Green 36 and C.I. I. High brightness that could not be obtained with a colored composition using a halogenated copper phthalocyanine pigment such as CI Pigment Green 7 can be obtained.

  The pigment used in the green coloring composition of the present invention can be subjected to a salt milling process and can be used in a refined product, and is preferably used in a refined product.

  Salt milling is a process in which a mixture of pigment, water-soluble inorganic salt and water-soluble organic solvent is heated using a kneader such as a kneader, two-roll mill, three-roll mill, ball mill, attritor, or sand mill. After kneading, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt works as a crushing aid, and it is thought that the pigment is crushed using the high hardness of the inorganic salt during salt milling, thereby generating an active surface and causing crystal growth. Yes. Therefore, the crushing of the pigment and the crystal growth occur simultaneously during the kneading, and the primary particle diameter of the pigment obtained varies depending on the kneading conditions.

  In order to promote crystal growth by heating, the heating temperature is preferably 40 to 150 ° C. When the heating temperature is less than 40 ° C., crystal growth does not occur sufficiently, and the shape of the pigment particles becomes close to amorphous, which is not preferable. On the other hand, when the heating temperature exceeds 150 ° C., crystal growth proceeds excessively and the primary particle diameter of the pigment becomes large, which is not preferable as a colorant for the color filter coloring composition. The kneading time for the salt milling treatment is preferably 2 to 24 hours from the viewpoint of the balance between the particle size distribution of the primary particles of the salt milling treatment pigment and the cost required for the salt milling treatment.

  By optimizing the conditions at the time of subjecting the pigment to salt milling, it is possible to obtain a pigment having a very fine primary particle diameter, a wide distribution range, and a sharp particle size distribution.

  It is preferable that the primary particle diameter calculated | required by TEM (transmission electron microscope) of the green pigment used for the green coloring composition of this invention is the range of 20-100 nm. When it becomes smaller than 20 nm, dispersion in an organic solvent becomes difficult. On the other hand, if it exceeds 100 nm, a sufficient contrast ratio cannot be obtained. A particularly preferable range is 25 to 85 nm.

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

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

  When performing the salt milling treatment, a resin may be added as necessary. The type of resin used is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like can be used. The resin used is solid at room temperature, preferably insoluble in water, and more preferably partially soluble in the organic solvent. The amount of the resin used is preferably in the range of 5 to 200% by weight based on the total weight of the pigment.

(Basic resin type dispersant)
The green coloring composition of the present invention is characterized in that zinc halide phthalocyanine having zinc as a central metal is used as a main pigment of a pigment component, and the halogenated zinc phthalocyanine is generally added to a green coloring composition. Compared to the copper halide phthalocyanine pigment used, it is an acidic pigment having zinc as the central metal, and the pigment surface has a negative charge. Therefore, unless a basic resin type dispersant having a high amine value is used as the resin type dispersant used at the time of pigment dispersion, the adsorption to the acidic pigment becomes insufficient, and the dispersion cannot obtain sufficient fluidity. .

  As a number average molecular weight of the basic resin type dispersing agent used by this invention, 500-50000 are preferable normally, and 3000-30000 are especially more preferable. When the number average molecular weight is less than 500, the effect of steric repulsion due to the pigment affinity group, the effect of compatibility with the pigment carrier, and the effect of compatibility with the pigment carrier and solvent when using a solvent are small, It may be difficult to prevent aggregation of the pigment, and the viscosity of the dispersion may increase. On the other hand, if the number average molecular weight is 50000 or more, the amount of resin added necessary for dispersion increases, resulting in a decrease in the pigment concentration in the coating film.

  In the present invention, a basic resin type dispersant having an amine value of 35 to 100 mgKOH / g is used. The amine value of the basic resin type dispersant is more preferably 50 to 75 mgKOH / g. When the amine value is less than 35 mgKOH / g, the pigment is not sufficiently adsorbed and dispersion is poor, and when it exceeds 100 mgKOH / g, the adsorption efficiency to the zinc halide phthalocyanine pigment is poor due to the adsorption or reaction to the acidic component in the pigment carrier. It becomes a dispersion | distribution defect.

  As the basic resin type dispersant having an amine value of 35 to 100 mgKOH / g, various types of resin systems such as vinyl, urethane, polyester, polyether, or polyamide can be used. A vinyl monomer copolymer type that is easy and excellent in various resistances is preferable. Specifically, N, N-disubstituted amino group-containing vinyl monomer units, alkyl (meth) acrylate monomer units, and other vinyl monomers Copolymer resins with units are preferred.

  As N, N-disubstituted amino group-containing vinyl monomer units, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, Examples thereof include N, N-diethylaminopropyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylamide, and N, N-diethylaminoethyl (meth) acrylamide, but are not necessarily limited thereto. These monomer units are adsorbed to a zinc halide phthalocyanine pigment having a high acidity as a basic group-containing monomer unit.

  As alkyl (meth) acrylate monomer units, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, It is obtained by the reaction of unsaturated monocarboxylic acid such as 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, or lauryl (meth) acrylate with alkyl alcohol having 1 to 18 carbon atoms (meta ) Acrylic esters and the like, but are not necessarily limited thereto. These monomer units act as pigment carrier affinity groups.

  Other vinyl monomer units include nitro group-containing vinyl monomers such as (meth) acrylonitrile, vinyl aromatic monomers such as styrene, α-methylstyrene, or benzyl (meth) acrylate, 2-hydroxyethyl ( Hydroxyl group-containing vinyl monomers such as (meth) acrylate, hydroxypropyl (meth) acrylate, or polyethylene glycol (meth) acrylate, (meth) acrylamide, N, N-dimethylacrylamide, N-isopropylacrylamide, diacetone acrylamide, etc. Amide group-containing vinyl monomers, vinyl monomers such as N-methylol (meth) acrylamide or dimethylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, or N-butoxime Alkoxymethyl group-containing vinyl monomers such as ru (meth) acrylamide, olefins such as ethylene, propylene or isoprene, dienes such as chloroprene or butadiene, methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, Examples thereof include vinyl ethers such as n-butyl vinyl ether or isobutyl vinyl ether, and fatty acid vinyls such as vinyl acetate or vinyl propionate, which are appropriately used according to the purpose, but are not necessarily limited thereto.

  Polymers having primary amino group-containing monomer units such as allylamine, or polyethyleneimine, polyethylene polyamine, polyxylylene poly (hydroxypropylene) polyamine, or poly (aminomethylated) epoxy resin, polyester resin, acrylic resin Alternatively, a comb-shaped basic resin dispersant modified with a polyether resin or the like can also be used.

  As a commercial item of such a basic resin type dispersant, for example, DISPERBYK 161, 162, 163, 164, 166, 167, 168, 174, 182, 183, 184, 185, 2000, 2050, 2150 of Big Chemie Japan Co., Ltd. , 2163, 2164, SOLPERSE 11200, 13240, 13650, 13940, 24000, 26000, 28000, 32000, 32500, 32550, 32600, 33000, 34750, 35100, 35200, 37500, 38500, 39000, 53095, 56000, Japan Lubrizol Corporation 7100, EFKA 4300, 4330, 4046, 4060, 4080, etc. manufactured by Ciba Japan.

  As the basic resin-type dispersant for the green coloring composition for color filters of the present invention, a block comprising a basic copolymer block (A) and a pigment carrier affinity copolymer block (B) is particularly preferred. It is a copolymer resin. Hereinafter, the block copolymer resin type basic dispersion resin will be described.

(Block copolymer resin type basic resin type dispersant)
The basic resin-type dispersant of the green coloring composition for color filter of the present invention has an effect of preventing the aggregation between the portion adsorbed on the pigment (hereinafter abbreviated as the adsorbing portion) and the pigment, and improving the dispersibility. And a portion having a high affinity for the pigment carrier (hereinafter abbreviated as an affinity portion). Since zinc halide phthalocyanine has high acidity, if the affinity part and the adsorption part are randomly arranged, the adsorption to the pigment becomes insufficient, resulting in poor dispersion. In the present invention, the basic copolymer block (A) which is an adsorption part for the zinc halide phthalocyanine pigment and the pigment carrier affinity copolymer block (B) which is an affinity part for the pigment carrier are on the same molecule. By using a block copolymer resin that exists separately as a resin-type dispersant, a green coloring composition in which a zinc halide phthalocyanine pigment is finely, low-viscosity and stably dispersed without impairing its color characteristics Things can be provided.

Various resin systems can be selected for the basic copolymer block (A) and the pigment carrier affinity copolymer block (B) constituting the block copolymer resin, but the resin design is easy. A vinyl copolymer excellent in various resistances is desirable.
Hereinafter, each copolymer block will be described.

<Basic copolymer block (A)>
Specific examples of the basic copolymer block (A) include N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N N, N-diethylaminopropyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide and the like having N, N-disubstituted amino group-containing vinyl monomer units Polymers, polymers having primary amino group-containing monomer units such as allylamine, polyethyleneimine, polyethylene polyamine, polyxylylene poly (hydroxypropylene) polyamine, poly (aminomethylated) epoxy resin, etc. Yes, but not necessarily limited to these Not.

  Among these, a copolymer having an N, N-disubstituted amino group-containing vinyl monomer unit, which is easy to design a resin of the block copolymer and excellent in various resistances, is preferable. The N, N-disubstituted amino group-containing vinyl monomer unit contained in the combined block (A) is 60 to 100% by weight, more preferably 80 to 100% by weight, and the N, N-disubstituted amino group is contained. The vinyl monomer unit other than the vinyl monomer unit is preferably a vinyl monomer unit described in the pigment carrier affinity copolymer block (B).

<Pigment carrier affinity copolymer block (B)>
The pigment carrier-affinity copolymer block (B) is a vinyl monomer copolymer that allows easy resin design of the block copolymer and is excellent in various resistances, and further, alkyl (meth) acrylate as a vinyl monomer unit. In particular, it is contained in the pigment carrier affinity copolymer block (B) in an amount of 60 to 100% by weight, more preferably 80 to 100% by weight. Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, It is obtained by the reaction of unsaturated monocarboxylic acid such as 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, or lauryl (meth) acrylate with alkyl alcohol having 1 to 18 carbon atoms (meta ) Acrylic esters and the like, but are not necessarily limited thereto.

  The pigment carrier affinity copolymer block (B) preferably contains 0% by weight of vinyl monomer units containing amino groups, but may be contained if it is less than 10% by weight.

Other vinyl monomer units that may be included in the basic copolymer block (A) and the pigment carrier affinity copolymer block (B) include nitro group-containing vinyl monomers such as (meth) acrylonitrile, Hydroxyl-containing vinyl such as styrene, α-methylstyrene, vinyl aromatic monomers such as benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, or polyethylene glycol (meth) acrylate Amide group-containing vinyl monomers such as methacrylic monomers, (meth) acrylamide, N, N-dimethylacrylamide, N-isopropylacrylamide, diacetone acrylamide, N-methylol (meth) acrylamide, dimethylol (meth) acrylamide, etc. Cycloalkenyl-based monomers, N- methoxymethyl (meth) acrylamide, or N- butoxymethyl (meth) alkoxymethyl group-containing vinyl monomers such as acrylamide, ethylene, propylene, or olefins such as isoprene;
Dienes such as chloroprene or butadiene, vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether, or fatty acid vinyls such as vinyl acetate and vinyl propionate However, it is not necessarily limited to these.

<Block copolymer resin>
The resin-type dispersant of the present invention can be produced by a known method. In particular, (1) a method using living polymerization, or (2) a basic copolymer block (A) having a functional group at the terminal. The polymer coupling method in which the precursor (a) of (2) is reacted with the precursor (b) of the pigment carrier affinity copolymer block (B) having a functional group at the terminal is preferred. Among these, (1) a method using living polymerization is particularly preferable.

(1) Living polymerization method In the living polymerization method, side reactions occurring in general radical polymerization are suppressed, and further, the growth of polymerization occurs uniformly, so that a block polymer or a resin having a uniform molecular weight can be easily synthesized.
Above all, the atom transfer radical polymerization method using organic halides and sulfonyl halide compounds as initiators and transition metal complexes as catalysts can be applied to a wide range of monomers and employs a polymerization temperature applicable to existing equipment. It is preferable in that it can be performed. An atom transfer radical polymerization method can be performed by the method described in the following references 1 to 8 and the like.
(Reference 1) Fukuda et al., Prog. Polym. Sci. 2004, 29, 329
(Reference 2) Matyjaszewski et al., Chem. R ev. 2001, 101, 2921
(Reference 3) Matyjaszewski et al. Am. Chem. Soc. 1995, 117, 5614
(Reference 4) Macromolecules 1995, 28, 7901, Science, 1996, 272, 866
(Reference 5) Pamphlet of International Publication No. 96/30421 (Reference 6) Pamphlet of International Publication No. 97/18247 (Reference 7) JP-A-9-208616 (Reference 8) JP-A-8-411117

  In the atom transfer radical polymerization method, a transition metal complex such as copper, ruthenium, iron and nickel is used as a redox catalyst. Specific examples of the transition metal complex include low-valent halogenated transition metals such as copper (I) chloride and copper (I) bromide. In order to control the polymerization rate, a well-known method is used. High valent transition metals such as copper (II) chloride and copper (II) bromide may be added to the polymerization system.

  An organic ligand is used for the metal complex. Organic ligands are used to allow reversible changes in solubility in the polymerization solvent and redox conjugated complexes. Examples of the metal coordination atom include a nitrogen atom, an oxygen atom, a phosphorus atom, and a sulfur atom, and a nitrogen atom or a phosphorus atom is preferable. Specific examples of the organic ligand include sparteine, 2,2′-bipyridyl and derivatives thereof, 1,10-phenanthroline and derivatives thereof, tetramethylethylenediamine, pentamethyldiethylenetriamine, tris (dimethylaminoethyl) amine, hexamethyl ( 2-aminoethyl) amine, triphenylphosphine, and tributylphosphine. Among the above catalysts, polymerization is preferably performed using a combination of copper halide and tetraethylenediamine in view of controlling the polymerization rate and the molecular weight of the block resin.

The transition metal and the organic ligand may be added separately to form a metal complex in the polymer, or the metal complex may be synthesized in advance and added to the polymerization system. In particular, when the transition metal is copper, the former method is preferable, and for the ruthenium, iron, and nickel, the latter method is preferable.
Specific examples of ruthenium, iron and nickel complexes synthesized in advance include tristriphenylphosphinoniruthenium chloride (Ru (Cl) ₂ (PPh ₃ ) ₃ , bistrisphenylphosphinoniiron chloride (Fe (Cl) ₂ (PPh ₃ ) ₂ ), nickel bistrisphenylphosphinonichloride (Ni (Cl) ₂ (PPh ₃ ) ₂ ), nickel bistributylphosphinonibromide (NiBr ₂ (PBu ₃ ) ₂ ), etc. It is done.

  As the initiator used in the atom transfer radical polymerization method, known initiators can be used, and organic halides having a highly reactive carbon halogen bond, sulfonyl halide compounds and the like are mainly used. Specific examples include ethyl bromoisobutyrate, ethyl bromobutyrate, ethyl chloroisobutyrate, ethyl chlorobutyrate, p-toluenesulfonic acid chloride, bromoethylbenzene, and chloroethylbenzene. These are used alone or in combination.

  In the above atom transfer radical polymerization, the initiator of the atom transfer radical polymerization is appropriately selected according to the molecular weight of the resin to be synthesized, but is preferably 0.001 to 10 mol% based on the total amount of the radical polymerizable monomer. Preferably it is used in a proportion of 0.01 to 1 mol%.

  The amount of transition metal used is preferably 0.03 to 3 moles, more preferably 0.1 to 2 moles per mole of initiator as a form of halide or the like. Further, the ligand is used in a proportion of usually 1 to 5 mol, preferably 1.2 to 3 mol, per 1 mol of the transition metal (form of halide, etc.). When the above-mentioned atom transfer radical polymerization initiator, transition metal and ligand are used in such proportions, it is preferable in terms of the reactivity of living radical polymerization, the molecular weight of the produced polymer, and the like.

  In addition, due to the characteristics of atom transfer radical polymerization, the resulting resin has an active carbon-halogen bond at the terminating end, which can be modified by a known method to introduce a functional group. Moreover, it can superpose | polymerize with the polymerization initiator which has a functional group, can introduce | transduce a functional group to the resin terminal, and can utilize for various reactions.

  Atom transfer radical polymerization can be carried out without a solvent, or may be carried out in the presence of a solvent such as butyl acetate, toluene, xylene, anisole, methyl ethyl ketone, or cyclohexanone. In particular, a ketone solvent is preferable from the viewpoint of polymerization rate, and methyl ethyl ketone is particularly preferable. In the case of using a solvent, in order to prevent a decrease in polymerization rate, the amount of the solvent used after the polymerization is preferably 50% by weight or less. Even when there is no solvent or a small amount of solvent, there is no particular safety problem with respect to control of polymerization heat and the like. Rather, reduction of the solvent is preferable in terms of economy and environmental measures.

  The polymerization conditions are 60 to 130 ° C. polymerization temperature from the point of polymerization rate and catalyst deactivation, and depending on the final molecular weight and polymerization temperature, the polymerization time may be about 1 to 100 hours. . The polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon in order to prevent deactivation of the polymerization catalyst by oxygen.

  After completion of the polymerization reaction, the polymerization reaction system is preferably cooled to 0 ° C. or lower, more preferably about −78 ° C. to stop the reaction, and the remaining monomer and / or solvent is removed according to a known method. Reprecipitation in the medium and filtration of the precipitated polymer can be performed by centrifugation, washing of the polymer and drying. The block resin used in the present invention can be obtained by removing the transition metal and the like contained in the polymerization system by a known method, if necessary, and then evaporating the volatile components. As the removal method, the reaction mixture is diluted with an organic solvent such as tetrahydrofuran, toluene, or methyl ethyl ketone, washed with water / dilute hydrochloric acid or an aqueous amine solution, and the resin solution is contacted with a cation exchange resin or a chelate resin. There are a method of passing through a silica or clay column or pad, a method of filtering and centrifuging after adding an adsorbent such as a reducing agent or hydrotalcite. From the viewpoint of ease of processing, it is preferable to add a cation exchange resin and an acid adsorbent such as hydrotalcite to the diluted resin solution and stir, and filter the ion exchange resin and the acid adsorbent to obtain a resin solution. .

  When water is mixed into the resin solution by the purification treatment, the reaction between the block resin used in the present invention and the curing agent may be hindered. For example, a solvent miscible with water may be added to the resin solution and subjected to azeotropic dehydration, etc. It is desirable to remove moisture from the resin solution by treatment.

  In the atom transfer radical polymerization used in the present invention, in order to suppress side reactions that occur during general radical polymerization, depending on the charging ratio of the initiator of the atom transfer radical polymerization added during polymerization and the radical polymerizable monomer, The molecular weight of the resin and the ratio of the basic copolymer block (A) or the pigment carrier affinity copolymer block (B) can be freely controlled.

(2) Polymer coupling method Functional group at the terminal of the precursor (a) of the basic copolymer block (A) and the precursor (b) of the pigment carrier affinity copolymer block (B) in the polymer coupling method Specific examples of preferable examples include a carboxyl group, a primary amino group, a hydroxyl group, and an alkoxysilyl group.

  As a method for introducing a terminal functional group into the precursor (a) of the basic copolymer block (A) and the precursor (b) of the pigment carrier affinity copolymer block (B), the functional groups listed above are used. A method of radical polymerization using a chain transfer agent having a thiol group is preferred. The chain transfer agent having a carboxyl group is mercaptopropionic acid, the chain transfer agent having a primary amino group is cysteamine, the chain transfer agent having a hydroxyl group is mercaptoethanol, and the chain transfer agent having an alkoxysilyl group is 3- Examples include mercaptopropylmethylmethoxysilane and 3-mercaptopropyltrimethoxysilane.

  The reaction between the precursor (a) and the precursor (b) can be carried out by a known reaction with a combination of the following Table 1, for example.

  Examples of the binder polyisocyanate compound include aromatic polyisocyanate, aliphatic polyisocyanate, araliphatic polyisocyanate, and alicyclic polyisocyanate. Examples of the aromatic polyisocyanate include 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6 -Tolylene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, or 4,4 ' , 4 "-triphenylmethane triisocyanate, etc. Examples of the aliphatic polyisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, Examples include tamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, or 2,4,4-trimethylhexamethylene diisocyanate. Examples of the polyisocyanate include ω, ω′-diisocyanate-1,3-dimethylbenzene, ω, ω′-diisocyanate-1,4-dimethylbenzene, ω, ω′-diisocyanate-1,4-diethylbenzene, 1, Examples include 4-tetramethylxylylene diisocyanate or 1,3-tetramethylxylylene diisocyanate, etc. Examples of the alicyclic polyisocyanate include 3-isocyanate methyl-3,5,5-trimethylcyclohexane. Xyl isocyanate, 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4′-methylenebis ( Cyclohexyl isocyanate), 1,4-bis (isocyanate methyl) cyclohexane, 1,4-bis (isocyanate methyl) cyclohexane, etc., but are not necessarily limited to these, and some of the above poly A trimethylolpropane adduct of isocyanate, a burette reacted with water, a trimer having an isocyanurate ring, and the like can also be used in combination.

  As the polyepoxy compound of the binder, a polyepoxy compound having at least two glycidyl groups is preferable. Specifically, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, trimethylolethane triglycidyl ether, sorbitol polyglycidyl ether, or penta Aliphatic polyepoxy compounds such as erythritol polyglycidyl ether, aromatic polyepoxy compounds of the bisphenol A or bisphenol F type, tetraglycidylaminophenylmethane, triglycidyl isocyanurate, or 1,3-bis (N, N-glycidylaminomethyl) ) Glycidylamine type epoxy compounds such as cyclohexane, but are not necessarily limited to these Not intended to be.

  The number average molecular weight of the block copolymer type basic resin dispersant used in the present invention is usually preferably 500 to 50000, more preferably 3000 to 30000. When the number average molecular weight is less than 500, the effect of steric repulsion by the pigment affinity copolymer block (B), the effect of compatibility with the pigment carrier, and the phase with the pigment carrier and the solvent when a solvent is used. The solubility effect is small, it is difficult to prevent pigment aggregation, and the viscosity of the dispersion may increase. On the other hand, if the number average molecular weight is 50000 or more, the amount of resin necessary for dispersion increases, leading to a decrease in the pigment concentration in the coating film.

  The amine value of the block copolymer type basic resin dispersant used in the present invention is 35 to 100 mgKOH / g, more preferably 50 to 75 mgKOH / g. If the amine value is less than 35 mgKOH / g, it will not be sufficiently adsorbed by the pigment, resulting in poor dispersion. If it exceeds 100 mgKOH / g, the adsorption efficiency to the pigment will deteriorate due to adsorption or reaction with acidic components in the pigment carrier, resulting in poor dispersion. It becomes.

  The constituent weight ratio of the basic copolymer block (A) and the pigment carrier affinity copolymer block (B) and the number average molecular weight of each block are the number average molecular weight and amine value of the resin type dispersant as a whole. It is preferable that it can be designed arbitrarily so as to be in the preferable range.

  In the green coloring composition of the present invention, the amount of the basic resin dispersant is preferably 0.001 to 50% by weight, more preferably 0.1 to 30% by weight, based on the total weight of the pigment component. Most preferably, it is 0.5 to 25% by weight. If the blending amount of the resin-type dispersant is less than 0.001% by weight based on the total weight of the pigment component, the dispersibility may be deteriorated, and if it exceeds 40% by weight, the heat resistance and light resistance may be deteriorated. is there.

(Pigment carrier)
In addition to the pigment component and the resin-type dispersant, the green coloring composition of the present invention includes a pigment carrier made of a resin, a precursor thereof, or a mixture thereof.

  The pigment carrier used in the green coloring composition of the present invention preferably has a spectral transmittance of 80% or more, more preferably 95% or more of a resin, a precursor thereof, or the like in the entire wavelength region of 400 to 700 nm in the visible light region. It is a mixture. Resins include thermoplastic resins, thermosetting resins, and active energy ray curable resins, and precursors thereof include monomers or oligomers that are cured by irradiation with active energy rays to form transparent resins, These can be used alone or in admixture of two or more. The pigment carrier can be used in an amount of 30 to 500% by weight, based on the total weight of the pigment component. If it is less than 30% by weight, the film formability and various resistances are insufficient, and if it exceeds 500% by weight, the pigment concentration is low and color characteristics cannot be expressed.

The resin constituting the pigment carrier is a resin that satisfies all of the following formulas (a), (b), and (c) simultaneously when the acid value is X (mg KOH / g) and the weight average molecular weight is Y: It is preferable that
(A) Y> −750X + 51000
(A) Y> 940X-79000
(U) Y> 8000

  If it is outside this range, the basic resin type dispersant adsorbed on the pigment surface will be peeled off, resulting in poor dispersion due to causes such as pigment aggregation. Further, Y ≦ 60000 is preferable, and Y ≦ 50000 is further preferable. When Y exceeds 60,000, it becomes unfavorable because developability becomes poor when used as an alkali development type colored resist described later.

  When the resin constituting the pigment carrier satisfies all the conditions of the above formulas (a), (b), and (c), the resin type is adsorbed on the pigment because it is in a good acid value range. Since the dispersant and the resin can maintain an appropriate interaction, and because it has a good molecular weight range, it can appropriately function as the steric hindrance of the carrier resin, so that a good dispersion This is preferable because the state can be maintained. In particular, a basic resin type dispersant described later and / or a dye derivative having a basic substituent described later can be favorably adsorbed on the pigment surface. Conversely, when the resin constituting the pigment carrier does not satisfy the condition of the formula (A), the interaction between the basic resin type dispersant adsorbed on the pigment surface and the resin is too weak. In addition, a good dispersion state cannot be maintained due to pigment aggregation or the like. If the condition of the formula (c) is not satisfied, the interaction is too strong, so the resin-type dispersant adsorbed on the pigment is peeled off, and a good dispersion state is maintained due to pigment aggregation and the like. I can't do it. Further, when the condition of the formula (d) is not satisfied, the molecular weight is too small, so that the resin does not act as a steric hindrance, resulting in poor dispersion due to causes such as pigment aggregation. Further, Y ≦ 60000 is preferable, and Y ≦ 50000 is further preferable. When Y exceeds 60000, it is not preferable because it may cause poor developability when used as an alkali development type colored resist described later.

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

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

  When used in the form of an alkali development type colored resist described later, an alkali-soluble resin having an acidic group such as a (meth) acrylic acid copolymer resin (alkali-soluble acrylic resin) is used. In order to satisfactorily disperse the halogenated zinc phthalocyanine pigment, the weight average molecular weight (Mw) of the alkali-soluble resin is preferably in the range of 10,000 to 100,000, and in the range of 30,000 to 80,000. It is more preferable that The number average molecular weight (Mn) is preferably in the range of 5,000 to 50,000, and the value of Mw / Mn is preferably 10 or less.

  As an active energy ray-curable resin, a linear polymer having a reactive substituent such as a hydroxyl group, a carboxyl group, or an amino group has a reactive substituent such as an isocyanate group, an aldehyde group, or an epoxy group ( A resin in which a photocrosslinkable group such as a (meth) acryloyl group or a styryl group is introduced into the linear polymer by reacting with a (meth) acrylic compound or cinnamic acid is used. In addition, a linear polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is converted into a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. Half-esterified products are also used.

Examples of monomers and oligomers that are resin precursors include:
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tertiary butyl (meth) acrylate, isoamyl (meth) acrylate, Octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cetyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, Linear or branched alkyl (meth) acrylates such as isomyristyl (meth) acrylate, stearyl (meth) acrylate, or isostearyl (meth) acrylate;
Cyclohexyl (meth) acrylate, Tertiarybutylcyclohexyl (meth) acrylate, Dicyclopentanyl (meth) acrylate, Dicyclopentanyloxyethyl (meth) acrylate, Dicyclopentenyl (meth) acrylate, Dicyclopentenyloxyethyl (meth) ) Acrylates or cyclic alkyl (meth) acrylates such as isobornyl (meth) acrylate;
Fluoroalkyl (meth) acrylates such as trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, or tetrafluoropropyl (meth) acrylate;
(Meth) acryloxy-modified polydimethylsiloxanes (silicone macromers);
(Meth) acrylates having a heterocyclic ring such as tetrahydrofurfuryl (meth) acrylate or 3-methyl-3-oxetanyl (meth) acrylate;
Benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, paracumylphenoxyethyl (meth) acrylate, paracumylphenoxypolyethylene glycol (meth) acrylate, or nonylphenoxypolyethylene glycol (meth) acrylate, etc. (Meth) acrylates having the following aromatic ring;
2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2-methoxypropyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, diethylene glycol monoethyl ether (meta ) Acrylate, triethylene glycol monomethyl ether (meth) acrylate, triethylene glycol monoethyl ether (meth) acrylate, diethylene glycol mono-2-ethylhexyl ether (meth) acrylate, dipropylene glycol monomethyl ether (meth) acrylate, tripropylene glycol mono (Meth) acrylate, polyethylene glycol monolauryl ether (meth) acrylate, or polyester Glycol monostearyl ether (meth) acrylate of (poly) alkylene glycol monoalkyl ether (meth) acrylates;
(Meth) acrylic acid, acrylic acid dimer, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxypropyl phthalate, 2- (meth) acryloyloxyethyl hexahydrophthalate, 2- (meth) (Meth) acrylates having a carboxyl group such as acryloyloxypropyl hexahydrophthalate, ethylene oxide-modified succinic acid (meth) acrylate, β-carboxyethyl (meth) acrylate, or ω-carboxypolycaprolactone (meth) acrylate;
2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-acryloyloxyethyl-2-hydroxyethyl (meth) Phthalates,
Diethylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, propylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate,
Polytetramethylene glycol mono (meth) acrylate, poly (ethylene glycol-propylene glycol) mono (meth) acrylate, poly (ethylene glycol-tetramethylene glycol) mono (meth) acrylate, poly (propylene glycol-tetramethylene glycol) mono ( (Meth) acrylates having hydroxyl groups such as meth) acrylate or glycerol (meth) acrylate;
Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tri Propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, poly (ethylene glycol-propylene glycol) di (meth) acrylate, poly (ethylene glycol-tetramethylene glycol) di (meth) acrylate, poly (propylene glycol- Tetramethylene glycol) di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, 1,3-butanediol di (Meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, or 2-ethyl, 2-butyl-propanediol di ( (Poly) alkylene glycol di (meth) acrylates such as (meth) acrylate,
Dimethylol dicyclopentane di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, stearic acid modified pentaerythritol di (meth) acrylate, ethylene oxide modified bisphenol A di (meth) acrylate, propylene oxide modified bisphenol A Di (meth) acrylate, tetramethylene oxide modified bisphenol A di (meth) acrylate, ethylene oxide modified bisphenol F di (meth) acrylate, propylene oxide modified bisphenol F di (meth) acrylate, tetramethylene oxide modified bisphenol F di (meth) Acrylate, zinc diacrylate, ethylene oxide-modified phosphate triacrylate, or glycerol di (meth) acrylate Di (meth) acrylate and the like;
(Meth) acrylates having a tertiary amino group such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminopropyl (meth) acrylate;
Glycerol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, or dipentaerythritol hexa (meth) acrylate Trifunctional or higher polyfunctional (meth) acrylates such as
Glycerol triglycidyl ether- (meth) acrylic acid adduct, glycerol diglycidyl ether- (meth) acrylic acid adduct, polyglycerol polyglycidyl ether- (meth) acrylic acid adduct, 1,6-butanediol diglycidyl ether- (Meth) acrylic acid adduct, alkyl glycidyl ether- (meth) acrylic acid adduct, allyl glycidyl ether- (meth) acrylic acid adduct, phenyl glycidyl ether- (meth) acrylic acid adduct, styrene oxide- (meth) Acrylic acid adduct, bisphenol A diglycidyl ether- (meth) acrylic acid adduct, propylene oxide modified bisphenol A diglycidyl ether- (meth) acrylic acid adduct, bisphenol F diglycidyl ether- (meth) acrylic Acid adduct, epichlorohydrin modified phthalic acid- (meth) acrylic acid adduct, epichlorohydrin modified hexahydrophthalic acid- (meth) acrylic acid adduct, ethylene glycol diglycidyl ether- (meth) acrylic acid adduct, polyethylene glycol diglycidyl Ether- (meth) acrylic acid adduct, propylene glycol diglycidyl ether- (meth) acrylic acid adduct, polypropylene glycol diglycidyl ether- (meth) acrylic acid adduct, phenol novolac type epoxy resin- (meth) acrylic acid addition , Cresol novolac type epoxy resin- (meth) acrylic acid adduct, or other epoxy resin- (meth) acrylic acid adduct, etc., epoxy (meth) acrylates;
(Meth) acryloyl-modified isocyanurate, (meth) acryloyl-modified polyurethane, (meth) acryloyl-modified polyester, (meth) acryloyl-modified melamine, (meth) acryloyl-modified silicone, (meth) acryloyl-modified polybutadiene, or (meth) acryloyl-modified rosin (Meth) acryloyl-modified resin oligomers such as;
Vinyls such as styrene, α-methylstyrene, vinyl acetate, vinyl (meth) acrylate, or allyl (meth) acrylate;
Vinyl ethers such as hydroxyethyl vinyl ether, ethylene glycol divinyl ether, or pentaerythritol trivinyl ether;
Amides such as (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, or N-vinylformamide; or
Examples include acrylonitrile. These can be used alone or in admixture of two or more, but are not necessarily limited thereto.

(Dye derivative)
In the coloring composition for a color filter of the present invention, a dye derivative can be used for the purpose of improving the dispersibility of the pigment. Examples of the dye derivative include a compound in which a basic substituent, an acidic substituent, or a phthalimidomethyl group which may have a substituent is introduced into an organic pigment, anthraquinone, acridone, or triazine.

  In the present invention, a basic derivative is particularly preferable, and the basic derivative is a compound represented by the following general formula (1), which is a derivative having a specific parent skeleton having a basic group. Although it will not specifically limit if it is a pigment derivative which has a basic group, The pigment derivative which has the triazine ring skeleton which has a basic group shown by following General formula (1) can be used conveniently.

General formula (1):
P-Lm
(However, in general formula (1),
P is an m-valent organic pigment residue, an anthraquinone skeleton, an acridone skeleton, or a triazine skeleton,
m is an integer of 1 to 4,
L is a substituent selected from the group represented by the general formulas (2), (3), and (4). )

  General formula (2):

  General formula (3):

  General formula (4):

[However, in the general formulas (2) to (4),
X _{is, -SO 2 -, - CO -} , - CH 2 -, - CH 2 NHCOCH 2 -, - CH 2 NHSO 2 CH 2 -, or a direct bond,
Y is —NH—, —O—, or a direct bond;
n is an integer of 1 to 10,
Y ¹ is —NH—, —NR ⁵⁸ —Z—NR ⁵⁹ —, or a direct bond;
R ⁵⁸ and R ⁵⁹ are each independently a hydrogen bond, an optionally substituted alkyl group having 1 to 36 carbon atoms, an optionally substituted alkenyl group having 2 to 36 carbon atoms, or A phenyl group which may have a substituent,
Z is an alkylene group which may have a substituent, or an arylene group which may have a substituent,
R ⁵⁰ and R ⁵¹ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 30 carbon atoms, an optionally substituted alkenyl group having 2 to 30 carbon atoms, or R ⁵⁰ and R ⁵¹ together are a heterocyclic ring which may further have a substituent containing a further nitrogen, oxygen or sulfur atom,
R ⁵² , R ⁵³ , R ⁵⁴ , and R ⁵⁵ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms that may have a substituent, or 2 to carbon atoms that may have a substituent. 20 alkenyl group, an arylene group having 6 to 20 carbon atoms which may have a substituent,
R ⁵⁶ is a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted alkenyl group having 2 to 20 carbon atoms,
R ⁵⁷ is a substituent represented by the general formula (2) or (3),
Q is a hydroxyl group, an alkoxyl group, a substituent represented by the general formula (2), or a substituent represented by the general formula (3). ]

  Examples of the amine component used for forming the substituents represented by the general formulas (2) to (4) include dimethylamine, diethylamine, methylethylamine, N, N-ethylisopropylamine, N, N-ethyl. Propylamine, N, N-methylbutylamine, N, N-methylisobutylamine, N, N-butylethylamine, N, N-tert-butylethylamine, diisopropylamine, dipropylamine, N, N-sec-butylpropylamine , Dibutylamine, di-sec-butylamine, diisobutylamine, N, N-isobutyl-sec-butylamine, diamylamine, diisoamylamine, dihexylamine, dicyclohexylamine, di (2-ethylhexyl) amine, dioctylamine, N, N-methyloctadeci Amine, didecylamine, diallylamine, N, N-ethyl-1,2-dimethylpropylamine, N, N-methylhexylamine, dioleylamine, distearylamine, N, N-dimethylaminomethylamine, N, N-dimethylamino Ethylamine, N, N-dimethylaminoamylamine, N, N-dimethylaminobutylamine, N, N-diethylaminoethylamine, N, N-diethylaminopropylamine, N, N-diethylaminohexylamine, N, N-diethylaminobutylamine, N , N-diethylaminopentylamine, N, N-dipropylaminobutylamine, N, N-dibutylaminopropylamine, N, N-dibutylaminoethylamine, N, N-dibutylaminobutylamine, N, N-diisobutylaminopen Ruamine, N, N-methyl-laurylaminopropylamine, N, N-ethylhexylaminoethylamine, N, N-distearylaminoethylamine, N, N-dioleylaminoethylamine, N, N-distearylaminobutylamine, Piperidine, 2-Pipecoline, 3-Pipecoline, 4-Pipecoline, 2,4-Lupetidine, 2,6-Lupetidine, 3,5-Lupetidine, 3-Piperidinmethanol, Pipecolic acid, Isonipecotic acid, Methyl isonipecotate, Isonicopetic acid Ethyl, 2-piperidineethanol, pyrrolidine, 3-hydroxypyrrolidine, N-aminoethylpiperidine, N-aminoethyl-4-pipecholine, N-aminoethylmorpholine, N-aminopropylpiperidine, N-aminopropyl-2-pipecholine, -Aminopropyl-4-pipecholine, N-aminopropylmorpholine, N-methylpiperazine, N-butylpiperazine, N-methylhomopiperazine, 1-cyclopentylpiperazine, 1-amino-4-methylpiperazine, 1-cyclopentylpiperazine, etc. Is mentioned.

  The pigment derivative, anthraquinone derivative, and acridone derivative having a basic substituent of the present invention can be synthesized by various synthetic routes. For example, after introducing the substituents represented by the general formulas (5) to (8) into an organic dye, anthraquinone, or acridone, the substituents represented by the general formulas (2) to (4) react with the above substituents. For example, N, N-dimethylaminopropylamine, N-methylpiperazine, diethylamine, or 4- [4-hydroxy-6- [3- (dibutylamino) propylamino] -1,3. It can be obtained by reacting 5-triazin-2-ylamino] aniline or the like.

General formula (5): -SO ₂ Cl
General formula (6): -COCl
Formula _{(7): -CH 2 NHCOCH 2} Cl
Formula (8): —CH ₂ Cl

  In the reaction of the substituents of the general formulas (5) to (8) with the amine component, a part of the substituents of the general formulas (5) to (8) are hydrolyzed so that chlorine is substituted with a hydroxyl group. It may be mixed. In that case, the general formula (5) and the general formula (6) are a sulfonic acid group and a carboxylic acid group, respectively. Or a salt with a monoamine.

  Further, when the organic dye is an azo dye, the substituent represented by the general formulas (2) to (4) is introduced into the diazo component or the coupling component in advance, and then the coupling reaction is performed, thereby performing the azo pigment. Derivatives can also be produced.

  The triazine derivative having a basic group of the present invention can be synthesized by various synthetic routes. For example, starting from cyanuric chloride, an amine component that forms a substituent represented by the general formulas (2) to (4) on at least one chlorine of cyanuric chloride, such as N, N-dimethylaminopropylamine or N- It can be obtained by reacting methylpiperazine or the like and then reacting the remaining chlorine of cyanuric chloride with various amines or alcohols.

  In the pigment composition of the present invention, the blending amount of the pigment derivative having a base substituent is preferably 1 to 50 parts by weight, more preferably 3 to 30 parts by weight, and most preferably 5 parts by weight with respect to 100 parts by weight of the pigment component. ~ 25 parts by weight. When the basic derivative is less than 1 part by weight with respect to 100 parts by weight of the pigment component, the dispersibility may be deteriorated, and when it exceeds 50 parts by weight, the heat resistance and light resistance may be deteriorated. Among these, those having a triazine structure in the basic substituent are preferable from the viewpoint of dispersion stability.

(dispersion)
The green coloring composition of the present invention comprises a pigment component containing at least a zinc halide phthalocyanine pigment together with the basic resin type dispersant, or the basic resin type dispersant and the pigment derivative having the basic substituent. The pigment carrier can be produced by finely dispersing the pigment carrier using various dispersing means such as the three-roll mill, two-roll mill, sand mill, kneader, and attritor. The green coloring composition of the present invention can also be produced by mixing several types of pigments separately dispersed on a pigment carrier.

  The green coloring composition of the present invention can be further prepared in the form of a solvent development type or alkali development type green resist by adding a photopolymerization initiator. When preparing in the form of an alkali developing type colored resist, an alkali-soluble material having an acidic group in a part of the pigment carrier is used.

(Photopolymerization initiator)
A photopolymerization initiator or the like is added to the green coloring composition for a color filter of the present invention when the composition is cured by ultraviolet irradiation or a filter segment is formed by a photolithographic method. The blending amount when using the photopolymerization initiator is preferably 5 to 200% by weight based on the total weight of the pigment component, and 10 to 150% by weight from the viewpoint of photocurability and developability. Is more preferable.

As the photopolymerization initiator, for example,
4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2- Such as benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one or 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one An acetophenone photopolymerization initiator;
Benzoin photopolymerization initiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyldimethyl ketal;
Benzophenone photopolymerization initiators such as benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, or 4-benzoyl-4'-methyldiphenyl sulfide;
A thioxanthone photopolymerization initiator such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, or 2,4-diisopropylthioxanthone;
2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s -Triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloromethyl) -s-triazine, 2,4-bis (trichloro) Methyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxy-naphth-1-yl) -4 , 6-Bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4-trichloromethyl (4′-methoxystyryl) -6 Triazine photopolymerization initiators such as triazine;
Borate photopolymerization initiator;
A carbazole photoinitiator; or
Although an imidazole series photoinitiator etc. are used, it is not necessarily limited to these.

  The above photopolymerization initiators are used alone or in combination of two or more. As sensitizers, α-acyloxy ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone. , Camphorquinone, ethyl anthraquinone, 4,4′-diethylisophthalophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, or 4,4′-diethylaminobenzophenone However, it is not necessarily limited to these.

  The blending amount when using the sensitizer is preferably 3 to 60% by weight based on the blending weight of the photopolymerization initiator contained in the colored composition, from the viewpoint of photocurability and developability. More preferably, it is 5 to 50% by weight.

(Dispersing aid)
When dispersing the pigment component in the pigment carrier, a dispersing aid such as a surfactant can be appropriately used in addition to the resin-type pigment dispersant of the present invention. The dispersion aid is excellent in pigment dispersion and has a great effect of preventing re-aggregation of the pigment after dispersion. Therefore, when a green coloring composition in which the pigment is dispersed in the pigment carrier using the dispersion aid is used. In this case, a color filter having a high spectral transmittance can be obtained.

As the surfactant, for example,
Sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate, monoethanolamine lauryl sulfate Anionic surfactants such as lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, or polyoxyethylene alkyl ether phosphate;
Nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate, or polyethylene glycol monolaurate;
Chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; or
Examples include alkylbetaines such as alkyldimethylaminoacetic acid betaines, and amphoteric surfactants such as alkylimidazolines, which can be used alone or in admixture of two or more, but are not necessarily limited thereto. .

  Furthermore, in the green coloring composition for a color filter of the present invention, the pigment is sufficiently dispersed in a pigment carrier, and applied to a transparent substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm. In order to make it easy to form a filter segment, a solvent can be contained and used in the form of “green ink” or “green resist ink”.

(solvent)
As the solvent, the following solvents which are usually used in the production of ink and resist ink can be used.

  Examples of these solvents include 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3 -Butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m -Dichlorobenzene, N, N-dimethylacetamide, N, N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, N-methylpyrrole Don, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol Diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether , Ethylene glycol monohexyl ether, ethylene glycol Methyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, Cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether Dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene Glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methylcyclohexanol, n-amyl acetate, n-butyl acetate, Acetate Amyl, isobutyl acetate, propyl acetate, or a dibasic acid ester and the like, but used alone or in admixture, not necessarily limited thereto. The solvent can be used in an amount of 800 to 4000% by weight, based on the total weight of the pigment component. Outside this range, it is difficult to adjust to an appropriate viscosity as described below, and a desired color filter having a uniform film thickness cannot be obtained.

  The green coloring composition for a color filter of the present invention has a viscosity immediately after dispersion (viscosity at 60 rpm at 25 ° C.) of 2 to 100 mPa · s, a thixo index immediately after dispersion (viscosity at 6 rpm and 25 rpm). Viscosity ratio is 1.4 or less, the viscosity increase rate with time after storage for 3 months under the condition of 10 ° C. (the condition of 10 ° C. after dispersion, based on the viscosity at a rotation speed of 60 rpm at 25 ° C. immediately after dispersion) The viscosity increase rate at a rotation speed of 60 rpm at 25 ° C. stored for 3 months) is preferably less than 20%. When the viscosity after dispersion is less than 2 mPa · s or more than 100 mPa · s, or when the thixo index immediately after dispersion exceeds 1.4, or when the rate of increase in viscosity over time is 20% or more, the coating uniformity is maintained. Therefore, a desired color filter having a uniform film thickness cannot be obtained. The viscosity and the thixo index can be measured using, for example, an E-type viscometer (“ELD viscometer” manufactured by Toki Sangyo Co., Ltd.).

(Storage stabilizer)
In addition, the green coloring composition of the present invention can contain a storage stabilizer in order to stabilize the viscosity with time of the composition.

Examples of storage stabilizers include:
Quaternary ammonium chlorides such as benzyltrimethylammonium chloride or diethylhydroxyamine;
Organic acids such as lactic acid or oxalic acid;
Methyl esters of the organic acids;
catechols such as t-butylpyrocatechol;
Organic phosphines such as triphenylphosphine, tetraethylphosphine, or tetraphenylphosphine; or
Examples thereof include phosphites.

(Removal of coarse particles and dust)
The green coloring composition of the present invention is a coarse particle having a size of 5 μm or more, preferably a coarse particle having a size of 1 μm or more, more preferably a coarse particle having a size of 0.5 μm or more. It is preferable to remove the mixed dust. When coarse particles are present, foreign matters remain in the color filter, causing problems in practical use, and in the coating process, foreign matters are clogged in the piping and nozzles, resulting in serious manufacturing problems. Thus, it is preferable that a green coloring composition does not contain a particle | grain of 0.5 micrometer or more substantially. More preferably, the particles contained in the green coloring composition are 0.3 μm or less (particle diameter by SEM).

  The average dispersed particle size is preferably 0.05 to 0.2 μm for increasing the brightness and contrast ratio, and more preferably 0.06 to 0.15 μm because the brightness and contrast ratio can be further increased. .

(Manufacture of color filters)
The color filter of the present invention can be produced by a printing method or a photolithography method.

  The formation of the filter segment by the printing method can be patterned simply by repeating the printing and drying of the coloring composition prepared as the printing ink. Therefore, the color filter manufacturing method is low in cost and excellent in mass productivity. Furthermore, a fine pattern having high dimensional accuracy and smoothness can be printed by the development of printing technology. In order to perform printing, it is preferable that the ink does not dry and solidify on the printing plate or on the blanket. Control of the fluidity of the ink on the printing machine is also important, and the ink viscosity can be adjusted with a dispersant or extender pigment.

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

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

  The color filter of the present invention can be produced by an electrodeposition method or a transfer method in addition to the above method, but the colored composition of the present invention can be used in any method. The electrodeposition method is a method for producing a color filter by using a transparent conductive film formed on a substrate and forming each color filter segment on the transparent conductive film by electrophoresis of colloidal particles. .

  The transfer method is a method in which a filter segment is formed in advance on the surface of a peelable transfer base sheet, and the filter segment is transferred to a desired substrate.

(Color filter)
Next, the color filter of the present invention will be described. The color filter of the present invention comprises at least one red filter segment, at least one blue filter segment, and at least one green filter segment, and the at least one green filter segment comprises the coloring composition for a color filter of the present invention. Formed using.

  The red filter segment can be formed using a normal red coloring composition. Examples of the red coloring composition include C.I. I. Pigment Red 7, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 57: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 122, 146, Red pigments such as 168, 177, 178, 184, 185, 187, 200, 202, 208, 210, 246, 254, 255, 264, 270, 272, 279 are used.

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

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

  Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In the examples and comparative examples, “part” means “part by weight”. Mn and Mw mean a number average molecular weight and a weight average molecular weight, respectively.

(Average molecular weight of basic resin type dispersant)
The number average molecular weight (Mn) and weight average molecular weight (Mw) of the basic resin type dispersant are HLC-8320GPC (manufactured by Tosoh Corporation) as a device, SUPER-AW3000 as a column, and 30 mM triethylamine as an eluent. And polystyrene-equivalent number average molecular weight (Mn) and weight average molecular weight (Mw) measured using an N, N-dimethylformamide solution of 10 mM LiBr.

(Amine value of basic resin type dispersant)
The amine value of the basic resin type dispersant is a value obtained by converting the total amine value (mgKOH / g) measured in accordance with the method of ASTM D 2074 into a solid content.

(Average molecular weight of the resin constituting the pigment carrier)
The number average molecular weight (Mn) and the weight average molecular weight (Mw) of the acrylic resin used as the resin for the pigment carrier are TPCgel columns (manufactured by Tosoh Corporation) and GPC equipped with an RI detector (manufactured by Tosoh Corporation, HLC-8120GPC ) And polystyrene-equivalent number average molecular weight (Mn) and weight average molecular weight (Mw) measured using THF as a developing solvent.

(Acid value of pigment carrier resin)
The acid value of the acrylic resin used as the resin for the pigment carrier is a value obtained by converting the measured acid value (mgKOH / g) into a solid content according to the potentiometric titration method of JIS K0070.
Next, prior to the examples, the resin-type dispersant used in the examples and comparative examples, its solution, a commercially available resin-type dispersant solution, an acrylic resin, and its solution will be described.

(Synthesis of Resin Type Dispersant 1 and Preparation of Solution)
A four-necked separable flask equipped with a thermometer, stirrer, distillation tube, and condenser was charged with 70 parts of methyl ethyl ketone, 76.0 parts of n-butyl acrylate, 2.8 parts of sparteine, and 1.9 parts of ethyl bromoisobutyrate. The temperature was raised to 40 ° C. under a nitrogen stream. 1.1 parts of cuprous chloride was added and the temperature was raised to 75 ° C. to initiate polymerization. After polymerization for 3 hours, the polymerization solution is sampled, and it is confirmed that the polymerization yield is 95% or more from the solid content of the polymerization, and 24.0 parts of N, N-dimethylaminoethyl methacrylate and 30.0 parts of MEK are added. Further, polymerization was performed. After 2 hours, it was confirmed that the polymerization yield was 97% or more from the solid content of the polymerization solution, and the polymerization was stopped by cooling to room temperature. 100 parts of the obtained resin solution was diluted with 100 parts of methyl ethyl ketone, 60 parts of cation exchange resin “Diaion PK228LH (Mitsubishi Chemical Corporation)” was added and stirred at room temperature for 1 hour. Part of "KYOWARD 500SN" (manufactured by Kyowa Chemical Industry Co., Ltd.) was added and stirred for 30 minutes. The polymerization catalyst residue was removed by removing the cation exchange resin and the adsorbent by filtration. Further, the resin solution was concentrated and replaced with ethylene glycol monomethyl ether acetate to obtain a solution of resin type dispersant 1 (Mn = 10200, Mw = 1200, amine value 86 mgKOH / g) having a nonvolatile content of 40% by weight.

(Synthesis of Resin Type Dispersant 2 and Preparation of Solution)
In the same manner as in Synthesis Example 1, 70 parts of methyl ethyl ketone, 75.0 parts of n-butyl acrylate, 10.0 parts of methyl methacrylate, 2.3 parts of sparteine, and 1.6 parts of ethyl bromoisobutyrate were prepared, and cuprous chloride was prepared. 0.9 parts were charged to initiate polymerization. After polymerization for 3 hours, 15.0 parts of N, N-dimethylaminoethyl methacrylate and 30.0 parts of MEK were added, and polymerization was further performed for 2 hours. Thereafter, the same polymerization catalyst residue as in Synthesis Example 1 was removed and an operation was performed to obtain a solution of resin-type dispersant 2 (Mn = 1900, Mw = 13200, amine value 54 mgKOH / g) having a nonvolatile content of 40% by weight. Obtained.

(Synthesis of Resin Type Dispersant 3 and Preparation of Solution)
In the same manner as in Synthesis Example 1 above, 70 parts of methyl ethyl ketone, 45.0 parts of ethyl acrylate, 43.0 parts of methyl methacrylate, 3.3 parts of sparteine, and 2.8 parts of ethyl bromoisobutyrate were charged. 4 parts were charged to initiate polymerization. After polymerization for 3 hours, 12.0 parts of N, N-dimethylaminoethyl methacrylate and 30.0 parts of MEK were added, and polymerization was further performed for 2 hours. Thereafter, the same polymerization catalyst residue as in Synthesis Example 1 was removed and an operation was performed to prepare a solution of resin-type dispersant 3 (Mn = 7000, Mw = 8500, amine value 43 mgKOH / g) having a nonvolatile content of 40% by weight. Obtained.

(Synthesis of Resin Type Dispersant 4 and Preparation of Solution)
In the same manner as in Synthesis Example 1 above, 70 parts of methyl ethyl ketone, 71.0 parts of n-butyl acrylate, 2.8 parts of sparteine and 1.9 parts of ethyl bromoisobutyrate were charged, and 1.4 parts of cuprous chloride were added. The polymerization was started. After polymerization for 3 hours, 29.0 parts of N, N-dimethylaminoethyl methacrylate and 30.0 parts of MEK were added and polymerization was performed for 2 hours. Thereafter, the same polymerization catalyst residue as in Synthesis Example 1 was removed and an operation was performed to prepare a solution of resin-type dispersant 4 (Mn = 10000, Mw = 12000, amine value 105 mgKOH / g) having a nonvolatile content of 40% by weight. Obtained.

(Synthesis of Resin Type Dispersant 5 and Preparation of Solution)
In the same manner as in Synthesis Example 1 above, 70 parts of methyl ethyl ketone, 66.0 parts of n-butyl acrylate, 2.8 parts of spartein and 1.9 parts of ethyl bromoisobutyrate were charged, and 1.4 parts of cuprous chloride were added. The polymerization was started. After polymerization for 3 hours, 34.0 parts of N, N-dimethylaminoethyl methacrylate and 30.0 parts of MEK were added, and polymerization was further performed for 2 hours. Thereafter, the same polymerization catalyst residue as in Synthesis Example 1 was removed, and an operation was performed to obtain a solution of resin-type dispersant 5 (Mn = 9800, Mw = 12000, amine value 121 mgKOH / g) having a nonvolatile content of 40% by weight. Obtained.

(Preparation of commercially available resin-type dispersant solution)
BYK161, 163, 164, 167, 174, 184, 2000, 2050 manufactured by Big Chemie Japan, which is a commercially available resin type dispersant, SOLPERSE 34750, 56000 manufactured by Nippon Lubrizol, EFKA 4330, 4046, 4060, 4080 manufactured by Ciba Japan Each of those with a non-volatile content of less than 40% was dried under reduced pressure to make the non-volatile content 60% or more, and then prepared into a 40% non-volatile solution using ethylene glycol monomethyl ether acetate, and a commercially available resin dispersion Used as an agent solution.

(Synthesis of acrylic resin A and preparation of its solution)
The reaction vessel was charged with 800 parts of cyclohexanone, heated to 100 ° C. while injecting nitrogen gas into the vessel, and at the same temperature, 80.0 parts of styrene, 40.0 parts of methacrylic acid, 85.0 N, N-methyl methacrylate. A mixture of 95.0 parts of n-butyl methacrylate and 10.0 parts of azobisisobutyronitrile was added dropwise over 1 hour to carry out a polymerization reaction.

  After the dropwise addition, the mixture was further reacted at 100 ° C. for 3 hours, then 2.0 parts of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 100 ° C. for 1 hour. A cyclohexanone solution of acrylic resin A having a weight average molecular weight of about 30,000 and an acid value of 87 mgKOH / g was obtained.

  After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. Then, ethylene glycol monomethyl was added to the previously synthesized resin solution so that the non-volatile content was 20% by weight. A solution of acrylic resin A was prepared by adding ether acetate.

(Synthesis of acrylic resins B to P and preparation of their solutions)
Acrylic resins B to P were synthesized in the same manner as the synthetic method of acrylic resin A with the monomer composition and initiator amount (azobisisobutyronitrile amount) shown in Table 2 below, and these solutions were prepared. Further, Table 2 shows the acid value and weight average molecular weight of the synthesized resin.

Explanation of abbreviations in Table 2 Styrene: Styrene (parts by weight)
MA: Methacrylic acid (parts by weight)
MMA: Methyl methacrylate (parts by weight)
nBMA: n-butyl methacrylate (parts by weight)
AIBN: Azobisisobutyronitrile (parts by weight)
Acid value (mgKOH / g)
Molecular weight: Weight average molecular weight (A) Formula: (A) Y> −750X + 51000
(A) Formula: (A) Y> 940X-79000
(U) Formula: (U) Y> 8000
X: Acid value of resin (mgKOH / g)
Y: weight average molecular weight of resin)

  Next, a method for measuring the primary particle size of the pigment and a method for preparing the pigment will be described.

(Primary particle size measurement method)
The average primary particle diameter of the pigment was measured by a method of directly measuring the size of the primary particles from an electron micrograph of a transmission electron microscope (TEM). Specifically, the minor axis diameter and major axis diameter of the primary particles of each pigment were measured, and the average was taken as the particle diameter of the pigment particles. Next, for 100 or more pigment particles, the volume (weight) of each particle was obtained by approximating the obtained particle size cube, and the volume average particle size was defined as the average primary particle size.

(Preparation of green pigment 1)
200 parts of zinc halide phthalocyanine green pigment (CI Pigment Green 58), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, this kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of green pigment 1 were obtained. The primary particle diameter determined by TEM (transmission electron microscope) was 50 nm.

(Preparation of green pigment 2)
A green pigment 2 is obtained in the same manner as the preparation of the green pigment 1, except that the halogenated zinc phthalocyanine green pigment (CI Pigment Green 58) is replaced with a halogenated copper phthalocyanine green pigment (CI Pigment Green 7). It was. The primary particle diameter determined by TEM (transmission electron microscope) was 60 nm.

[Example 1] Preparation of green resist material 1 11.0 parts of green pigment 1 (CI pigment green 58), 2.5 parts of SOLPERSE-56000 solution prepared according to the method for preparing a solution of the above-mentioned commercially available resin type dispersant. Then, a mixture of 40.0 parts of the acrylic resin A solution and 46.5 parts of ethylene glycol monomethyl ether acetate was uniformly stirred and mixed, and then, using zirconia beads having a diameter of 0.5 mm, Eiger Mill (manufactured by Eiger Japan Co., Ltd.). (Mini model M-250 MKII)) for 5 hours, and then filtered through a 5.0 μm filter to prepare a green pigment dispersion.
Next, 60.0 parts of the green pigment dispersion, 11.0 parts of the solution of the acrylic resin A, 4.2 parts of trimethylolpropane triacrylate (“NK ester ATMPT” manufactured by Shin-Nakamura Chemical Co., Ltd.), a photopolymerization initiator ( Ciba Japan "Irgacure 907") 1.2 parts, sensitizer (Hodogaya Chemical "EAB-F") 0.4 parts, and a mixture of ethylene glycol monomethyl ether acetate 23.2 parts uniformly After stirring and mixing as described above, the mixture was filtered through a 1.0 μm filter to obtain an alkali developing type green resist material 1.

[Examples 2 to 24] Preparation of Green Resist Materials 2 to 24 Using the resin-type dispersant solution, the pigment derivative, and the acrylic resin solution shown in Table 3, the same method as that of Example 1 was used. Thus, alkali developing resist materials 2 to 24 were obtained. Table 4 shows the types of resin-type dispersants (either block type or non-block type).

[Example 25] Preparation of green resist material 25 10.0 parts of green pigment 1 (CI pigment green 58), 2.5 parts of SOLPERSE-56000 resin solution (non-volatile content 40 wt%), the following general formula ( 9):

で示される塩基性官能基を有する色素誘導体１．０部、上記アクリル樹脂Ａの溶液４０．０部、及びエチレングリコールモノメチルエーテルアセテート４６．５部の混合物を均一に撹拌混合した後、直径０．５ｍｍのジルコニアビーズを用いて、アイガーミル（アイガージャパン社製「ミニモデルＭ−２５０ ＭＫＩＩ」）で５時間分散した後、５．０μmのフィルタで濾過し緑色顔料分散体を作製した。

A mixture of 1.0 part of a pigment derivative having a basic functional group represented by formula (1), 40.0 parts of the above acrylic resin A solution, and 46.5 parts of ethylene glycol monomethyl ether acetate was uniformly stirred and mixed, and then a diameter of 0. Using 5 mm zirconia beads, the mixture was dispersed in an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 5 hours, and then filtered through a 5.0 μm filter to prepare a green pigment dispersion.

  Next, 60.0 parts of the green pigment dispersion, 11.0 parts of the solution of the acrylic resin A, 4.2 parts of trimethylolpropane triacrylate (“NK ester ATMPT” manufactured by Shin-Nakamura Chemical Co., Ltd.), a photopolymerization initiator ( Ciba Japan "Irgacure 907") 1.2 parts, sensitizer (Hodogaya Chemical "EAB-F") 0.4 parts, and a mixture of ethylene glycol monomethyl ether acetate 23.2 parts uniformly After stirring and mixing as described above, the mixture was filtered through a 1.0 μm filter to obtain an alkali developing type green resist material 25.

[Examples 26 to 48] Preparation of green resist materials 26 to 48 Using the solution of the resin-type dispersant, the dye derivative, and the solution of the acrylic resin shown in Table 5, the method shown in Example 25 and Similarly, alkali developing resist materials 26 to 48 were obtained.

[Example 49] Preparation of green resist material 49 10.0 parts of green pigment 1 (CI pigment green 58), 2.5 parts of SOLPERSE-56000 solution (non-volatile content 40 wt%), the following general formula (10) :

で示される、アンカー部がベンズイミダゾロンである塩基性官能基を有するトリアジン環骨格を持った色素誘導体１．０部、上記アクリル樹脂Ａの溶液４０．０部、及びエチレングリコールモノメチルエーテルアセテート４６．５部の混合物を均一に撹拌混合した後、直径０．５ｍｍのジルコニアビーズを用いて、アイガーミル（アイガージャパン社製「ミニモデルＭ−２５０ ＭＫＩＩ」）で５時間分散した後、５．０μmのフィルタで濾過し緑色顔料分散体を作製した。

1.0 part of a pigment derivative having a triazine ring skeleton having a basic functional group whose anchor part is benzimidazolone, 40.0 parts of the solution of the acrylic resin A, and ethylene glycol monomethyl ether acetate 46. After 5 parts of the mixture was stirred and mixed uniformly, the mixture was dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then a 5.0 μm filter. To give a green pigment dispersion.

  Next, 60.0 parts of the green pigment dispersion, 11.0 parts of the solution of the acrylic resin A, 4.2 parts of trimethylolpropane triacrylate (“NK ester ATMPT” manufactured by Shin-Nakamura Chemical Co., Ltd.), a photopolymerization initiator ( Ciba Japan "Irgacure 907") 1.2 parts, sensitizer (Hodogaya Chemical "EAB-F") 0.4 parts, and a mixture of ethylene glycol monomethyl ether acetate 23.2 parts uniformly After stirring and mixing as described above, the mixture was filtered through a 1.0 μm filter to obtain an alkali developing type green resist material 49.

[Examples 50 to 72] Preparation of green resist materials 50 to 72 The method shown in Example 49 using the solution of the resin-type dispersant, the dye derivative, and the solution of the acrylic resin shown in Table 6 Similarly, alkali developing resist materials 50 to 72 were obtained.

[Comparative Examples 1 to 15] Preparation of green resist materials 73 to 87 Instead of the solution of SOLPERSE-56000 used in Example 1, a solution of the dispersant shown in Table 7 (nonvolatile content: 40% by weight) was used. Were obtained in the same manner as in Example 1 to obtain alkali developing resist materials 73 to 87.

[Comparative Example 16] Preparation of green resist material 88 As in Example 3, except that green pigment 2 (CI pigment green 36) was used instead of green pigment 1 (CI pigment green 58). Thus, an alkali developing resist material 88 was obtained.

(Evaluation methods)
Using the obtained alkali developing resist materials 1 to 88, in order to evaluate fluidity, viscosity characteristics, in order to evaluate brightness and contrast ratio (CR), brightness and contrast ratio, In order to evaluate the stability, the rate of change in contrast ratio with time and the rate of increase in viscosity with time were measured by the following methods.

(Measurement method of viscosity characteristics)
The viscosity of the obtained alkali developing resist material was measured at a rotation speed of 20 rpm using an E type viscometer (“ELD type viscometer” manufactured by Toki Sangyo Co., Ltd.). Furthermore, the ratio of the viscosity at the number of revolutions of 6 rpm and 60 rpm (referred to as thixo index, the larger the value, the higher the thixotropic property) was obtained, and the thixotropic property was evaluated.

(Measurement method of viscosity increase rate with time)
Using an E-type viscometer (“ELD type viscometer” manufactured by Toki Sangyo Co., Ltd.), the initial viscosity of the next day after the alkali-developable resist material was prepared and the time-lapse viscosity accelerated at 40 ° C. for 1 week. The measurement was performed at 25 ° C. under the condition of a rotation speed of 20 rpm. The initial viscosity thus measured and the viscosity with time were applied to the following equation, and the rate of increase in viscosity with time was measured.

  [Rate of increase in viscosity with time] = (Viscosity with time / initial viscosity) × 100

(Brightness measurement method)
The obtained alkali development type resist material was applied with a spin coater at three points so that the chromaticity y in the CIE color system was 0.62, 0.6, 0.58 by changing the rotation speed. A substrate was produced. After coating, the film was dried in a hot air oven at 80 ° C. for 30 minutes, and each film thickness was measured. The brightness at a chromaticity y of 0.6 was determined from the three points of data by the first-order correlation method. The chromaticity was measured using a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.).

(Measurement method of contrast ratio of coating film)
The contrast ratio at a chromaticity y of 0.6 was determined from the three-point data by the primary correlation method using the substrate used for the brightness measurement. The chromaticity was measured using a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.).

An apparatus for measuring the contrast ratio of the coating film and a method for calculating the value will be described with reference to FIG.
The light emitted from the backlight unit for liquid crystal display (7) passes through the polarizing plate (6), is polarized, and passes through the dried coating film (4) of the colored composition applied on the glass substrate (5). And reaches the polarizing plate (3). If the polarization planes of the polarizing plate (6) and the polarizing plate (3) are parallel, light is transmitted through the polarizing plate (3), but if the polarization plane is perpendicular, the light is transmitted by the polarizing plate (3). Blocked. However, when light polarized by the polarizing plate (6) passes through the dried coating film (4) of the colored composition, scattering by pigment particles or the like occurs, and a part of the polarization plane is displaced. Is parallel, the amount of light transmitted through the polarizing plate (3) is reduced, and when the polarizing plate is orthogonal, a part of the light is transmitted through the polarizing plate (3). This transmitted light was measured as the luminance on the polarizing plate, and the ratio (contrast ratio) between the luminance when the polarizing plate was parallel and the luminance when it was orthogonal was calculated.

  (Contrast ratio) = (Luminance when parallel) / (Luminance when direct)

  Accordingly, when scattering occurs due to the pigment of the dried coating film (4) of the coloring composition, the brightness when parallel is reduced and the brightness when perpendicular is increased, the contrast ratio is lowered.

  A color luminance meter (“BM-5A” manufactured by Topcon Corporation) was used as the luminance meter (1), and a polarizing plate (“NPF-G1220DUN” manufactured by Nitto Denko Corporation) was used as the polarizing plate. In the measurement, a black mask (2) having a 1 cm square hole was applied to the measurement portion in order to block unnecessary light.

(Measurement method of contrast ratio over time)
The obtained alkali developing resist material was allowed to stand at 40 ° C. for 7 days, and the rate of change in CR after standing for 7 days with respect to the initial CR was determined. (See the formula below)
Rate of CR change over time = (CR after standing for 7 days over time) / (initial CR)

  If the change rate of the contrast ratio with time is 90% or more, it can withstand a practical level. Preferably, it is 95% or more. If it exceeds this range, the storage stability is inferior and the green colored composition for a color filter is not established.

(Maximum transmittance measurement method)
The maximum transmittance was measured using the coated substrate used for the brightness measurement. After measuring the chromaticity using a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.), the maximum transmittance at a chromaticity y of 0.6 was determined by the primary correlation method.

  Next, a method for measuring and preparing a dispersed particle size of the green resist materials obtained in Examples 1 to 72 and Comparative Examples 1 to 16 will be described.

(Dispersed particle size measurement)
The same result may not be obtained even if the same particle size is measured depending on the measurement principle, equipment, sample preparation method, parameter setting, etc., but in the present invention, the dynamic light scattering method (FFT power The spectrum method is used for measurement.

  Using Nikkiso Microtrac UPA-EX150 employing dynamic light scattering (FFT power spectrum method), the particle permeability was absorption mode, the particle shape was non-spherical, and D50 was the average diameter. The diluent solvent for measurement was the same as that used for the dispersion, and the sample treated with ultrasonic waves was measured immediately after preparation.

(Particle size by SEM)
The particle diameter of the pigment by SEM was measured by a method of directly measuring the maximum particle size from an electron micrograph of a scanning electron microscope (SEM). Specifically, 50 pigment particles are photographed, the short axis diameter and the major axis diameter of the primary particle of each pigment are measured, the average is the particle diameter of the pigment particle, and the maximum is the one Expressed with one significant digit after the decimal point.

  The resist obtained as described above has a thixo index, viscosity, rate of increase in viscosity over time, contrast ratio (CR), rate of change in contrast ratio (CR) over time, brightness, maximum transmittance, dispersed particle size, and SEM. The results of the dispersed particle size are shown in Tables 8 to 11.

ＣＲ：コントラスト比

CR: Contrast ratio

ＣＲ：コントラスト比

CR: Contrast ratio

ＣＲ：コントラスト比

CR: Contrast ratio

ＣＲ：コントラスト比

CR: Contrast ratio

  As in Examples 1 to 72 (green resist materials 1 to 72), when a basic resin type dispersant having an amine value of 35 to 100 mgKOH / g is used, the fluidity is good and the storage stability with time is excellent. A green coloring composition that achieves high brightness, high contrast ratio, and high transmittance can be obtained.

  When the resin type dispersant is a block copolymer resin composed of the basic copolymer block (A) and the pigment carrier affinity copolymer block (B), the contrast ratio is further increased.

  Furthermore, when a pigment derivative having a basic functional group is used in combination with the resin-type dispersant, the initial contrast ratio is increased, and the viscosity characteristics and stability over time are generally improved. In addition, when X is the acid value and Y is the average molecular weight, (a) Y> −750X + 51000, (A) Y> 940X−79000, and (C) Y> 8000 simultaneously satisfy all the conditions. When the resin constituting the carrier is used, the best green coloring composition can be obtained.

  On the other hand, Comparative Examples 1 to 15 (green resist materials 73 to 88) are green colored compositions having both poor fluidity and storage stability and low contrast ratio and transmittance. Moreover, in the comparative example 16, since the halogenated copper phthalocyanine green is used, it becomes a green coloring composition with inferior brightness.

It is a conceptual diagram of the measuring apparatus for measuring a contrast ratio.

Explanation of symbols

(1) Luminance meter (2) Mask (3) Polarizing plate (4) Colored composition dry coating film (5) Glass substrate (6) Polarizing plate (7) Backlight unit

Claims (8)

  A green pigment component containing at least a zinc halide phthalocyanine pigment, a basic resin type dispersant having an amine value of 35 to 100 mgKOH / g, and a pigment carrier comprising a resin, a precursor thereof, or a mixture thereof. A green coloring composition for a color filter.   The green coloring composition for a color filter according to claim 1, wherein the content of the basic resin dispersant is 0.001 to 50% by weight based on the total weight of the green pigment component.   The color according to claim 1 or 2, wherein the basic resin type dispersant is a block copolymer resin comprising a basic copolymer block (A) and a pigment carrier affinity copolymer block (B). Green coloring composition for filters.   The green colored composition for a color filter according to claim 3, wherein the block copolymer resin is a block copolymer resin obtained by living radical polymerization.   Furthermore, the green coloring composition for color filters in any one of Claims 1-4 formed by containing the pigment derivative which has a basic substituent.   The green coloring composition for a color filter according to claim 5, wherein the content of the dye derivative having a basic substituent is 0.001 to 40% by weight based on the total weight of the green pigment component. When the resin constituting the pigment carrier has an acid value of X (mg KOH / g) and a weight average molecular weight of Y, all of the following formulas (a), (b), and (c) are satisfied simultaneously. The green coloring composition for color filters according to any one of claims 1 to 6, which is a resin.
(A) Y> −750X + 51000
(A) Y> 940X-79000
(U) Y> 8000   A color filter comprising a green filter segment formed from the green coloring composition for a color filter according to claim 1.

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