CN103529646A - Green colored composition for color filter, and color filter - Google Patents

Abstract

This invention relates to the green coloring composition for color filters, and a color filter. Disclosed is a green coloring composition for color filters, comprising (A) a pigment component comprising at least a zinc halide phthalocyanine pigment, and (B) a pigment carrier comprising a resin, a precursor thereof, or a mixture thereof, and further comprising (a) ) at least one of a basic resin type dispersant having an amine value of 35 to 100 mg KOH/g, (b) a pigment derivative having a basic substituent, and (c) a mixed organic solvent containing a solubility Parameter (SP value) is 8.0～10.0(cal/cm ³ ) ^1/2 , the boiling point under 760mmHg is the organic solvent (c1) of 140～159 ℃; And solubility parameter (SP value) is 8.0～10.0(cal/cm 3 ) 1/2 cm ³ ) ^1/2 , an organic solvent (c2) having a boiling point of 160 to 200°C at 760 mmHg.

Description

Green coloring composition for color filter and color filter

This application is a divisional application of an application with a filing date of November 24, 2008, an application number of 200810182161.1, and an invention title of "Green Coloring Composition for Color Filter and Color Filter".

technical field

The present invention relates to a green coloring composition for color filters used in the production of color filters used in color liquid crystal display devices, color pickup tube elements, and the like, and to color filters formed using the same.

Background technique

A liquid crystal display device is a display device that displays by controlling the degree of polarization of light passing through the first polarizing plate and controlling the amount of light passing through the second polarizing plate through a liquid crystal layer sandwiched between two polarizing plates. A type of nematic (TN) type liquid crystal is becoming a mainstream type. Liquid crystal display devices can perform color display by placing a color filter between two polarizing plates. In recent years, since color filters have begun to be used in TVs and personal computer monitors, etc., their high contrast ratio and high brightness requirements have increased.

The color filter includes a color filter in which two or more kinds of fine band (stripe) color filter segments (Filtase gment) of different hues are arranged in parallel or cross on the surface of a transparent substrate such as glass, or a fine filter The color filter section is a color filter configured in a certain vertical and horizontal arrangement. The color filter segments are neatly arranged in a fine arrangement of several micrometers to hundreds of micrometers 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 the color filter by vapor deposition or sputtering, and an alignment film for aligning the liquid crystal in a certain direction is formed thereon. In order to sufficiently obtain the performance of these transparent electrodes and alignment films, they need to be formed at a high temperature of generally 200°C or higher, preferably 230°C or higher. Therefore, currently, a method called a pigment dispersion method in which a pigment excellent in light resistance and heat resistance is used as a colorant has become a mainstream method as a production method of a color filter.

However, in general, color filters in which pigments are dispersed have a problem in that the degree of polarization controlled by liquid crystals is disturbed due to light scattering or the like caused by the pigments. That is, when it is necessary to shield light (OFF state), light leaks, and when it is necessary to transmit light (ON state), the transmitted light attenuates, so the ratio (contrast ratio) of brightness on the display device in the ON state and the OFF state is low. question.

In order to realize higher brightness and higher contrast ratio of color filters, pigments contained in color filter segments have been miniaturized until now. However, even if the pigment (the particles prepared by a chemical reaction with a particle size of 10 to 100 μm, which is called a crude product (Krud)) is treated by pigmentation until it becomes a mixture of primary particles and secondary particles formed by agglomeration Pigments) are miniaturized by various miniaturization methods. Pigments that have undergone miniaturization of primary particles or secondary particles are generally easy to agglomerate, and when they are too miniaturized, huge lumps of pigment solids are formed. Furthermore, even if the finely divided pigment is dispersed in a pigment carrier containing a resin or the like, and the secondary particle of the pigment is brought as close as possible to the primary particle to stabilize it, a stable coloring composition can be obtained. It is also very difficult.

A coloring composition obtained by dispersing a finely divided pigment in a pigment carrier tends to cause aggregation of pigment particles over time, resulting in high viscosity and thixotropy. The increased viscosity and poor fluidity of such a coloring composition cause problems in production operations or cause various problems in product value. For example, the color filter segments of a color filter are generally formed by spin-coating a coloring composition, which disperses a pigment in a pigment carrier containing a monomer and a resin, on a glass substrate, and if a high-viscosity, A coloring composition with poor fluidity is not preferable because a coating film with uniform film thickness cannot be obtained due to poor spin coatability, poor leveling, and the like.

The color filter is produced by applying and drying the coloring composition for color filter (hereinafter also referred to as coating liquid) on a transparent substrate to form a coating film having a thickness of about 0.2 to 5 μm. The coating method includes a spin coating method, a die coating method, etc., and can be used appropriately according to the characteristics.

The spin coating method is widely used to form a thin film on a small substrate. In this coating method, while rotating the transparent substrate at a certain number of rotations, the coating liquid is dripped at the center of the transparent substrate, and the coating liquid is dispersed by centrifugal force. Spread thinly, and form a coating film with a desired film thickness on the surface of the transparent substrate by controlling the number of rotations or the rotation time of the transparent substrate suitable for the coating liquid. However, due to the principle that the coating film is spread thinly by the centrifugal force caused by the rotation, there is a disadvantage that the coating film thickness of the rotation center part and the peripheral part of the transparent substrate is too thick compared with the middle part. Patent Document 1 describes a coating liquid for a spin coating method that is excellent in surface smoothness of a coating film made of a composition containing 50% by weight or more of a solvent having a boiling point or a vapor pressure within a specific range.

When the size of the substrate is large, a method of rotating the substrate, such as the spin coating method, imposes a large load on the apparatus, so the die coating method is used. The die coating method is a coating method in which a coating liquid is discharged from a slit, and a coating film having a desired film thickness is formed on the surface of a transparent substrate on the substrate while moving the slit. However, this structure tends to generate stripe-like irregularities perpendicular to the direction of advance of the slit, and at the opening of the slit, the coating liquid is exposed to the atmosphere to dry and solidify, thereby generating aggregates. , strip-shaped unevenness in the coating advance direction occurs, and the aggregates are mixed into the coating, forming coating film defects. Furthermore, there is a problem that the outer peripheral portion of the coating film is raised, and the coating film becomes thicker than the center portion of the substrate.

In order to solve such a problem of coating film unevenness in the die coating method, attempts are made as described in the following patent documents.

Patent Documents 2 and 3 disclose a method in which a coating liquid is prevented from drying and solidifying without generating aggregates by containing a high-boiling-point solvent.

[Patent Document 1] JP-A-6-3521

[Patent Document 2] JP-A-2003-55566

[Patent Document 3] JP-A-2004-346218

On the other hand, for the above-mentioned color filters, not only a high contrast ratio but also high brightness are required. Generally, in order to obtain high brightness, when the pigment is dispersed in the pigment carrier, make it close to the primary particle, improve the transparency of the dispersion, and make the dispersion have high transmittance in the spectral spectrum, thereby obtaining high brightness .

However, green as one of the three primary colors (red, blue, green; RGB) of the color filter substrate generally uses a copper halide phthalocyanine pigment (for example, C.I. Pigment Green 36 or C.I. Pigment Green 7) as a main pigment, but As long as copper halide phthalocyanine is used, it is difficult to achieve both high contrast ratio and high brightness.

In order to solve these problems, zinc halide phthalocyanine pigments in which the central metal is replaced by zinc from existing copper halide phthalocyanine pigments have been used as high tinting strength pigments that can exhibit bright hues and a wide range of color display areas. color materials.

[Patent Document 4] Japanese Unexamined Patent Publication No. 10-130547

[Patent Document 5] JP-A-2001-141922

[Patent Document 6] JP-A-2007-204658

However, zinc halide phthalocyanine green pigments have higher acidity than copper halide phthalocyanine green pigments. Therefore, zinc halide phthalocyanine green pigments are more difficult to disperse than copper halide phthalocyanine green pigments. A poorly dispersed coloring composition tends to cause aggregation of pigment particles over time, resulting in high viscosity and thixotropy. The increased viscosity and poor fluidity of such a coloring composition cause problems in production operations or cause various problems in product value. For example, the color filter segments of a color filter are generally formed by spin-coating a coloring composition on a glass substrate, the coloring composition dispersing a pigment in a pigment carrier containing a monomer and a resin, and if a high-viscosity, flowable A coloring composition with poor performance is not preferable because a coating film with a uniform film thickness cannot be obtained due to poor spin coating properties, poor leveling, and the like.

In addition, zinc halide phthalocyanine pigments are known to be chemically different from conventional copper halide phthalocyanine pigments and difficult to disperse. Therefore, it is difficult to stably disperse the zinc halide phthalocyanine pigment while maintaining its excellent color characteristics using only a dispersant suitable for the existing copper halide phthalocyanine pigment or other pigments.

On the other hand, in order to obtain a high-fluidity zinc halide phthalocyanine pigment dispersion, it is necessary to use a large amount of dispersant that will have a bad influence on each resistance. In order to maintain a high pigment concentration, it is necessary to reduce the amount of pigment that maintains each resistance. As a result, it is difficult to balance the properties of resistance, fluidity and color.

Furthermore, the zinc halide phthalocyanine pigment is different from the existing copper halide phthalocyanine pigment in that the solubility of the pigment itself is different, so for the most suitable solvent for dispersing the copper halide phthalocyanine pigment, the affinity of the zinc halide phthalocyanine pigment with it is too high. Well, when these solvents are used to disperse zinc phthalocyanine pigments, the pigment itself dissolves in the solvent, and there is a problem that a dispersion having a high contrast ratio and high brightness cannot be obtained.

Furthermore, for the coloring compositions (Patent Documents 1 to 3) using a zinc halide phthalocyanine pigment dispersed in a solvent used for dispersing a copper halide phthalocyanine pigment, due to the above-mentioned spin coating method or die coating Due to such a coating method and the properties of the coating liquid used therein, there are disadvantages of uneven film thickness or uneven stripes.

Here, the film thickness unevenness means that the uniformity of the film thickness is insufficient, and can be divided into "uniformity of film thickness (end part)", that is, film thickness uniformity of the end part and "uniformity of film thickness (other than the end part)". , That is, the two types of uniformity from the center of the substrate to the end surface. In addition, streak unevenness can be divided into two types: "horizontal streak unevenness", that is, streak-like unevenness that occurs in the direction perpendicular to the advancing direction of the slit in the die coating method, and "horizontal streak unevenness" "Longitudinal streak unevenness" refers to strip-like unevenness in the direction of slit advance caused by aggregates at the opening of the slit in the die coating system.

Contents of the invention

Therefore, an object of the present invention is to provide a stable green coloring composition for color filters excellent in fluidity and various resistances, and a color filter using the same with high brightness and contrast ratio.

In addition, the object of the present invention is to provide a green coloring composition for color filters (green resist material), and a color filter having color filter segments formed using the same, the green coloring composition for color filters can reduce the A color filter with high brightness and high contrast ratio can be formed by taking advantage of the shortcomings observed in the coating film of the coated product formed by the spin coating method and the die coating method.

The above-mentioned problems can be solved by a green coloring composition for color filters containing:

(A) a pigment component containing at least a zinc halide phthalocyanine pigment, and

(B) a pigment vehicle comprising a resin, a precursor thereof, or a mixture thereof, and

Contains selected from:

(a) Basic resin type dispersant with an amine value of 35-100 mg KOH/g,

(b) pigment derivatives having basic substituents, and

(c) It is obtained by mixing at least one kind of organic solvent, and the mixed organic solvent contains a solubility parameter (SP value) of 8.0 to 10.0 (cal/cm ³ ) ^1/2 and a boiling point at 760 mmHg of 140 to 159°C an organic solvent (c1); and an organic solvent (c2) having a solubility parameter (SP value) of 8.0 to 10.0 (cal/cm ³ ) ^1/2 and a boiling point of 160 to 200°C at 760 mmHg.

In a preferred version of the green coloring composition for color filters of the present invention, when the acid value is denoted as X (mg KOH/g) and the weight average molecular weight is denoted as Y, the resins constituting the above-mentioned pigment carrier (B) are simultaneously all Resins satisfying the conditions of the following formulas (F), (G) and (H):

(F)Y＞-750X+51000

(G)Y＞940X-79000

(H)Y>8000.

In a preferred aspect of the green coloring composition for color filters of the present invention, based on the total weight of the above-mentioned pigment component (A) containing a zinc halide phthalocyanine pigment [hereinafter referred to simply as pigment component (A)] , The content of the above-mentioned basic resin type dispersant (a) is 0.001 to 50% by weight.

In a preferred aspect of the green coloring composition for color filters of the present invention, the above-mentioned basic resin type dispersant (a) is composed of a basic copolymer block (a1) and a pigment carrier affinity copolymer block (a2) Block copolymer resins, such as block copolymer resins obtained by living polymerization.

In a preferred aspect of the green coloring composition for color filters of the present invention, the content of the pigment derivative (b) is 0.001 to 40% by weight based on the total weight of the pigment component (A).

In a preferred version of the green coloring composition for color filter of the present invention, the above-mentioned organic solvent (c1) is selected from propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether Acetate and at least one or more solvents of ethylene glycol monoethyl ether acetate.

In a preferred version of the green coloring composition for color filters of the present invention, the above-mentioned organic solvent (c2) is selected from cyclohexyl acetate, propylene glycol diacetate, diethylene glycol diethyl ether, and 3-ethoxy At least one or more solvents of ethyl propionate.

In a preferred embodiment of the green coloring composition for color filter of the present invention, based on the total amount of the above-mentioned mixed organic solvent (c), the above-mentioned organic solvent (c1) is 50% by weight to 95% by weight, and the above-mentioned organic solvent ( c2) is 5% by weight to 50% by weight.

In a preferable aspect of the green coloring composition for color filters of this invention, a photoinitiator is contained further.

In a preferable aspect of the green coloring composition for color filters of the present invention, the above-mentioned basic resin type dispersant (a) and the above-mentioned dye derivative (b) are contained.

In a preferable aspect of the green coloring composition for color filters of this invention, the said basic resin type dispersant (a) and the said mixed organic solvent (c) are contained.

In a preferred aspect of the green coloring composition for color filters of the present invention, the above-mentioned dye derivative (b) and the above-mentioned mixed organic solvent (c) are contained.

In a preferred aspect of the green coloring composition for color filters of the present invention, the above-mentioned basic resin type dispersant (a), the above-mentioned dye derivative (b) and the above-mentioned mixed organic solvent (c) are contained.

Moreover, this invention relates to the color filter which has the green color filter segment (green filter segment) formed from the said green coloring composition for color filters, It is characterized by the above-mentioned.

The green coloring composition for color filters of the present invention contains (A) a pigment component containing at least a zinc halide phthalocyanine pigment; and (B) a pigment carrier containing a resin, a precursor thereof, or a mixture thereof, and further contains a base selected from At least one of the permanent resin type dispersant (a), the above-mentioned pigment derivative (b), and the above-mentioned mixed organic solvent (c) can form a highly fluid and stable pigment dispersion. By using this composition, it is possible to form Color filter with high brightness and high contrast ratio. In addition, it is possible to form a color filter having reduced conventional defects observed in a coating film of a coating material and having a high contrast ratio and brightness.

In particular, when the above-mentioned basic resin type dispersant (a) is a block copolymer resin comprising a basic copolymer block (a1) and a pigment carrier affinity copolymer block (a2), it becomes possible to form Pigment dispersion for color filters with high contrast ratio.

Furthermore, when the above-mentioned basic resin type dispersant (a) and the dye derivative (b) having a basic substituent are contained, the initial contrast ratio becomes high and the temporal stability is also good.

Description of drawings

[ Fig. 1 ] A schematic explanatory diagram of a measuring device for measuring a contrast ratio.

Symbol Description

(1) Brightness meter

(2) mask

(3) polarizer

(4) Dried coating film of coloring composition

(5) Glass substrate

(6) polarizer

(7) Backlight unit

Detailed ways

First, the green coloring composition for color filters of this invention is demonstrated in detail by citing preferable embodiment.

In addition, in the description, when expressed as "(meth)acryloyl ((Meta) Acryl)", "(meth)acryl ((Meta) Acryl)", "(meth)acryl", "(meth) "Acrylic acid ester" and "(meth)acryloyloxy" means "acryloyl and/or methacryloyl", "acryloyl and/or methacryloyl", respectively, unless otherwise specified ”, “acrylic and/or methacrylic”, “acrylate and/or methacrylate”, and “acryloxy and/or methacryloxy”.

The green coloring composition for color filters of the present invention comprises (A) a pigment component comprising at least a zinc halide phthalocyanine pigment; and (B) a pigment carrier comprising a resin, a precursor thereof, or a mixture thereof, and in the first embodiment, It further contains (a) a basic resin type dispersant with an amine value of 35-100 mg KOH/g;

In the second embodiment, the above-mentioned basic resin type dispersant (a) and/or (b) contains a pigment derivative having a basic substituent;

In the third embodiment, the above-mentioned basic resin type dispersant (a) and/or the above-mentioned pigment derivative (b) and/or (c) contain a solubility parameter (SP value) of 8.0 to 10.0 (cal/cm ³ ) An organic solvent ^{(c1) with a boiling point of 140-159°C at 1/2 , 760mmHg} ; A mixed organic solvent of an organic solvent (c2) at ~200°C.

That is, any two or all three of the above-mentioned basic resin-type dispersant (a), the above-mentioned dye derivative (b) and the above-mentioned mixed organic solvent (c) may be contained together.

[Pigment component (A)]

The green coloring composition for color filters of this invention uses the pigment component (A) containing at least a zinc halide phthalocyanine pigment as a main pigment, It is characterized by the above-mentioned.

When typical zinc halide phthalocyanine pigments are represented by a color index (C.I) number, C.I. Pigment Green 58 and the like can be cited. By using a zinc halide phthalocyanine pigment as the main pigment, high brightness that cannot be obtained with other green pigments can be obtained. Furthermore, pigments obtained by known production methods can be used. In particular, the following pigments can be used, that is, when using the method described in Coloring Materials, 67 [9], 547-554 (1994), and using n-hexylamine as a basic substance for measurement, the pigment surface The amount of acidic functional groups is preferably 100 μmol/g or more, more preferably 200 μmol/g or more.

In the pigment component (A), not only zinc halide phthalocyanine as a main pigment is contained, but other green pigments or yellow pigments may be used in combination for the purpose of color adjustment or color compensation.

Other green pigments that can be used in combination include green pigments such as C.I. Pigment Green 7, 10, 36, and 37. In addition, examples of yellow pigments that can be used in combination include C.I. 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, Yellow pigments of 180, 181, 182, 185, 187, 188, 193, 194, 198, 199, 213, 214, etc.

Among them, it is preferable to use C.I. Pigment Yellow 138, 139, 150, 185, etc. in combination because the chromaticity region can be expanded.

From the viewpoint of obtaining sufficient color reproducibility in the total non-volatile components of the coloring composition of the present invention, the concentration of the pigment component (A) is preferably 10 to 90% by weight, more preferably 15 to 80% by weight, Most preferably 20 to 70% by weight. When the concentration of the pigment component (A) 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 becomes low and the stability of the coloring composition deteriorates.

As a particularly preferable ratio of the pigment, for example, based on the total weight of the pigment component (A), the zinc halide phthalocyanine pigment is 50 to 100% by weight, the copper halide phthalocyanine pigment is 0 to 50% by weight, and the yellow pigment is 0% by weight. ~50% by weight.

More preferably, based on the pigment component (A), the zinc halide phthalocyanine pigment is 50 to 90% by weight, the copper halide phthalocyanine pigment is 5 to 45% by weight, and the yellow pigment is 5 to 45% by weight. Utilizing the composition ratio of such pigments, the chroma area can be expanded.

For the green coloring composition of the present invention using a zinc halide phthalocyanine pigment, when it is coated on a glass substrate or the like, to form the same chromaticity as a green coloring composition using a copper halide phthalocyanine, and measure The transmittance of the coating film shows higher transmittance than the coating film of the coloring composition using copper phthalocyanine from around 450 nm to around 530 nm. In particular, the peak value of the transmittance shows a high transmittance of about 50%, and a value of about 90%. Therefore, by combining with a backlight commonly used in color liquid crystal display devices, high brightness that cannot be obtained with a coloring composition using a copper phthalocyanine pigment such as C.I. Pigment Green 36 or C.I. Pigment Green 7 can be obtained.

[Minification of Pigment]

The pigment used in the green coloring composition of the present invention can be used in a miniaturized form by subjecting it to a salt grinding treatment, and it is preferable to use a miniaturized pigment.

Salt milling means heating a mixture of pigments, water-soluble inorganic salts, and water-soluble organic solvents using a kneader such as a kneader, two-roll mill, three-roll mill, ball mill, attritor mill, or sand mill. After performing mechanical kneading, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing. Water-soluble inorganic salts function as crushing aids, and the high hardness of inorganic salts is used to crush pigments during salt grinding, thereby generating active surfaces and growing crystals. Therefore, the crushing of the pigment and the crystal growth proceed simultaneously during kneading, and the primary particle size of the obtained pigment 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 lower than 40° C., crystal growth cannot sufficiently occur, and the shape of the pigment particles is close to an amorphous shape, which is not preferable. On the other hand, when the heating temperature exceeds 150° C., crystal growth proceeds too much and the primary particle diameter of the pigment becomes large, so it is not preferable as a coloring raw material of the coloring composition for color filters. In addition, the kneading time of the salt grinding treatment is preferably 2 to 24 hours from the viewpoint of the balance between the particle size distribution of the primary particle of the salt grinding treatment pigment and the cost required for the salt grinding treatment.

By optimizing the conditions for salt milling the pigment, it is possible to obtain a pigment having a very fine primary particle size, a narrow distribution range, and a narrow particle size distribution.

The primary particle size of the green pigment used in the green coloring composition of the present invention as measured by TEM (transmission electron microscope) is preferably in the range of 20 to 100 nm. When it is smaller than 20 nm, dispersion in an organic solvent becomes difficult. Also, when it is larger than 100 nm, a sufficient contrast ratio cannot be obtained. A particularly preferable range is the range of 25 to 85 nm.

As the water-soluble inorganic salt used in the salt grinding treatment, sodium chloride, barium chloride, potassium chloride, or sodium sulfate can be used, and sodium chloride (salt) is preferably used from the viewpoint of price. From the viewpoints of processing efficiency and production efficiency, the amount of the water-soluble inorganic salt is preferably 50-2000% by weight, most preferably 300-1000% by weight, based on the total weight of the pigment component (A).

The water-soluble organic solvent has the function of wetting the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (mixes) in water and hardly dissolves the inorganic salt used. However, since the temperature rises during salt grinding, the solvent tends to evaporate, so from the viewpoint of safety, a high boiling point solvent having a boiling point of 120° C. or higher is preferable. For example, 2-methoxyethanol, 2-butoxyethanol, 2-(isoamyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol Alcohol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol alcohol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, or liquid polypropylene glycol, etc. The water-soluble organic solvent is preferably used in an amount of 5 to 1000% by weight, most preferably in an amount of 50 to 500% by weight, based on the total weight of the pigment component (A).

When performing the salt grinding treatment, a resin may be added as necessary. The type of resin to be used is not particularly limited, and natural resins, modified natural resins, synthetic resins, or synthetic resins modified from natural resins can be used. The resin used is solid at room temperature, preferably it is water-insoluble, and further preferably partially soluble in the above-mentioned organic solvent. The amount of resin used is preferably in the range of 5 to 200% by weight based on the total weight of the pigment component (A).

[Pigment Carrier (B)]

In addition to the pigment component (A), the green coloring composition of this invention contains the pigment carrier (B) containing resin, its precursor, or their mixture.

The pigment carrier (B) used in the green coloring composition of the present invention is a resin whose spectral transmittance is preferably 80% or more, more preferably 95% or more, and its precursor in the entire wavelength region of 400 to 700 nm in the visible light region. or a mixture of them. The resin contains a thermoplastic resin, a thermosetting resin, or an active energy ray-curable resin, and its precursor includes monomers or oligomers that are cured by irradiation with active energy rays to form a transparent resin. These can be used alone or in combination of two or more to use. The pigment carrier (B) can be used in an amount of 30 to 500% by weight based on the total weight of the pigment component (A). When it is less than 30% by weight, the film-forming properties and various resistances are insufficient, and when it is more than 500% by weight, the pigment concentration is low, and color characteristics cannot be expressed.

When the acid value is denoted as X (mg KOH/g) and the weight average molecular weight is denoted as Y, it is preferable that the resin constituting the above-mentioned pigment carrier (B) satisfies the following formulas (F), (G) and (H) at the same time Conditioned Resin:

(F)Y＞-750X+51000

(G)Y＞940X-79000

(H)Y>8000.

When the resin constituting the above-mentioned pigment carrier (B) satisfies all the conditions of the above formulas (F), (G) and (H), since it has a good acid value range, the resin-type dispersant adsorbed on the pigment and the above-mentioned resin Appropriate interaction can be maintained, and because of a good molecular weight range, it can moderately function as a steric barrier of the carrier resin and can maintain a good dispersion state, so it is preferable. In particular, the basic resin-type dispersant (a) used in the first embodiment of the present invention described below and/or the pigment derivative (b) used in the second embodiment of the present invention described below can be favorably adsorbed on the paint surface. On the contrary, when the resin constituting the above-mentioned pigment carrier (B) does not satisfy the condition of the above formula (F), the interaction between the above-mentioned basic resin type dispersant (a) adsorbed on the surface of the pigment and the above-mentioned resin is too weak, so due to Pigment aggregation and other reasons cannot maintain a good dispersion state. When the condition of the above formula (G) is not satisfied, the above-mentioned interaction is too strong, so the resin-type dispersant adsorbed on the pigment is peeled off, and a good dispersion state cannot be maintained due to pigment aggregation or the like. In addition, when the condition of the above formula (H) is not satisfied, since the molecular weight is too small, the above-mentioned resin cannot function as a steric hindrance, resulting in poor dispersion due to pigment aggregation or the like. In addition, Y≦60000 is preferable, and Y≦50000 is more preferable. When Y exceeds 60000, since developability may become poor when used as an alkali-developing type coloring resist mentioned later, it is unpreferable.

Examples of thermoplastic resins include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane-based Resin, polyester resin, acrylic resin, alkyd resin, polystyrene resin, polyamide resin, rubber resin, cyclized rubber resin, cellulose, polyethylene (HDPE, LDPE), polybutadiene, polyimide resin, etc.

Moreover, examples of thermosetting resins include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenolic resins.

When used as an alkali-developing type colored resist described below, it is preferable to use an alkali-soluble resin having an acidic group such as a (meth)acrylic copolymer resin (alkali-soluble acrylic resin). In order to well disperse the zinc halide phthalocyanine pigment, the weight average molecular weight (Mw) of the alkali-soluble resin is preferably in the range of 10,000 to 100,000, more preferably in the range of 30,000 to 80,000. In addition, 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.

In addition, in the present invention, the molecular weight distribution [weight average molecular weight (Mw), number average molecular weight (Mn)] of the resin is measured by GPC on the following conditions.

Device: GPC-150C (ウオタタズ社)

Column: GMH-HT30cm2 (manufactured by Tosoh Corporation)

Temperature: 135°C

Solvent: o-dichlorobenzene (add 0.1% 2,6-di-tert-butyl-4-methylphenol (Aionol))

Flow rate: 1.0ml/min

Sample: Inject 0.4ml of 0.15% sample

The measurement was performed under the above conditions, and when calculating the molecular weight of the sample, a molecular weight calibration curve prepared using monodisperse polystyrene standard samples was used. Furthermore, it computed by polyethylene conversion using the conversion formula derived from the Mark-Houwink viscosity formula.

The active energy ray-curable resin can be a resin that reacts a (meth)acrylic compound or cinnamic acid having a reactive substituent such as an isocyanate group, an aldehyde group, or an epoxy group with a hydroxy, carboxyl, or amino group. It is formed by reacting a linear polymer with a permanent substituent to introduce a photocrosslinkable group such as a (meth)acryloyl group or a styryl group into the linear polymer. In addition, a resin obtained by copolymerizing styrene-maleic anhydride copolymer or α-olefin-maleic anhydride with a (meth)acrylic compound having a hydroxyl group such as hydroxyalkyl (meth)acrylate can also be used. It is formed by half-esterification of linear polymers containing acid anhydrides.

As the monomer and oligomer of the resin precursor, for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, (meth)acrylate Base) butyl acrylate, isobutyl (meth) acrylate, tert-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, (meth)acrylate ) tridecyl acrylate, isomyristyl (meth)acrylate, stearyl (meth)acrylate, or isostearyl (meth)acrylate, etc. ) alkyl acrylate;

Cyclohexyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, dicyclopentyl (meth)acrylate, dicyclopentyloxyethyl (meth)acrylate, dicyclopentanyl (meth)acrylate Cycloalkyl (meth)acrylates such as alkenyl esters, dicyclopentenyloxyethyl (meth)acrylate, or isobornyl (meth)acrylate;

(Meth)acrylic acid such as trifluoroethyl (meth)acrylate, octafluoropentyl (meth)acrylate, perfluorooctylethyl (meth)acrylate, or tetrafluoropropyl (meth)acrylate Fluoroalkyl esters;

(Meth)acryloyloxy modified polydimethylsiloxane (siloxane macromer);

Heterocyclic (meth)acrylates such as tetrahydrofurfuryl (meth)acrylate or 3-methyl-3-oxetanyl (meth)acrylate;

Benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, p-cumylphenoxyethyl (meth)acrylate, p-cumyl (meth)acrylates having an aromatic ring such as phenoxy polyethylene glycol (meth)acrylate or nonylphenoxy polyethylene glycol (meth)acrylate;

(meth)acrylate-2-methoxyethyl, (meth)acrylate-2-ethoxyethyl, (meth)acrylate-3-methoxybutyl, (meth)acrylate-2- Methoxypropyl ester, Diethylene glycol monomethyl ether (meth)acrylate, Diethylene glycol monoethyl ether (meth)acrylate, Triethylene glycol monomethyl ether (meth)acrylate, Triglycerol Alcohol monoethyl ether (meth)acrylate, diethylene glycol mono-2-ethylhexyl ether (meth)acrylate, dipropylene glycol monomethyl ether (meth)acrylate, tripropylene glycol mono(meth)acrylate (poly)alkylene glycol monoalkyl ether such as acrylate, polyethylene glycol monolauryl ether (meth)acrylate, or polyethylene glycol monostearyl ether (meth)acrylate (meth)acrylates;

(Meth)acrylic acid, acrylic acid dimer, 2-(meth)acryloyloxyethyl phthalate, 2-(meth)acryloyloxypropyl phthalate, 2-(meth)acryloyloxyethyl phthalate, 2-(meth)acryloyloxypropyl hexahydrophthalate, ethylene oxide modified succinic acid (meth)acrylic acid Carboxyl-containing (meth)acrylates such as esters, (meth)acrylate-β-carboxyethyl ester, or ω-carboxypolycaprolactone (meth)acrylate;

2-Hydroxyethyl (meth)acrylate, 2-Hydroxypropyl (meth)acrylate, 2-Hydroxybutyl (meth)acrylate, 4-Hydroxybutyl (meth)acrylate ester, 2-acryloyloxyethyl-2-hydroxyethyl(methyl)phthalate, 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-butylene glycol) mono(meth)acrylate, poly(propylene glycol-butylene glycol) mono(meth)acrylate, or glycerol (meth) (meth)acrylates with hydroxyl groups such as acrylates;

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 ) acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, poly(ethylene glycol-propylene glycol) di(meth)acrylate ester, poly(ethylene glycol-butylene glycol) di(meth)acrylate, poly(propylene glycol-butylene 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 base) acrylate, or (poly)alkylene glycol di(meth)acrylates such as 2-ethyl, 2-butylpropylene glycol di(meth)acrylate;

Dimethylol dicyclopentane di(meth)acrylate, hydroxytrimethyl acetate neopentyl glycol di(meth)acrylate, stearic acid modified pentaerythritol di(meth)acrylate, ethylene oxide Alkane modified bisphenol A di(meth)acrylate, Propylene oxide modified bisphenol A di(meth)acrylate, Tetrahydrofuran modified bisphenol A di(meth)acrylate, Ethylene oxide modified Bisphenol F di(meth)acrylate, propylene oxide modified bisphenol F di(meth)acrylate, tetrahydrofuran modified bisphenol F di(meth)acrylate, zinc diacrylate, ethylene oxide modified Phosphoric acid triacrylate, or di(meth)acrylates such as glycerol di(meth)acrylate;

Dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, or diethylaminopropyl (meth)acrylate having a tertiary amino group (meth)acrylates;

Glycerol tri(meth)acrylate, Trimethylolpropane tri(meth)acrylate, Pentaerythritol tri(meth)acrylate, Pentaerythritol tetra(meth)acrylate, Dipentaerythritol penta(meth)acrylate esters, or dipentaerythritol hexa (meth) acrylate and other trifunctional or more multi-functional (meth) acrylates;

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 product, phenyl glycidyl ether-(meth)acrylic acid adduct, styrene oxide-(meth)acrylic acid adduct, bisphenol A diglycidyl ether-(meth)acrylic acid adduct, epoxy Propane modified bisphenol A diglycidyl ether-(meth)acrylic acid adduct, bisphenol F diglycidyl ether-(meth)acrylic acid adduct, epichlorohydrin modified phthalic acid-(methyl) ) acrylic acid adduct, epichlorohydrin modified hexahydrophthalic acid-(meth)acrylic acid adduct, ethylene glycol diglycidyl ether-(meth)acrylic acid adduct, polyethylene glycol diglycidic acid adduct Glyceryl ether-(meth)acrylic acid adduct, Propylene glycol diglycidyl ether-(meth)acrylic acid adduct, Polyethylene glycol diglycidyl ether-(meth)acrylic acid adduct, Phenol novolac Type epoxy resin (Feno-Lunobolak-type Epokish resin)-(meth)acrylic acid adduct, cresol novolak-type epoxy resin (Kreze-Lunobolak-type Epokish resin)-(meth)acrylic acid adduct, Or other epoxy (meth)acrylates such as epoxy resin-(meth)acrylic acid adducts;

(Meth)acryloyl-modified isocyanurate, (meth)acryloyl-modified polyurethane, (meth)acryloyl-modified polyester, (meth)acryloyl-modified melamine, (meth)acrylic Acyl-modified polysiloxane, (meth)acryl-modified polybutadiene, or (meth)acryl-modified resin oligomers such as (meth)acryl-modified rosin;

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-methylol (meth)acrylamide, or N-vinylformamide; or

Acrylonitrile etc. These compounds may be used alone or in combination of two or more, but are not limited to these compounds.

[Basic resin type dispersant (a)]

The green coloring composition of the present invention is characterized in that a zinc halide phthalocyanine having zinc as the central metal is used as the main pigment of the pigment component (A), and the zinc halide phthalocyanine and the copper halide generally used in green coloring compositions Compared with cyanine pigments, it is an acidic pigment with zinc in the center metal, and the surface of the pigment has a negative charge. Therefore, in the first embodiment of the present invention, by using a basic resin type dispersant (a) having a high amine value of 35 to 100 mg KOH/g as the resin type dispersant used when the pigment is dispersed, it is possible to make Its adsorption to the acidic pigment becomes sufficient, and the dispersion can obtain sufficient fluidity.

The number average molecular weight of the basic resin-type dispersant (a) used in the present invention is usually preferably 500 to 50,000, particularly, more preferably 3,000 to 30,000. When the above-mentioned number average molecular weight is less than 500, the steric repulsion effect caused by the pigment affinity group, the effect of the compatibility with the pigment carrier, and the effect of the compatibility with the pigment carrier and the solvent when a solvent is used become small, It is difficult to prevent the aggregation of the pigment, and the viscosity of the dispersion increases. In addition, when the number-average molecular weight exceeds 50,000, the amount of resin added required for dispersion increases, resulting in a decrease in the pigment concentration in the coating film.

In the first embodiment of the present invention, a basic resin type dispersant (a) having an amine value of 35 to 100 mg KOH/g is used. The amine value of the basic resin type dispersant (a) is more preferably 50 to 75 mgKOH/g. When the amine value is less than 35mg KOH/g, it cannot be fully adsorbed on the pigment to form poor dispersion. When it exceeds 100mg KOH/g, due to the adsorption or reaction of the acidic component in the pigment carrier, it is difficult for the zinc halide phthalocyanine The adsorption efficiency of the pigment becomes poor, resulting in poor dispersion.

Basic resin type dispersant (a) with an amine value of 35 to 100 mg KOH/g can use various types of resins such as vinyl, urethane, polyester, polyether, or polyamide , but preferred are vinyl monomer copolymers that are easy to design resins and have excellent resistance, specifically, vinyl monomer units containing N,N-disubstituted amino groups and alkyl (meth)acrylate monomers are preferred. Units and other vinyl monomer units of the copolymer resin.

Containing N, the vinyl monomer unit of N-disubstituted amino group can enumerate, (meth)acrylic acid-N, N-dimethylamino ethyl ester, (meth)acrylic acid-N, N-diethylamino ethyl ester, ( Meth)acrylate-N,N-dimethylaminopropyl ester, (meth)acrylate-N,N-diethylaminopropyl ester, N,N-dimethylaminoethyl (meth)acrylamide, or N, N-diethylaminoethyl (meth)acrylamide and the like, but it is not limited to these compounds. These monomer units are adsorbed as basic group-containing monomer units on the zinc halide phthalocyanine pigment with high acidity.

Alkyl (meth)acrylate monomer units include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, (meth)acrylate ) n-butyl acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, or (meth)acrylate (meth)acrylic esters obtained by reacting unsaturated monocarboxylic acid such as lauryl acrylate and alkyl alcohol having 1 to 18 carbon atoms, but are not limited to these compounds. These monomer units function as pigment carrier affinity groups.

Other vinyl monomer units include vinyl monomers containing nitrile groups such as (meth)acrylonitrile, vinyl groups such as styrene, α-methylstyrene, and benzyl (meth)acrylate. Aromatic monomers, vinyl monomers containing hydroxyl groups such as 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, or polyethylene glycol (meth)acrylate, Vinyl monomers containing amide groups such as (meth)acrylamide, N,N-dimethylacrylamide, N-isopropylacrylamide, or diacetone acrylamide, N-methylol (methyl) ) acrylamide or dimethylol (meth)acrylamide and other vinyl monomers, N-methoxymethyl (meth)acrylamide or N-butoxymethyl (meth)acrylamide, etc. Alkoxymethyl vinyl-based monomers, olefins such as ethylene, propylene, or isoprene, dienes such as chloroprene or butadiene, methyl vinyl ether, ethyl vinyl Vinyl ethers such as ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether, fatty acids such as vinyl acetate or vinyl propionate Vinyl esters and the like may suitably use the above-mentioned compounds according to the purpose, but are not limited to these compounds.

Also exemplified are polyester resins, acrylic resins, or polyether resins, etc., polymers having monomer units containing primary amino groups such as allylamine, or polyethyleneimine, polyethylenepolyamine, parylene, etc. Comb-shaped basic resin type dispersant modified by (hydroxypropylene) polyamine (polykisililenpoly) or poly(aminomethylated) epoxy resin.

Commercially available products of such a basic resin type dispersant include, for example, BYK-161, 163, 164, 167, 174, 184, 2000, 2050 of BITSUKCHEMY JAPAN CORPORATION, or SOLSPERSE- 34750, 56000, EFKA4300, 4330, 4046, 4060, 4080 of Chiba Japan Corporation, etc.

As the basic resin type dispersant (a) of the green coloring composition for color filters of the present invention, a block comprising a basic copolymer block (a1) and a pigment carrier-affinity copolymer block (a2) is particularly preferable Copolymer resin. Hereinafter, the basic resin type dispersant will be described.

(basic resin type dispersant)

The basic resin-type dispersant of the green coloring composition for color filters of the present invention has a site adsorbed on the pigment (hereinafter simply referred to as an adsorption site) and has an effect of preventing aggregation between pigments and improving dispersibility. The part with high affinity of the carrier (hereinafter simply referred to as the affinity part). Since the halide zinc phthalocyanine has a high acidity, when the affinity portion and the adsorption portion are randomly arranged, the adsorption to the pigment becomes insufficient, resulting in poor dispersion. In the first embodiment of the present invention, by using the following block copolymer resin as the resin type dispersant (a), it is possible to provide a fine and low-viscosity dispersant that does not impair the color characteristics of the zinc halide phthalocyanine pigment. Stably dispersed green coloring composition, the block copolymer resin is a basic copolymer block (a1) as an adsorption part for a zinc halide phthalocyanine pigment and a pigment carrier affinity part as an affinity part for a pigment carrier The neutral copolymer block (a2) exists separately on the same molecule.

Various resin systems can be selected for the basic copolymer block (a1) and the pigment carrier-affinity copolymer block (a2) constituting the block copolymer resin, but vinyl copolymers, which are easy to design and have excellent resistance to each, are preferred. thing.

Each copolymer block will be described below.

<Basic copolymer block (a1)>

Specific examples of the basic copolymer block (a1) include (meth)acrylic acid-N,N-dimethylaminoethyl ester, (meth)acrylic acid-N,N-diethylaminoethyl ester, (methyl) ) Acrylic acid-N,N-dimethylaminopropyl ester, (meth)acrylic acid-N,N-diethylaminopropyl ester, N,N-dimethylaminoethyl (meth)acrylamide, or N,N- Copolymers of vinyl monomer units containing N,N-disubstituted amino groups such as diethylaminoethyl (meth)acrylamide, polymers of monomer units containing primary amino groups such as allylamine, or polyethylene Amines, polyethylene polyamines, parylene poly(hydroxypropylene) polyamines, or poly(aminomethylated) epoxy resins, etc., but are not limited to these compounds.

Among them, a copolymer having a vinyl monomer unit containing an N,N-disubstituted amino group, which is easy to design the resin of the block copolymer and has excellent resistance, is particularly preferable. In this case, the basic copolymer block (a1) The vinyl monomer unit containing N, N-disubstituted amino group contained in is preferably 60 to 100% by weight, more preferably 80 to 100% by weight, as the vinyl monomer unit containing N, N-disubstituted amino group The vinyl-based monomer units other than the unit are preferably the vinyl-based monomer units described in the pigment carrier-affinity copolymer block (a2).

<Pigment Carrier Affinity Copolymer Block (a2)>

The pigment carrier-compatible copolymer block (a2) is a vinyl-based monomer copolymer that is easy to design the resin of the block copolymer and is excellent in each resistance, and furthermore, the vinyl-based monomer unit preferably contains a (meth)acrylic acid alkyl group. In particular, the ester is preferably contained in an amount of 60 to 100% by weight, more preferably 80 to 100% by weight, in the pigment carrier-substantiated copolymer block (a2). Alkyl (meth)acrylates include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, (meth)acrylic acid n-butyl, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, or (meth) (Meth)acrylic esters obtained by reacting unsaturated monocarboxylic acid such as lauryl acrylate with alkyl alcohol having 1 to 18 carbon atoms, etc., but are not limited to these compounds.

In the pigment carrier-compatible copolymer block (a2), the amino group-containing vinyl monomer unit is preferably 0% by weight, but may be contained in an amount of less than 10% by weight.

Examples of other vinyl-based monomer units that may be contained in the basic copolymer block (a1) and the pigment-carrier-affinity copolymer block (a2) include (meth)acrylonitrile, etc., containing a nitrile group. Vinyl-based monomers, vinyl-based aromatic monomers such as styrene, α-methylstyrene, or benzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, ( Hydroxypropyl methacrylate, polyethylene glycol (meth)acrylate and other hydroxyl-containing vinyl monomers, (meth)acrylamide, N,N-dimethylacrylamide, N-iso Vinyl monomers containing amide groups such as propylacrylamide or diacetone acrylamide, vinyl monomers such as N-methylol (meth)acrylamide or dimethylol (meth)acrylamide Vinyl monomers containing alkoxymethyl groups such as N-methoxymethyl (meth)acrylamide or N-butoxymethyl (meth)acrylamide, ethylene, propylene, or isoprene Olefins such as alkenes,

Dienes such as chloroprene or butadiene, methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl Vinyl ethers such as vinyl vinyl ether, or fatty acid vinyl esters such as vinyl acetate or vinyl propionate, etc., but are not limited to these compounds.

<Block copolymer resin>

The above-mentioned resin type dispersant (a) used in the first embodiment of the present invention can be prepared by a known method, and in particular, it is preferable to (1) use a living polymerization method, or (2) make a A polymer coupling method in which the precursor (a11) of the basic copolymer block (a1) reacts with the precursor (a21) of the pigment carrier-affinity copolymer block (a2) having a functional group at the terminal. Among them, (1) the method using living polymerization is particularly preferable.

(1) Living polymerization method

The living polymerization method can suppress the side reactions that occur in general radical polymerization, and since the growth of the polymerization can proceed uniformly, it is possible to easily synthesize block polymers or resins with uniform molecular weights. Among them, it is preferable to use an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst in view of being applicable to a wide range of monomers and adopting a polymerization temperature suitable for existing equipment. Atom moving radical polymerization. The atom transfer radical polymerization method can be carried out using the methods described in the following reference documents 1 to 8 and the like.

(Reference 1) Fukuda et al., Prog. Polym. Sci. 2004, 29, 329

(Reference 2) Matyjaszewski et al., Chem.Rev.2001, 101, 2921

(Reference 3) Matyjaszewski et al., J.Am.Chem.Soc.1995, 117, 5614

(Reference 4) Macromolecules 1995, 28, 7901, Science, 1996, 272, 866

(References 5) International publication No. 96/30421 pamphlet

(references 6) International Publication No. 97/18247 pamphlet

(Reference 7) JP-A-9-208616

(Reference Document 8) JP-A-8-41117

In the atom moving radical polymerization method, a transition metal complex such as copper, ruthenium, iron, or nickel is used as a redox catalyst. Specific examples of transition metal coordination compounds can include copper (I) chloride or copper (I) bromide and other low-valent halogenated transition metals, but in order to control the polymerization rate, it is also possible to add in the polymerization system according to known methods. High valence transition metals such as copper(II) chloride or copper(II) bromide.

Organic ligands can be used in the above-mentioned metal complexes. Organic ligands are used in order to have solubility in polymerization solvents and reversible changes in redox-conjugated coordination compounds. A nitrogen atom, an oxygen atom, a phosphorus atom, or a sulfur atom can be used as a metal coordinating atom, and a nitrogen atom or a phosphorus atom is preferable. Specific examples of organic ligands can include spartine, or 2,2'-bipyridine and its derivatives, 1,10-phenanthroline or its derivatives, tetramethylethylenediamine, pentamethyldi Ethylenetriamine, tris(dimethylaminoethyl)amine, hexamethyl(2-aminoethyl)amine, triphenylphosphine, or tributylphosphine, etc. Among the above catalysts, it is preferable to perform polymerization using a combination of copper halide and butanediamine, from the viewpoint of the polymerization rate and the control of the molecular weight of the block resin.

The above-mentioned transition metal and organic coordination compound can be added separately to form a metal coordination compound in the polymer, or the metal coordination compound can be synthesized in advance and then added to the polymerization system. In particular, the former method is preferred when the transition metal is copper, and the latter method is preferred when the transition metal is ruthenium, iron, or nickel. Specific examples of pre-synthesized ruthenium, iron or nickel coordination compounds can include tri(triphenylphosphine) ruthenium dichloride (Ru(Cl) ₂ (PPh ₃ ) ₃ , bis(triphenylphosphine) ferric dichloride (Fe(Cl) ₂ (PPh ₃ ) ₂ ), bis(triphenylphosphine)nickel dichloride (Ni(Cl) ₂ (PPh ₃ ) ₂ ), or bis(tributylphosphine)nickel dibromide ( NiBr ₂ (PBu ₃ ) ₂ ), etc.

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

In the above-mentioned atom moving radical polymerization, the initiator of atom moving radical polymerization can be appropriately selected according to the molecular weight of the synthesized resin, and it is preferably 0.001 to 10 mol%, more preferably 0.01 ~1 mol% ratio is used. In addition, the amount of transition metal used is preferably 0.03 to 3 moles, more preferably 0.1 to 2 moles, relative to 1 mole of the initiator in the form of a halide or the like. Furthermore, the ligand is usually used in a ratio of 1 to 5 moles, preferably 1.2 to 3 moles, based on 1 mole of the transition metal (in the form of a halide or the like). When the above-mentioned initiator of atom moving radical polymerization, transition metal and ligand are used in such a ratio, it is preferable in terms of reactivity of living radical polymerization, molecular weight of resulting polymer, and the like.

In addition, in terms of the characteristics of atom moving radical polymerization, the resulting resin has an active carbon-halogen bond at the terminal end, which can be modified by a known method to introduce a functional group. In addition, polymerization can be carried out using a polymerization initiator having a functional group, and the functional group can be introduced at the terminal of the resin and used for various reactions.

Atom moving radical polymerization can be performed without a solvent, or can be performed in the presence of a solvent such as butyl acetate, toluene, xylene, anisole, methyl ethyl ketone, or cyclohexanone. In particular, from the viewpoint of the polymerization rate, a ketone solvent is preferable, and methyl ethyl ketone is particularly preferable. When a solvent is used, it is preferably used in an amount such that the concentration of the solvent after polymerization is 50% by weight or less in order to prevent a decrease in the polymerization rate. Even when there is no solvent or a small amount of solvent, there is no safety problem related to the control of polymerization heat, etc., and the solvent is reduced, which is also preferable in terms of economic efficiency and environmental measures.

As the polymerization conditions, in view of the polymerization rate and the deactivation of the catalyst, the polymerization temperature is 60 to 130° C., and the polymerization time is also dependent on the final molecular weight or the polymerization temperature, but it only needs to be in the range of about 1 to 100 hours. . In addition, during the polymerization reaction, in order to prevent deactivation of the polymerization catalyst by oxygen, it is preferable to carry out under an inert gas atmosphere such as nitrogen or argon.

In addition, after the polymerization reaction is completed, the polymerization reaction system is cooled to preferably below 0°C, more preferably about -78°C, to terminate the reaction. According to known methods, residual monomers and/or solvents can be removed. Reprecipitation, filtration of precipitated polymers by centrifugation, washing and drying of polymers. The block resin used in the present invention can be obtained by evaporating volatile components after removing transition metals and the like contained in the polymerization system by a known method if necessary. The removal method is to dilute the reaction mixture with an organic solvent such as tetrahydrofuran, toluene or methyl ethyl ketone, wash with water, dilute hydrochloric acid or ammonia solution, etc., and make the resin solution contact with cation exchange resin or chelating resin. - A method of passing through a column or pad of silica or clay, a method of adding a reducing agent or an adsorbent such as hydrotalcite, followed by filtration and centrifugation, etc. From the viewpoint of ease of handling, it is preferable to add and stir a cation exchange resin and an acid adsorbent such as hydrotalcite to the diluted resin solution, and then filter off the ion exchange resin and acid adsorbent to obtain a resin solution.

When water is mixed into the resin solution by refining treatment, the reaction between the block resin used in the present invention and the curing agent may be hindered, and it is preferable to add a solvent mixed with water to the resin solution and perform azeotropic dehydration or the like. Instead, moisture is removed from the resin solution.

For the atom moving radical polymerization used in the present invention, since the side reactions that occur in general radical polymerization can be suppressed, the initiator of the atom moving radical polymerization added during the polymerization and the loading of the radical polymerizable monomer can be used. The proportion can freely control the molecular weight of the resin or the proportion of the basic copolymer block (a1) or the pigment carrier-affinity copolymer block (a2).

(2) Polymer coupling method

As the terminal functional group of the precursor (a11) of the basic copolymer block (a1) of the polymer coupling method and the precursor (a21) of the pigment carrier affinity copolymer block (a2), the preferred functional group is specifically A carboxyl group, a primary amino group, a hydroxyl group, an alkoxysilyl group, etc. are mentioned.

As a method for introducing terminal functional groups into the precursor (a11) of the basic copolymer block (a1) and the precursor (a21) of the pigment carrier-affinity copolymer block (a2), it is preferable to use Functional groups and chain transfer agents with mercapto groups, a method for free radical polymerization. The chain transfer agent with carboxyl group can enumerate mercaptopropionic acid, the chain transfer agent with primary amino group can enumerate cysteamine, the chain transfer agent with hydroxyl group can enumerate mercaptoethanol, and the chain transfer agent with alkoxysilyl group can enumerate 3 - mercaptopropylmethylmethoxysilane, or 3-mercaptopropyltrimethoxysilane.

The reaction of the precursor (a11) and the precursor (a21) may be, for example, a known reaction performed in combination in Table 1 below.

Examples of the polyisocyanate compound of the binder include aromatic polyisocyanate, aliphatic polyisocyanate, araliphatic polyisocyanate, or alicyclic polyisocyanate. Aromatic polyisocyanates include, for example, 1,3-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,4-benzene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4- Benzylidene diisocyanate, 2,6-benzylidene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanatotoluene, 1,3,5-triisocyanatobenzene, bimethano Oxyaniline diisocyanate, 4,4'-diphenyl ether diisocyanate, or 4,4',4"-triphenylmethane triisocyanate, etc. Examples of aliphatic polyisocyanate include propylene diisocyanate, diisocyanate tetramethylene diisocyanate, hexamethylene diisocyanate, pentylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1 diisocyanate , 3-butylene ester, dodecamethylene diisocyanate, or 2,4,4-trimethylhexyl diisocyanate, etc. Aromatic aliphatic polyisocyanates can be listed, for example, ω, ω′-di Isocyanate-1,3-dimethylbenzene, ω,ω′-diisocyanate-1,4-dimethylbenzene, ω,ω′-diisocyanate-1,4-diethylbenzene, 1,4-tetra Methyl xylene diisocyanate, or 1,3-tetramethyl xylene diisocyanate, etc. Examples of alicyclic polyisocyanates include 3-isocyanatomethyl (ISO CYANE-TOMECHIL)-3,5,5-tri Methylcyclohexane 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'-methylene bis(cyclohexyl isocyanate), 1,4-bis(isocyanatomethyl)cyclohexane, or 1,4- Two (isocyanatomethyl) cyclohexane etc., but not limited to these compounds.In addition, also can use the trimethylol propane adduct of a part of above-mentioned polyisocyanate, the biuret thing that reacts with water, have Trimers of isocyanurate rings, etc.

The polyepoxide of the binder is preferably a polyepoxide having at least 2 glycidyl groups. Specifically, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, trimethylol propane triglycidyl ether, trimethylol propane Aliphatic polyepoxides such as ethane triglycidyl ether, sorbitol polyglycidyl ether, or pentaerythritol polyglycidyl ether, bisphenol A or bisphenol F aromatic polyepoxides, tetraglycidyl Glycidylamine-type epoxy compounds such as aminophenylmethane, triglycidyl isocyanurate, or 1,3-bis(N,N-glycidylaminomethyl)cyclohexane, but not limited in these compounds.

The number average molecular weight of the block copolymer type basic resin type dispersant used in the first embodiment of the present invention is usually preferably from 500 to 50,000, more preferably from 3,000 to 30,000. However, when the above-mentioned number average molecular weight is less than 500, the steric repulsion effect caused by the pigment-affinity copolymer block (a2), the effect of compatibility with the pigment carrier, and the compatibility with the pigment carrier and the solvent when using a solvent The effect becomes smaller, it is difficult to prevent the aggregation of the pigment, and the viscosity of the dispersion increases. In addition, when the number-average molecular weight exceeds 50,000, the amount of resin added required for dispersion increases, resulting in a decrease in the pigment concentration in the coating film.

In addition, the block copolymer type basic resin type dispersant used in the first embodiment of the present invention has an amine value of 35 to 100 mg KOH/g, more preferably 50 to 75 mg KOH/g. When the amine value is less than 35mg KOH/g, it cannot be fully adsorbed on the pigment, resulting in poor dispersion. When it exceeds 100mg KOH/g, the adsorption efficiency of the pigment is reduced due to the adsorption or reaction of the acidic component in the pigment carrier. Deterioration, resulting in poor dispersion.

The composition weight ratio of the basic copolymer block (a1) or the pigment carrier affinity copolymer block (a2) and the number average molecular weight of each block can preferably be designed arbitrarily, so that the overall number average of the resin type dispersant The molecular weight and amine value are within the above-mentioned preferred ranges.

In the green coloring composition according to the first embodiment of the present invention, based on the total weight of the pigment component (A), the compounding amount of the basic resin type dispersant (a) is preferably 0.001 to 50% by weight, more preferably 0.1 to 30% by weight, most preferably 0.5 to 25% by weight. If the amount of the resin-type dispersant (a) based on the total weight of the pigment component (A) is less than 0.001% by weight, the dispersibility may deteriorate, and if it exceeds 40% by weight, the heat resistance, When the light fastness deteriorates.

[Pigment derivative (b) having a basic substituent]

The green coloring composition of the present invention is characterized in that a zinc halide phthalocyanine having zinc as the central metal is used as the main pigment of the pigment component (A), and the zinc halide phthalocyanine and the copper halide generally used in green coloring compositions Compared with cyanine pigments, it is an acidic pigment with zinc in the center metal, and the surface of the pigment has a negative charge. Therefore, when a dispersant having a basic substituent is used, adsorption to an acidic pigment becomes sufficient, and the pigment dispersion can find sufficient fluidity and color characteristics. In the second embodiment of the present invention, a preferable pigment dispersion can be obtained by using the pigment derivative (b) having a basic substituent as a dispersant.

As described above, in the second embodiment of the coloring composition for color filters of the present invention, the pigment derivative (b) can be used for the purpose of improving the dispersibility of the pigment. Examples of pigment derivatives include organic pigments, anthraquinones, acridones, or triazines, in which basic substituents, acidic substituents, or phthalimide methyl groups that may have substituents are introduced.

In the present invention, basic derivatives are particularly preferred, and basic derivatives are compounds represented by the following general formula (1), which are derivatives with a specific parent skeleton, and the specific parent skeleton has a basic group . It is not particularly limited as long as it is a pigment derivative having a basic group, but it is preferable to use a pigment derivative having a triazine ring skeleton having a basicity as represented by the following general formula (4). group.

General formula (1):

P-Lm

(wherein, in general formula (1),

P is an m-valent organic pigment residue, anthraquinone skeleton, acridone skeleton, triazine skeleton, etc.,

m is an integer of 1 to 4,

L is a substituent selected from the groups represented by the general formulas (2), (3), and (4). )

General formula (2):

General formula (3):

General formula (4):

[Wherein, in general formula (2)～(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 from 1 to 10,

Y ¹ is -NH-, -NR ⁵⁸ -Z-NR ⁵⁹ -, or a direct bond,

R ⁵⁸ and R ⁵⁹ each independently represent a hydrogen atom, an alkyl group with 1 to 36 carbon atoms that may also have a substituent, an alkenyl group with 2 to 36 carbon atoms that may also have a substituent, or may have Phenyl substituent,

Z represents an alkylene group which may also have a substituent or an arylene group which may also have a substituent,

R ⁵⁰ and R ⁵¹ each independently represent 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 A heterocyclic ring which may have a substituent integrally with R ⁵¹ and further contains a nitrogen, oxygen or sulfur atom.

R ⁵² , R ⁵³ , R ⁵⁴ and R ⁵⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an alkene group having 2 to 20 carbon atoms which may have a substituent A group, an arylene group having 6 to 20 carbon atoms that may also have substituents,

^R56 is a hydrogen atom, an alkyl group with 1 to 20 carbon atoms that may also have a substituent, or an alkenyl group with 2 to 20 carbon atoms that may also have a substituent,

R ⁵⁷ is a substituent shown in general formula (2) or a substituent shown in general formula (3),

Q is a hydroxyl group, an alkoxy group, a substituent represented by the above general formula (2), or a substituent represented by the above general formula (3). 〕

The amine components used to form substituents represented by general formulas (2) to (4) include, for example, dimethylamine, diethylamine, methylethylamine, N,N-ethylisopropylamine, N,N- Ethylpropylamine, 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-methyloctadecylamine, didecylamine, diallylamine, N,N-ethyl-1,2-dimethylpropylamine, N , N-methylhexylamine, dioleylamine, distearylamine, N,N-dimethylaminomethylamine, N,N-dimethylaminoethylamine, N,N-dimethylaminopentylamine , N,N-Dimethylaminobutylamine, N,N-Diethylaminoethylamine, N,N-Diethylaminopropylamine, N,N-Diethylaminohexylamine, N,N-Diethylamine Aminobutylamine, N,N-diethylaminopentylamine, N,N-dipropylaminobutylamine, N,N-dibutylaminopropylamine, N,N-dibutylaminoethylamine, N, N-dibutylaminobutylamine, N,N-diisobutylaminopentylamine, N,N-methyl-laurylaminopropylamine, N,N-ethyl-hexylaminoethylamine, N,N-di Stearylaminoethylamine, N,N-Dioleylaminoethylamine, N,N-Distearylaminobutylamine, Piperidine, 2-Methylpiperidine, 3-Methylpiperidine, 4-Methylpiperidine Basepiperidine, 2,4-dimethylpiperidine, 2,6-dimethylpiperidine, 3,5-dimethylpiperidine, 3-piperidinemethanol, pipecolic acid, hexahydroisonicotinic acid, Methyl hexahydroisonicotinate, ethyl hexahydroisonicotinate, 2-piperidine ethanol, pyrrolidine, 3-hydroxypyrrolidine, N-aminoethylpiperidine, N-aminoethyl-4-methylpiperidine Pyridine, N-aminoethylmorpholine, N-aminopropylpiperidine, N-aminopropyl-2-methylpiperidine, N-aminopropyl-4-methylpiperidine, N-aminopropylpiperidine Phyloline, N-methylpiperazine, N-butylpiperazine, N-methylhomopiperidine, 1-cyclopentylpiperazine, 1-amino-4-methylpiperazine, 1-cyclopentylpiperazine wait.

The pigment derivatives having basic substituents, anthraquinone derivatives, and acridone derivatives used in the second embodiment of the present invention can be synthesized by various synthesis routes. For example, after introducing substituents shown in formulas (5) to (8) into organic pigments, anthraquinones or acridones, they can react with the above substituents to form formulas (2) to (4) The above amine components of the indicated substituents are reacted, such as N,N-dimethylaminopropylamine, N-methylpiperazine, diethylamine, or 4-[4-hydroxyl-6 -[3-(dibutylamino)propylamino]-1,3,5-triazine-2-amino]aniline and the like.

Formula (5): -SO ₂ Cl

Formula (6): -COCl

Formula (7): -CH ₂ NHCOCH ₂ Cl

Formula (8): -CH ₂ Cl

When the substituents of the formulas (5) to (8) react with the above-mentioned amine component, some of the substituents of the formulas (5) to (8) are hydrolyzed, so that chlorine may be mixed with a hydroxyl group. At this time, formula (5) and formula (6) become sulfonic acid group and carboxylic acid group respectively, they all can maintain the state of free acid, or also can be the salt that forms with 1～3 valent metal or above-mentioned monoamine .

In addition, when the organic pigment is an azo pigment, substituents represented by general formulas (2) to (4) are preliminarily introduced into the diazo component or the coupling component, and then the coupling reaction is performed, thereby also producing Azo pigment derivatives.

The triazine derivative having a basic group used in the second embodiment of the present invention can be synthesized by various synthetic routes. For example, using cyanuric chloride as a starting material, by making an amine component forming a substituent represented by general formulas (2) to (4), such as N,N-dimethylaminopropylamine or N-methylpiperazine, etc. It can be obtained by reacting at least one chlorine of uric acid chloride, and then reacting the remaining chlorines of cyanuric chloride with various amines or alcohols.

In the pigment composition of the present invention, the compounding amount of the pigment derivative having a basic substituent is preferably 1 to 50 parts by weight, more preferably 3 to 30 parts by weight, and most preferably 100 parts by weight of the pigment component (A). 5 to 25 parts by weight. When the amount of the basic derivative is less than 1 part by weight relative to 100 parts by weight of the pigment, the dispersibility may deteriorate, and when it exceeds 50 parts by weight, heat resistance and light resistance may deteriorate. Among them, compounds having a triazine structure in the basic substituent are preferable in terms of dispersion stability.

[Organic solvent (c)]

In the third embodiment of the green coloring composition of the present invention, in order to sufficiently disperse the pigment component (A) in the pigment carrier (B), and to easily apply it on a substrate such as a glass substrate with a dry film thickness of 0.2 to 5 μm to form color filter segments and contain an organic solvent (c).

The organic solvent (c) uses an organic solvent (c1) containing a solubility parameter (SP value) of 8.0 to 10.0 (cal/cm ³ ) ^1/2 and a boiling point of 140 to 159° C. at 760 mmHg; and a solubility parameter ( SP value) is 8.0 to 10.0 (cal/cm ³ ) ^1/2 and a mixed organic solvent of an organic solvent (c2) having a boiling point at 760 mmHg of 160 to 200°C.

In the present specification, the solubility parameter (SP value) refers to a value obtained from the physical quantity (evaporation heat, etc.) of an organic solvent, and is a value described in various documents.

More preferably, the organic solvent (c) is an organic solvent (c1) containing a solubility parameter (SP value) of 8.0 to 10.0 (cal/cm ³ ) ^1/2 and a boiling point of 144 to 157°C at 760mmHg; and A mixed organic solvent of an organic solvent (c2) whose parameter (SP value) is 8.0 to 10.0 (cal/cm ³ ) ^1/2 and whose boiling point at 760 mmHg is 164 to 192°C.

Here, the organic solvent (c1) is preferably at least one selected from, for example, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate. In addition, the organic solvent (c2) is preferably, for example, one or more solvents selected from cyclohexyl acetate, propylene glycol diacetate, diethylene glycol diethyl ether, and ethyl 3-ethoxypropionate . Also, cyclohexyl acetate is also called cyclohexanol acetate.

The green coloring composition for color filters according to the third embodiment of the present invention has a high contrast to organic solvents (c1) and organic solvents (c2) having a solubility parameter (SP value) and a boiling point in a specific range in a specific ratio. Ratio and high brightness. In addition, the coating film coated with the coloring composition has excellent performance with reduced film thickness unevenness and streaky unevenness, uniform film thickness.

When the solubility parameter (SP value) is less than 8.0 (cal/cm ³ ) ^1/2 hours, the dispersion of the zinc halide phthalocyanine pigment becomes worse, and when it is greater than 10.0 (cal/cm ³ ) ^1/2 , the zinc halide phthalocyanine pigment Pigments dissolve in organic solvents, resulting in reductions in brightness and contrast ratio.

When the boiling point of the solvent used as the organic solvent (c1) is lower than 140° C., unevenness in film thickness or streaky unevenness will occur, which is never preferable. In addition, when the boiling point of the solvent used as the organic solvent (c2) is higher than 200° C., tackiness (tuckiness) remains, which is not preferable.

The mixed organic solvent (c) can be used in an amount of 800 to 4,000% by weight based on the total amount of the above-mentioned pigment component (A). Moreover, it is preferable that the organic solvent (c1) is 50 to 95% by weight and the organic solvent (c2) is 5 to 50% by weight in the total amount of blending of the mixed organic solvent (c). More preferably, the organic solvent (c1) is 65 to 95% by weight, and the organic solvent (c2) is 5 to 35% by weight. If the ratio of the organic solvent (c1) exceeds the range of 50 to 95%, there is a problem that unevenness in film thickness or stripes may occur in the coating liquid. In this way, in order to perform preferable dispersion of the zinc halide phthalocyanine pigment, it is important to mix the organic solvent (c1) and the organic solvent (c2).

In addition, as described above, the organic solvent (c1) used when dispersing the zinc halide phthalocyanine pigment and the organic solvent (c2) added to improve the defects in the coating film coated with the green coloring composition for color filters of the present invention Without being limited to a specific solvent, in order to easily form the coloring composition into a color filter segment, the following organic solvent can be added as an auxiliary solvent.

烷、2-庚酮、2-甲基-1，3-丙二醇、3，5，5-三甲基-2-环己烷-1-酮、3，3，5-三甲基环己酮、3-甲基-1，3-丁烷二醇、3-甲氧基-3-甲基-1-丁醇、3-甲氧基-3-甲基丁基乙酸酯、3-甲氧基丁醇、3-甲氧基丁基乙酸酯、4-庚酮、间二甲苯、间二乙基苯、间二氯苯、N，N-二甲基乙酰胺、N，N-二甲基甲酰胺、正丁醇、正丁基苯、乙酸正丙酯、N-甲基吡咯烷酮、邻二甲苯、邻氯甲苯、邻二乙基苯、邻二氯苯、对氯甲苯、对二乙基苯、仲丁基苯、叔丁基苯、γ-丁内酯、异丁醇、异佛尔酮、乙二醇二乙基醚、乙二醇二丁基醚、乙二醇单异丙基醚、乙二醇单乙基醚、乙二醇单叔丁基醚、乙二醇单丁基醚、乙二醇单丁基醚乙酸酯、乙二醇单丙基醚、乙二醇单己基醚、乙二醇单甲基醚、二异丁基酮、二甘醇二甲基醚、二甘醇单异丙基醚、二甘醇单乙基醚乙酸酯、二甘醇单丁基醚、二甘醇单丁基醚乙酸酯、二甘醇单甲基醚、环己醇、环己酮、双丙甘醇二甲基醚、双丙甘醇甲基醚乙酸酯、双丙甘醇单乙基醚、双丙甘醇单丁基醚、双丙甘醇单丙基醚、双丙甘醇单甲基醚、双丙酮醇、甘油三乙酸酯、三丙二醇单丁基醚、三丙二醇单甲基醚、丙二醇苯基醚、丙二醇单乙基醚、丙二醇单丁基醚、丙二醇单丙基醚、丙二醇单甲基醚、丙二醇单甲基醚丙酸酯、苄醇、甲基异丁基酮、甲基环己醇、乙酸正戊酯、乙酸正丁酯、乙酸异戊酯、乙酸异丁酯、乙酸丙酯、或者二元酸酯等。1,2,3-trichloropropane, 1,3-butanediol (1,3-butanediol), 1,3-butanediol (1,3-butanediol), 1, 3-butanediol diacetate, 1,4-di

Alkanes, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexane-1-one, 3,3,5-trimethylcyclohexanone , 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxy Oxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N,N-dimethylacetamide, N,N- Dimethylformamide, n-butanol, n-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p- Diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutanol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol mono Isopropyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-tert-butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethyl Glycol monohexyl ether, ethylene glycol monomethyl ether, diisobutyl ketone, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol Alcohol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether Ester, Dipropylene Glycol Monoethyl Ether, Dipropylene Glycol Monobutyl Ether, Dipropylene Glycol Monopropyl Ether, Dipropylene Glycol Monomethyl Ether, Diacetone Alcohol, Glycerin Triacetate, Three Propylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether propionate , benzyl alcohol, methyl isobutyl ketone, methyl cyclohexanol, n-pentyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, or dibasic acid ester, etc.

In order to obtain the preferable green coloring composition of this invention, it is preferable that the total of organic solvent (c1) and organic solvent (c2) is 70 weight% or more in all mixed organic solvents (c). Moreover, it is more preferable that the total thereof is 80% by weight. It is particularly preferable that the total is 85% by weight or more. When a large amount of auxiliary solvents other than the organic solvent (c1) and the organic solvent (c2) are added, the stability of the zinc halide phthalocyanine pigment dispersion and the coatability of the coating film coated with the coloring composition are deteriorated. effect and is therefore not preferred.

[dispersion]

In the green coloring composition of the present invention, a pigment component containing at least a zinc halide phthalocyanine pigment ( A) Finely dispersing the above-mentioned basic resin-type dispersant (a) or the above-mentioned basic resin-type dispersant (a) and the above-mentioned pigment derivative (b) having a basic substituent in the above-mentioned pigment carrier (B) in for preparation. In addition, the green coloring composition of this invention can also mix and prepare what disperse|distributed several types of pigments in the pigment carrier (B), respectively.

The green coloring composition of the present invention may further add a photopolymerization initiator or the like to prepare it as a solvent-developing type or alkali-developing type green resist. When preparing as an alkali-developable colored resist, an alkali-soluble material having an acidic group is used as a part of the pigment carrier.

[Photopolymerization Initiator]

A photopolymerization initiator or the like may be added to the green coloring composition for color filters of the present invention when curing the composition by ultraviolet irradiation or forming color filter segments by photolithography. The compounding quantity when using a photoinitiator is based on the total weight of a pigment component (A), Preferably it is 5-200 weight%, More preferably, it is 10-150 weight% from a viewpoint of photocurability and developability.

The photopolymerization initiator can use 4-phenoxydichloroacetophenone, 4-tert-butyldichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2- Hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butane-1- Ketones, or acetophenone-based photopolymerization initiators such as 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, benzoin, benzoin Benzoin-based photopolymerization initiators such as methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyl dimethyl ketal, benzophenone, benzoylbenzoic acid, benzoin Methyl formylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylylated benzophenone, or 4-benzoyl-4'-methyldiphenyl sulfide, etc. A benzophenone-based photopolymerization initiator, thioxanthone such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, or 2,4-diisopropylthioxanthone Ketone photopolymerization initiator, 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxy Phenyl)-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(trichloromethyl)-6-styryl-s-triazine, 2-(naphthalene-1-yl) -4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy-naphthalen-1-yl)-4,6-bis(trichloromethyl)-s-triazine , 2,4-trichloromethyl-(piperonyl)-6-triazine, or 2,4-trichloromethyl(4′-methoxystyryl)-6-triazine and other triazine series Photopolymerization initiators, borate-based photopolymerization initiators, carbazole-based photopolymerization initiators, or imidazole-based photopolymerization initiators, etc., but are not limited to these compounds.

The above-mentioned photopolymerization initiators can be used alone or in combination of two or more kinds, and can also be used as a sensitizer, such as α-acyloxyester (α-Ashirokysyster), acylphosphine oxide, methylphenyl glyoxylate, etc. , dibenzoyl, 9,10-phenanthrene quinone, camphor quinone (canf a quinone), ethyl anthraquinone, 4,4'-diethylisophthaloylbenzene, 3,3',4,4' - Compounds such as tetrakis(t-butylperoxycarbonyl)benzophenone or 4,4'-diethylaminobenzophenone, but are not limited to these compounds.

Based on the compounding weight of the photopolymerization initiator contained in the coloring composition, the compounding amount when using a sensitizer is preferably 3 to 60% by weight, and more preferably 5 to 60% by weight from the viewpoint of photocurability and developability. 50% by weight.

[Dispersion Auxiliary]

When dispersing the pigment in the pigment carrier (B), a resin-type pigment dispersant other than the above-mentioned basic resin-type dispersant (a) or a dispersion aid such as a surfactant can be used appropriately. The dispersing aid makes the dispersion of the pigment excellent, and has a greater effect of preventing the re-aggregation of the pigment after dispersion. Therefore, when the following green coloring composition is used, a color filter with high spectral transmittance can be obtained. The composition is obtained by dispersing the pigment in the pigment carrier (B) using a dispersing aid.

Other resin-type pigment dispersants different from the above-mentioned basic resin-type dispersant (a) also have a pigment-affinity site having a pigment adsorbed on the pigment and a site compatible with the pigment carrier. As a property, the dispersant is adsorbed on the pigment to perform the function of stabilizing the dispersion of the pigment in the pigment carrier (B). As the resin-type pigment dispersant, other known resin-type pigment dispersants different from the above-mentioned basic resin-type dispersant (a) can be used. Specifically, polycarboxylates such as polyurethanes or polyacrylates, unsaturated polyamides, etc. can be used. , polycarboxylic acid, (partial) amine salt of polycarboxylate, ammonium polycarboxylate, alkylamine polycarboxylate, polysiloxane, long-chain polyaminoamide phosphate, polycarboxylate containing hydroxyl groups, or Their modified products, oily dispersants such as amides or their salts formed by the reaction of poly(lower alkylene imines) and polyesters with free carboxyl groups, (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-styrene copolymers, base) acrylic acid-(meth)acrylate copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, or water-soluble polymer such as polyvinylpyrrolidone, polyester, modified polyacrylic acid An ester type, an ethylene oxide/propylene oxide addition compound, or a phosphoric acid ester type, etc. These compounds can be used individually or in mixture of 2 or more types.

Surfactants include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali metal salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkylnaphthalenesulfonate , sodium alkyl diphenyl ether disulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl Anionic surfactants such as ether phosphates; polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitol mono Nonionic surfactants such as stearate and polyethylene glycol monolauryl ester; cationic surfactants such as alkyl quaternary ammonium salts or their ethylene oxide adducts; alkyl dimethylamino Alkyl betaines such as betaine acetate, amphoteric surfactants such as alkyl imidazolines, these compounds may be used alone or in combination of two or more, but are not limited to these compounds.

Furthermore, in the green coloring composition for color filters of the present invention, in order to sufficiently disperse the pigment in the pigment carrier (B) and to easily apply it on a transparent substrate such as a glass substrate, the dry film thickness is 0.2 to 5 μm. Coating is performed to form color filter segments, and it contains a solvent, and can be used as "green ink" or "green resist ink".

The above-mentioned solvent uses the above-mentioned mixed organic solvent (c) in the third embodiment of the present invention, but in the first and second embodiments of the present invention, it can be selected from the organic solvent (c1), the organic solvent (c2) and the auxiliary solvent. Choose to use.

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

[storage stabilizer]

Moreover, the green coloring composition of this invention may contain a storage stabilizer in order to stabilize the viscosity of a composition over time.

Storage stabilizers can include, for example, quaternary ammonium chlorides such as benzyltrimethylammonium chloride or diethylhydroxylamine;

Organic acids such as lactic acid or oxalic acid;

Methyl esters of the above organic acids;

Catechols such as tert-butylpyrocatechol;

Organic phosphines such as triphenylphosphine, tetraethylphosphine, or tetraphenylphosphine; or

Phosphites etc.

[Removal of Coarse Particles or Dust]

For the green coloring composition of the present invention, it is preferable to remove coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm or more coarse particles and mixed dust by means of centrifugal separation, sintering filter, or membrane filter. . When there are coarse particles, impurities remain in the color filter, which not only poses a practical problem, but also causes serious problems in production because impurities clog pipes or nozzles in the coating process. Such a green coloring composition preferably does not substantially contain particles of 0.5 μm or larger. More preferably, the particles contained in the green coloring composition are 0.3 μm or less (particle diameter measured by SEM).

In addition, in order to improve the brightness or contrast ratio, the average dispersed particle size is preferably 0.05 to 0.2 μm, and it is more preferable to be 0.06 to 0.15 μm because the brightness or contrast ratio can be further improved.

[Preparation of color filter]

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

The formation of color filter segments using the printing method can be patterned only by repeatedly printing and drying the coloring composition prepared as printing ink. Therefore, as a production method of color filters, mass production at low cost Excellent. Furthermore, with the development of printing technology, it is possible to print fine patterns with high dimensional accuracy and smoothness. For printing, it is preferable to form such a composition that the ink is not dried but cured on the printing plate or the surface layer (blanket). In addition, it is also important to control the fluidity of the ink on the printing press, and it is also possible to adjust the viscosity of the ink by using a dispersant or an extender pigment.

When the color filter segment is formed by photolithography, it can be used as the above-mentioned solvent developing type or alkali developing type colored resist by a coating method such as a spray coating method, a spin coating method, a slit coating method, or a roll coating method. The prepared coloring composition is applied on a transparent substrate so that the dry film thickness is 0.2 to 5 μm. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern placed in contact or non-contact with the film. Thereafter, the uncured portion is removed by immersing in a solvent or alkaline developer or sprayed with a sprayer to form a desired pattern, and the same operation can be repeated for other colors to prepare a color filter. Furthermore, in order to accelerate the polymerization of a colored resist, heating may be performed as needed. According to the photolithography method, a highly precise color filter can be produced by the printing method described above.

At the time of development, an aqueous solution such as sodium carbonate or sodium hydroxide may be used as an alkali developing solution, or an organic base such as dimethylbenzylamine or triethanolamine may be used. In addition, an antifoaming agent or a surfactant may be added to the developer.

In addition, in order to improve the sensitivity of ultraviolet exposure, after coating and drying the above-mentioned colored resist, a water-soluble or alkali water-soluble resin, such as polyvinyl alcohol or water-soluble acrylic resin, can be coated and dried to form an anti-oxidation layer. The resulting polymerized hindered film was then subjected to UV exposure.

The color filter of the present invention can be produced by an electrodeposition method, a transfer method, or the like other than the methods described above, and the coloring composition of the present invention can be used in either method. In addition, the electrodeposition method is a method of preparing a color filter by utilizing a transparent conductive film formed on a substrate and electrodepositing color filter segments of various colors on the transparent conductive film through electrophoresis of colloidal particles.

In addition, the transfer method is a method in which color filter segments are previously formed on the surface of a peelable transfer substrate, and the color filter segments are transferred onto a desired substrate.

[color filter]

Next, the color filter of the present invention will be described. The color filter of the present invention has at least one red color filter segment, at least one blue color filter segment, and at least one green color filter segment, and the at least one green color filter segment uses The color filter of the present invention is formed using a coloring composition.

The red color filter segments can be formed using common red coloring compositions. In red coloring compositions for example C.I. Pigment Red 7, 14, 41, 48:1, 48:2, 48:3, 48:4, 57:1, 81, 81:1, 81:2, 81: 3, 81: 4, 122, 146, 168, 177, 178, 184, 185, 187, 200, 202, 208, 210, 246, 254, 255, 264, 270, 272, 279 and other red pigments.

In the red coloring composition, orange pigments such as C.I. Pigment Orange 43, 71, 73 and/or C.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, Yellow pigments of 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 198, 199, 213, 214, etc.

In addition, the blue color filter segment can be formed using a general blue coloring composition. Blue pigments such as C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 60, 64, etc. can be used in the blue coloring composition. In addition, purple pigments such as C.I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, and 50 may be used in combination in the purple coloring composition.

[Example]

Hereinafter, although this invention is demonstrated based on an Example, this invention is not limited to these Examples. In addition, in Examples and Comparative Examples, "parts" means "parts by weight". In addition, Mn and Mw represent number average molecular weight and weight average molecular weight, respectively.

(1) Average molecular weight of basic resin type dispersant (a)

In the following examples and comparative examples, 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 the device, and SUPER-AW3000 is used As a column, with 30mM triethylamine and 10mM LiBr's N,N-dimethylformamide as the eluent, the number average molecular weight (Mn) and weight average molecular weight (Mw) of the polystyrene conversion measured.

(2) Amine value

The amine value of the basic resin type dispersant is a value obtained by converting the measured total amine value (mgKOH/g) into solid content according to the method of ASTM D2074.

(3) The average molecular weight of the resin of the pigment carrier (B)

The number-average molecular weight (Mn) and weight-average molecular weight (Mw) of the acrylic resin used as the resin of the pigment carrier (B) were obtained by using a TSKgel column (manufactured by Tosoh Co., Ltd.) and GPC (Tosoh Co., Ltd.) equipped with an RI detector. Co., Ltd., HLC-8120GPC), and polystyrene-equivalent number average molecular weight (Mn) and weight average molecular weight (Mw) measured using THF in a developing solvent.

(4) The acid value of the resin of the pigment carrier (B)

The acid value of the acrylic resin used as the resin of the pigment carrier (B) is a value obtained by converting the measured acid value (mgKOH/g) into solid content in accordance with the potentiometric titration method of JIS K0070.

(first embodiment)

The green coloring composition containing the said basic resin type dispersant (a) as an essential component is demonstrated using an Example (Example I series) and a comparative example (Comparative Example I series).

First, the resin-type dispersants used in the series of Examples I and the series of Comparative Examples I, their solutions, commercially available resin-type dispersant solutions, acrylic resins, and solutions thereof will be described.

Synthesis example I-1: Synthesis of resin type dispersant I-1 and preparation of its solution

In a four-neck detachable flask with a thermometer, a stirrer, a distillation tube and a cooler, add 70 parts of methyl ethyl ketone, 76.0 parts of n-butyl acrylate, 2.8 parts of spartine, and ethyl bromoisobutyrate 1.9 parts of ester were heated up 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 3 hours of polymerization, the polymerization solution was sampled, and the polymerization yield was confirmed to be 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 were added to further carry out polymerization . From the solid content of the polymerization solution after 2 hours, it was confirmed that the polymerization yield was 97% or more, and the polymerization was terminated by cooling to room temperature. Dilute 100 parts of the obtained resin solution with 100 parts of methyl ethyl ketone, add 60 parts of cation exchange resin "Diaion PK228LH (manufactured by Mitsubishi Chemical Co., Ltd.)" and stir at room temperature for 1 hour, and then add 10 parts of water Talc (キヨ一ワード 500SN: manufactured by Kyowa Chemical Industry Co., Ltd.) was used as a neutralizing agent, and stirring was performed for 30 minutes. The residue of the polymerization catalyst 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 resin-type dispersant I-1 (Mn=10200, Mw=12200, amine value 86 mgKOH/g) with a non-volatile content of 40% by weight. The solution.

Synthesis example I-2: Synthesis of resin type dispersant I-2 and preparation of its solution

Add 70 parts of methyl ethyl ketone, 75.0 parts of n-butyl acrylate, 10.0 parts of methyl methacrylate, 2.3 parts of spartine, and ethyl bromoisobutyrate in the same manner as in Synthesis Example I-1 above. 1.6 parts, and add 0.9 parts of cuprous chloride to initiate polymerization. After 3 hours of polymerization, 15.0 parts of N,N-dimethylaminoethyl methacrylate and 30.0 parts of MEK were added, and further polymerization was performed for 2 hours. Afterwards, the operation of removing the residue of the polymerization catalyst was carried out in the same manner as in the above-mentioned Synthesis Example I-1 to obtain a resin-type dispersant I-2 (Mn=11900, Mw=13200, amine value 54 mgKOH/ g) solution.

Synthesis example I-3: Synthesis of resin type dispersant I-3 and preparation of its solution

Add 70 parts of methyl ethyl ketone, 45.0 parts of ethyl acrylate, 43.0 parts of methyl methacrylate, 3.3 parts of spartine, and 2.8 parts of ethyl bromoisobutyrate in the same manner as the above synthesis example I-1. part, and added 1.4 parts of cuprous chloride to initiate polymerization. After 3 hours of polymerization, 12.0 parts of N,N-dimethylaminoethyl methacrylate and 30.0 parts of MEK were added, and further polymerization was performed for 2 hours. Afterwards, the operation of removing the residue of the polymerization catalyst was carried out in the same manner as in Synthesis Example I-1 above to obtain a resin-type dispersant I-3 (Mn=7000, Mw=8500, amine value 43 mgKOH/ g) solution.

Synthesis example I-4: Synthesis of resin type dispersant I-4 and preparation of its solution

Add 70 parts of methyl ethyl ketone, 71.0 parts of n-butyl acrylate, 2.8 parts of spartine, and 1.9 parts of ethyl bromoisobutyrate in the same manner as the above synthesis example I-1, and add chlorinated Copper 1.4 parts initiates polymerization. After the polymerization for 3 hours, 29.0 parts of N,N-dimethylaminoethyl methacrylate and 30.0 parts of MEK were added, and polymerization was further performed for 2 hours. Afterwards, the operation of removing the residue of the polymerization catalyst was carried out in the same manner as in Synthesis Example I-1 above to obtain a resin-type dispersant I-4 (Mn=10000, Mw=12000, amine value 105 mgKOH/ g) solution.

Synthesis example I-5: Synthesis of resin type dispersant I-5 and preparation of its solution

Add 70 parts of methyl ethyl ketone, 66.0 parts of n-butyl acrylate, 2.8 parts of spartine, and 1.9 parts of ethyl bromoisobutyrate in the same method as the above synthesis example I-1, and add chlorinated Copper 1.4 parts initiates polymerization. After 3 hours of polymerization, 34.0 parts of N,N-dimethylaminoethyl methacrylate and 30.0 parts of MEK were added, and further polymerization was performed for 2 hours. Afterwards, the operation of removing the residue of the polymerization catalyst was carried out in the same manner as in Synthesis Example I-1 above to obtain a resin-type dispersant I-5 (Mn=9800, Mw=12000, amine value 121 mgKOH/ g) solution.

Synthesis Example I-6: Preparation of Commercially Available Resin-Type Dispersant Solution

BYK-161, 163, 164, 167, 174, 184, 2000, 2050 manufactured by Vitsuku Chemical Japan Co., Ltd., SOLSPERSE-34750, 56000 manufactured by Nippon Ruble Japan Co., Ltd., Chiba Japan Co., Ltd. For EFKA4330, 4046, 4060, and 4080 produced by the company, for those with less than 40% of non-volatile content, dry under reduced pressure to make the non-volatile content more than 60%, and then use ethylene glycol monomethyl ether acetate to prepare the non-volatile content of A 40% by weight solution was used as a solution of a commercially available resin-type dispersant.

Synthesis Example I-A: Synthesis of Acrylic Resin I-A and Preparation of Its Solution

Add 800 parts of cyclohexanone to the reaction container, and heat to 100°C while injecting nitrogen gas into the container. At the same temperature, 80.0 parts of styrene, 40.0 parts of methacrylic acid, and methacrylic acid-N are added dropwise over 1 hour. A mixture of 85.0 parts of N-methyl ester, 95.0 parts of n-butyl methacrylate, and 10.0 parts of azobisisobutyronitrile was subjected to polymerization reaction.

After the dropwise addition, the reaction was further carried out at 100°C for 3 hours, a solution obtained by dissolving 2.0 parts of azobisisobutyronitrile in 50 parts of cyclohexanone was added, and the reaction was continued at 100°C for 1 hour to obtain the weight average molecular weight About 30000, acid value is the cyclohexanone solution of acrylic resin I-A of 87mgKOH/g.

After cooling to room temperature, sample about 2 g of the resin solution, heat and dry it at 180°C for 20 minutes, measure the non-volatile content, and add ethylene glycol monomethyl ether acetate to the previously synthesized resin solution to make it non-volatile. Composition 20% by weight A solution of acrylic resin I-A was thus prepared.

Synthesis examples I-B to I-P: Synthesis of acrylic resins I-B to I-P and preparation of their solutions

Using the monomer composition and initiator amount (azobisisobutyronitrile amount) shown in Table 2 below, acrylic resins I-B to I-P were synthesized in the same manner as the above acrylic resin I-A, and their solutions were prepared. In addition, the acid value and weight average molecular weight of the synthesized resin are shown in Table 2.

[Table 2]

Explanation of abbreviations in Table 2

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

(F) formula: Y>-750X+51000

(G) formula: Y>940X-79000

(H) formula: Y>8000

X: acid value of resin (mgKOH/g)

Y: weight average molecular weight of the resin

[Embodiment 1-1]

11.0 parts of zinc halide phthalocyanine green pigment (C.I. Pigment Green 58), 2.5 parts of SOLSPERSE-56000 solution prepared according to the preparation method of the above-mentioned resin dispersion type dispersant solution, 40.0 parts of the above-mentioned acrylic resin I-A solution, and ethylene glycol After the mixture of 46.5 parts of alcohol monomethyl ether acetate was uniformly stirred and mixed, the zirconia beads with a diameter of 0.5 mm were used to grind the mixture in an Aiger mill ("Minimodel M-250MKII" manufactured by Aiga Japan Co., Ltd.) ) for 5 hours, and filtered through a 5.0 μm filter to prepare a green pigment dispersion.

Next, stirring and mixing were carried out so that 60.0 parts of the above-mentioned green pigment dispersion, 11.0 parts of the solution of the above-mentioned acrylic resin I-A, 4.2 parts of trimethylolpropane triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd. "NK Ester ATMPT"), and photopolymerized A mixture of 1.2 parts of an initiator ("Irugakiyua-907" manufactured by Chiba Japan Corporation), 0.4 parts of a sensitizer ("EAB-F" manufactured by Hodo Ketani Chemical Co., Ltd.), and 23.2 parts of ethylene glycol monomethyl ether acetate was uniformly was formed, and then filtered through a 1.0 μm filter to obtain an alkali-developing type green resist material I-1.

[Example I-2 to I-24]

Using the solution of the above-mentioned resin type dispersant shown in Table 3, the above-mentioned pigment derivative, and the solution of the above-mentioned acrylic resin, an alkali-developing type resist material I- was obtained in the same manner as in Example I-1. 2 to I-24. Table 4 shows the types of resin-type dispersants (either block type or non-block type).

[table 3]

[Table 4]

[Embodiment 1-25]

With 10.0 parts of zinc halide phthalocyanine green pigment (C.I. Pigment Green 58), 2.5 parts of resin solution of SOLSPERSE-56000 (non-volatile content is 40% by weight), following formula I-9:

The mixture of 1.0 parts of pigment derivatives with basic functional groups, 40.0 parts of the above-mentioned acrylic resin I-A solution, and 46.5 parts of ethylene glycol monomethyl ether acetate was uniformly stirred and mixed, and then used a diameter of 0.5mm The zirconia beads were dispersed in an Egger mill ("Minimodel M-250MKII" manufactured by Aiga Japan Co., Ltd.) for 5 hours, and filtered through a 5.0 μm filter to prepare a green pigment dispersion.

Next, stirring and mixing were carried out so that 60.0 parts of the above-mentioned green pigment dispersion, 11.0 parts of the solution of the above-mentioned acrylic resin I-A, 4.2 parts of trimethylolpropane triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd. "NK Ester ATMPT"), and photopolymerized A mixture of 1.2 parts of an initiator ("Irugakiyua-907" manufactured by Chiba Japan Corporation), 0.4 parts of a sensitizer ("EAB-F" manufactured by Hodo Ketani Chemical Co., Ltd.), and 23.2 parts of ethylene glycol monomethyl ether acetate was uniformly was formed, and then filtered through a 1.0 μm filter to obtain an alkali-developing type green resist material I-25.

[Example I-26 to I-48]

Using the solution of the above-mentioned resin type dispersant shown in Table 5, the above-mentioned pigment derivative, and the solution of the above-mentioned acrylic resin, the alkali-developing type resist material I- was obtained in the same manner as in Example I-25. 26 to I-48.

[table 5]

[Example I-49]

With 10.0 parts of zinc halide phthalocyanine green pigment (C.I. Pigment Green 58), 2.5 parts of SOLSPERSE-56000 solution (40% by weight of non-volatile components), the following formula I-10:

1.0 parts of pigment derivatives having a triazine ring skeleton having an anchor part (anka part) of a basic functional group of benzimidazolone shown, 40.0 parts of a solution of the above-mentioned acrylic resin I-A, and ethylene glycol monomethyl ether After the mixture of 46.5 parts of acetate was uniformly stirred and mixed, it was dispersed in an Egger mill ("Minimodel M-250MKII" manufactured by Aiga Japan Co., Ltd.) using zirconia beads with a diameter of 0.5 mm. A 5.0 μm filter was used to prepare a green pigment dispersion.

Next, stirring and mixing were carried out so that 60.0 parts of the above-mentioned green pigment dispersion, 11.0 parts of the solution of the above-mentioned acrylic resin I-A, 4.2 parts of trimethylolpropane triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd. "NK Ester ATMPT"), and photopolymerized A mixture of 1.2 parts of an initiator ("Irugakiyua-907" manufactured by Chiba Japan Corporation), 0.4 parts of a sensitizer ("EAB-F" manufactured by Hodo Ketani Chemical Co., Ltd.), and 23.2 parts of ethylene glycol monomethyl ether acetate was uniformly was formed, and then filtered through a 1.0 μm filter to obtain an alkali-developing type green resist material I-49.

[Embodiment I-50～I-72]

As shown in Table 6, using the solution of the above-mentioned resin type dispersant, the solution of the above-mentioned pigment derivative and the above-mentioned acrylic resin, an alkali-developing type resist material I-50 was obtained in the same manner as in Example I-49. ~I-72.

[Table 6]

[Comparative Examples I-1 to I-15]

Except that the solution of the dispersant shown in Table 7 (non-volatile content is 40% by weight) was used instead of the SOLSPERSE-56000 solution used in Example I-1, the other was the same as in Example I-1 to obtain an alkali-developing type resist. Etching materials I-73 to I-87.

[Table 7]

[Comparative Example I-16]

Except for using a copper halide phthalocyanine green pigment (C.I. Pigment Green 36) instead of a zinc halide phthalocyanine green pigment (C.I. Pigment Green 58), the alkali-developable resist material I-88 was obtained in the same manner as in Example I-3. .

(Evaluation method)

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

(1) Measurement method of viscosity characteristics

The viscosity of the obtained alkali-developing resist material was obtained by measuring the viscosity at a rotational speed of 20 rpm using an E-type viscometer ("ELD-type viscometer" manufactured by Toki Sangyo Co., Ltd.). Furthermore, the ratio of the viscosities (called thixotropy index, the larger the value, the higher the thixotropy) at the rotation speed of 6 rpm and 60 rpm was obtained, and the thixotropy was evaluated.

(2) Determination method of viscosity increase rate over time

Using an E-type viscometer ("ELD-type viscometer" manufactured by Toki Sangyo Co., Ltd.), the initial viscosity and The time-dependent viscosity was performed by standing at 40 degreeC for 1 week. The initial viscosity and time-lapse viscosity thus measured were substituted into the following formula, and the time-lapse viscosity increase rate was measured.

[Time-lapse viscosity increase rate]=(time-lapse viscosity/initial viscosity)×100

(3) Measurement method of brightness

The resulting alkali-developable resist material was prepared by using a spin coater and changing the number of rotations to prepare three coated substrates so that the dry film thickness and the chromaticity y in the CIE chromaticity system were 0.62, 0.6, and 0.58. After coating, dry in a hot air oven at 80°C for 30 minutes, then measure the film thickness respectively, and use the linear correlation method to obtain the brightness when the chromaticity y is 0.6 from the data of 3 pieces. Chromaticity was measured using a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.).

(4) Determination method of contrast ratio of coating film

The contrast ratio when the chromaticity y is 0.6 was calculated|required by the linear correlation method from the data of 3 board|substrates used for brightness measurement. Chromaticity was measured using a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.).

The measuring apparatus and numerical value calculation method of the contrast ratio of a coating film are demonstrated using the following FIG. 1. FIG.

The light emitted from the backlight unit (7) for liquid crystal displays is polarized by the polarizer (6), passes through the dry coating film (4) of the coloring composition coated on the glass substrate (5), and reaches the polarizer (3) . If the polarization plane of the polarizer (6) is parallel to the polarizer (3), the light passes through the polarizer (3), but when the polarization plane is vertical, the light is blocked by the polarizer (3). However, when the light polarized by the polarizer (6) passes through the dry coating film (4) of the coloring composition, scattering or the like caused by pigment particles occurs, and dislocation occurs in a part of the polarization plane, then when the polarizer is parallel to The amount of light passing through the polarizer (3) decreases, and when the polarizer is vertical, part of the light passes through the polarizer (3). The transmitted light was measured as luminance on the polarizing plate, and the ratio (contrast ratio) of the luminance when the polarizing plate was parallel to the luminance when the polarizing plate was perpendicular was calculated.

(Contrast ratio) = (brightness when parallel) / (brightness when vertical)

Therefore, if scattering by the pigment of the dried coating film (4) of the coloring composition occurs, the luminance at the time of parallelism decreases and the luminance at the time of perpendicularity increases, so the contrast ratio becomes low.

In addition, 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 addition, in order to shield unnecessary light during the measurement, a black mask (2) with a square hole of 1 cm side length opened in the measurement portion was placed.

(5) Determination of the time-dependent change rate of the contrast ratio

The obtained alkali-developing resist material was left to stand at 40° C. for seven days, and the rate of change in CR (contrast ratio) after standing for seven days relative to the initial CR (contrast ratio) was calculated from the following formula.

Rate of change in CR over time = (CR after seven days of standing)/(initial CR)

If the rate of change of the time-dependent contrast ratio is 90% or more, it can reach a practical level. Preferably it is 95% or more. When it exceeds this range, storage stability will be inferior, and it cannot become a green coloring composition for color filters.

Tables 8-11 show the results of the thixotropic index, viscosity, time-lapse viscosity increase rate, contrast ratio (CR), time-lapse ratio change rate of the contrast ratio (CR) and brightness of the resists obtained as described above.

[Table 8]

CR: Contrast Ratio

[Table 9]

CR: Contrast Ratio

[Table 10]

CR: Contrast Ratio

[Table 11]

CR: Contrast Ratio

As shown in the series of Examples I, when using a basic resin-type dispersant with an amine value of 35 to 100 mgKOH/g, a dispersant with good fluidity, excellent storage stability over time, and high brightness and high contrast ratio can be obtained. Green coloring composition.

When the above resin type dispersant is a block copolymer resin comprising a basic copolymerization block (a1) and a pigment carrier affinity copolymerization block (a2), a high contrast ratio can further be formed.

Furthermore, when a dye derivative having a basic functional group is used in combination with the above-mentioned resin-type dispersant, the initial contrast ratio becomes high, and the viscosity characteristics and temporal stability are generally good. Furthermore, the most excellent green coloring composition can be obtained when it is used in combination with a resin such as (F)Y>-750X+51000 when X is the acid value and Y is the average molecular weight. , and (G)Y>940X-79000, and (H)Y>8000 of the resin represented by the range.

On the other hand, in Comparative Examples I-1 to I-15, both fluidity and storage stability were inferior, and the green coloring composition with a low contrast ratio was formed. In addition, in Comparative Example I-16, since copper halide phthalocyanine green was used, a green coloring composition having poor brightness was formed.

(second embodiment)

Next, the green coloring composition containing the said pigment derivative (b) as an essential component is demonstrated using an Example (Example II series) and a comparative example (Comparative Example II series).

First, the acrylic resin solutions used in the series of Examples II and the series of Comparative Examples II will be described.

Synthesis Example II-A: Synthesis of Acrylic Resin II-A and Preparation of Its Solution

Put 800 parts of cyclohexanone into the reaction container, heat it to 100°C while injecting nitrogen into the container, and add 80.0 parts of styrene, 40.0 parts of methacrylic acid, and 85.0 parts of methyl methacrylate dropwise at the same temperature for 1 hour. Parts, 95.0 parts of n-butyl methacrylate, and 2.0 parts of azobisisobutyronitrile were polymerized.

After the dropwise addition, and reacted at 100°C for 3 hours, a solution obtained by dissolving 2.0 parts of azobisisobutyronitrile with 50 parts of cyclohexanone was added, and the reaction was continued at 100°C for 1 hour to obtain a weight average molecular weight of about 30000, the cyclohexanone solution of acrylic resin II-A with an acid value of 87 mgKOH/g.

After cooling to room temperature, sample about 2 g of the resin solution, heat and dry it at 180°C for 20 minutes, measure the non-volatile content, and add ethylene glycol monomethyl ether acetate to the previously synthesized resin solution to make it non-volatile. Composition 20% by weight A solution of acrylic resin II-A was thus prepared.

Synthesis examples II-B to II-P: Synthesis of acrylic resins II-B to II-P and preparation of their solutions

Using the monomer composition and initiator amount (azobisisobutyronitrile amount) shown in Table 12 below, acrylic resins II-B to II-P were synthesized in the same way as the above-mentioned acrylic resin II-A synthesis method, and prepared their solutions. In addition, the acid value and weight average molecular weight of the synthesized resin are shown in Table 12.

[Table 12]

Explanation of abbreviations in Table 12

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

(F) formula: Y>-750X+51000

(G) formula: Y>940X-79000

(H) formula: Y>8000

X: acid value of resin (mgKOH/g)

Y: weight average molecular weight of the resin

[Example II-1]

11.0 parts of zinc halide phthalocyanine green pigment (C.I. Pigment Green 58), the following formula II-9:

1.0 parts of pigment derivatives having a triazine ring skeleton whose anchor portion is a basic functional group of benzimidazolone, 40.0 parts of acrylic resin II-A solution, and 48.0 parts of ethylene glycol monomethyl ether acetate After uniform stirring and mixing of the mixture, zirconia beads with a diameter of 0.5 mm were dispersed in an Egger mill ("Minimodel M-250MKII" manufactured by Aiga Japan Co., Ltd.) for 5 hours, and then filtered through a 5.0 μm filter. filter to prepare a green pigment dispersion.

Next, stirring and mixing were carried out so that 60.0 parts of the above-mentioned green pigment dispersion, 11.0 parts of acrylic resin II-A solution, 4.2 parts of trimethylolpropane triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd. "NK Ester ATMPT"), and light 1.2 parts of a polymerization initiator ("Irugakiyua-907" manufactured by Chiba Specialty Chemical Co., Ltd.), 0.4 parts of a sensitizer ("EAB-F" manufactured by Hodo Ketani Chemical Co., Ltd.), and 23.2 parts of ethylene glycol monomethyl ether acetate A mixture of two parts was uniformly formed, and then filtered through a 1.0 μm filter to obtain an alkali-developing type green resist material II-1.

[Example II-2]

In addition to making the solution of acrylic resin II-A 37.0 parts, and adding ethylene glycol monomethyl ether acetate so that the non-volatile content is 20% by weight, an acrylic polymer dispersant (Chiba Japan Except for 3 parts of solutions of "EFKA4300 manufactured by the company, 56 mgKOH/g of amine value"), it carried out similarly to Example II-1, and obtained the alkali developing type resist material II-2.

[Example II-3]

In addition to making the solution of acrylic resin II-A 37.0 parts, and adding ethylene glycol monomethyl ether acetate so that the non-volatile content was 20% by weight, a urethane-based polymer dispersant ( Alkali-developing resist material II-3 was obtained in the same manner as in Example II-1, except for 3 parts of the solution of "BYK-163, amine value 10 mgKOH/g" manufactured by Vitsuku Chemical Co., Ltd.

[Example II-4]

Except that the pigment derivative having the triazine ring skeleton with the basic substituent of benzimidazolone as the anchor portion is changed into the following formula II-10:

An alkali-developable resist material II-4 was obtained in the same manner as in Example II-1 except for the dye derivative having a triazine ring skeleton having a basic substituent whose anchor portion was anthraquinone.

[Example II-5]

Except changing 11.0 parts of zinc halide phthalocyanine green pigment (C.I. Pigment Green 58) to 9.0 parts of zinc halide phthalocyanine green pigment (C.I. Pigment Green 58) and metal complex yellow pigment (C.I. Yellow Pigment E4GN") 2.0 parts, other than Example II-1, the alkali-developing type resist material II-5 was obtained.

[Example II-6]

Except that 1.0 parts of the pigment derivative having a triazine ring skeleton with a basic substituent having an anchor portion of benzimidazolone is changed into the following formula II-11:

Except for 1.0 part of the dye derivative having the basic substituent whose anchor portion is benzimidazolone, an alkali-developable resist material II-6 was obtained in the same manner as in Example II-1.

[Example II-7]

Except that 1.0 parts of the pigment derivative having a triazine ring skeleton with a basic substituent having an anchor portion of benzimidazolone is changed into the following formula II-12:

Alkali-developable resist material II-7 was obtained in the same manner as in Example II-1, except for 1.0 part of the dye derivative having a basic substituent whose anchor portion was anthraquinone.

[Example II-8 to II-15]

Except having changed the solution of acrylic resin II-A into the solution of acrylic resin II-B, it carried out similarly to Example II-1, and obtained alkali-developing type resist material II-8. Hereinafter, except that only the solution of the acrylic resin II-A was changed to the solution of the acrylic resins II-C to II-I, the alkali-developing type resist materials II-9 to II-1 were obtained in the same manner as in Example II-1. 15.

[Comparative Example II-1]

An alkali-developing type resist material II-16 was obtained in the same manner as in Example II-1, except that the solution of the acrylic resin II-A was 41.0 parts and the pigment derivative was removed.

[Comparative Example II-2]

In addition to changing 11.0 parts of zinc halide phthalocyanine green pigment (C.I. Pigment Green 58) to 11.0 parts of copper halide phthalocyanine green pigment (C.I. Pigment Green 36, Toyo Ink Manufacturing Co., Ltd. “Rio Nol Green 6YK”), other Alkali-developing type resist material II-17 was obtained similarly to Example II-1.

[Comparative Example II-3]

Except changing 11.0 parts of the zinc halide phthalocyanine green pigment (C.I. Pigment Green 58) to 11.0 parts of the copper halide phthalocyanine green pigment (C.I. Pigment Green 7, Toyo Ink Manufacturing Co., Ltd. “Rio Nol Green YS-07”) , Others were similar to Example II-1 to obtain alkali-developing type resist material II-18.

[Example II-16 to II-22]

Except having changed the solution of acrylic resin II-A into the solution of acrylic resin II-J, it carried out similarly to Example II-1, and obtained alkali-developing type resist material II-19. Hereinafter, except that only the solution of the acrylic resin II-A was changed to the solution of the acrylic resin II-K to II-P, the alkali developing type resist materials II-20 to II-P were obtained in the same manner as in Example II-1. 25.

(Evaluation method)

Table 13 shows the results of evaluating the viscosity, thixotropic index, brightness of the coating film, and contrast ratio of the resist obtained above in the same manner as the first embodiment.

Table 13

As shown in the series of Examples II, if a pigment derivative having a basic substituent is used when dispersing a zinc halide phthalocyanine pigment, a coloring composition with excellent fluidity can be obtained, and a high brightness and a high contrast ratio can be simultaneously achieved. coating film. In particular, when a pigment derivative having a triazine skeleton is used, brightness and contrast ratio show favorable values. Furthermore, it is particularly good when used in combination with a resin solution where Y>-750X+51000 and Y>940X-79000 and The resin solution represented by the range of Y>8000. On the other hand, the resist material using the coloring composition of Comparative Example II-1 had a significantly higher viscosity than the resist material obtained in Examples, and the brightness and contrast ratio of the coating film were also low. s level. In addition, the viscosity of the resist materials using the coloring compositions of Comparative Examples II-2 and II-3 was at the same level as that of the resist materials obtained in Examples, and the contrast ratio of the coating film was also almost at the same level. level, but its brightness is a lower value than the coating films obtained in Examples.

(third embodiment)

Furthermore, the green coloring composition containing the said mixed organic solvent (c) as an essential component is demonstrated using an Example (Example III series) and a comparative example (Comparative Example III series).

First, the evaluation method of resist coatability and the acrylic resin solution used in the series of Examples III and the series of Comparative Examples III will be described.

[Evaluation method of coatability]

Evaluation of applicability will be described.

Coating was performed using a die coating system and a spin coating system to form an average film thickness of 2.0 μm on a glass substrate with a size of 360 mm×465 mm, and the resulting coated substrate was subjected to 20 minutes at 70° C. pre-baking to obtain a dry coating film. Hereinafter, evaluation items, contents, and display methods of results will be described.

<Spin coating method only>

(Film thickness uniformity)

"Film thickness uniformity (end part)": The film thickness was measured every 5 mm from the center part of the short edge part of the coated substrate along the substrate center direction to 5 cm in length. The maximum film thickness is T ₁ , the minimum film thickness is T ₂ , and the average film thickness is T, and the film thickness uniformity (edge) is calculated by the following formula (A).

"Film thickness uniformity (other than end portions)": The film thickness was measured every 2 cm in the length from the center of the coated substrate in the diagonal direction up to 26 cm. In the same manner as above, the film thickness uniformity (except for the edge portion) was calculated by the following formula (A).

Film thickness uniformity [%]=((T ₁ -T ₂ )/T)×100(A)

The film thickness uniformity [%] is preferably a small value, and less than 4% is marked as ○, 4% or more and less than 10% is marked as Δ, and 10% or more is marked as ×.

<Die coating method only>

(Vertical unevenness)

"Vertical streaks": For die-coated coated substrates, "vertical streaks" as streaks in the slit advancing direction as aggregates originating from the opening of the slit were evaluated using white transmitted light. Uneven". When there was no vertical unevenness by visual inspection, it was marked as ◯, and when vertical unevenness was observed, it was marked as ×.

(maximum transmittance)

The resulting alkali-developable resist material was prepared by using a spin coater and changing the number of rotations to prepare three coated substrates so that the dry film thickness and the chromaticity y in the CIE chromaticity system were 0.62, 0.6, and 0.58. After coating, dry in a hot air oven at 80°C for 30 minutes, then measure the film thickness respectively, and use the linear correlation method to obtain the maximum transmittance when the chromaticity y is 0.6 from the data of 3 pieces. Chromaticity was measured using a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.).

Next, the acrylic resin solutions and pigments used in the series of Examples III and the series of Comparative Examples III will be described.

Synthesis Example III-A: Preparation of Acrylic Resin III-A Solution

Put 800 parts of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMAC) into the reaction vessel, heat to 100° C. while injecting nitrogen gas into the vessel, and add 60.0 parts of styrene and formaldehyde dropwise at the same temperature for 1 hour. A mixture of 60.0 parts of methacrylic acid, 65.0 parts of methyl methacrylate, 65.0 parts of butyl methacrylate, and 10.0 parts of azobisisobutyronitrile was polymerized.

After dropping, react at 100° C. for 3 hours, then add a solution obtained by dissolving 2.0 parts of azobisisobutyronitrile with 50 parts of PGMAC, and continue the reaction at 100° C. for 1 hour to obtain a weight average molecular weight (Mw) of 40,000 solution of acrylic resin III-A.

After cooling to room temperature, sample about 2 g of the resin solution, heat and dry it at 180°C for 20 minutes, measure the non-volatile content, and add PGMAC to the previously synthesized resin solution so that the non-volatile content becomes 20% by weight to prepare acrylic acid Solution of Resin III-A.

Pigment preparation example

Next, the method of measuring the primary particle diameter of the pigment and the preparation method of the pigment will be described.

(Primary particle size measurement method)

The average primary particle size of a pigment is measured by the method of directly measuring the size of a primary particle from the electron micrograph of a transmission electron microscope (TEM). Specifically, the minor-axis diameter and the major-axis diameter of the primary particle of each pigment were measured, and the average value was used as the particle diameter of the pigment particle. Next, for 100 pigment particles, the volume (weight) of each particle was approximated to a cube of the desired particle diameter, and the volume average particle diameter was expressed as the average primary particle diameter.

(modulation of green pigment III-1)

200 parts of zinc halide phthalocyanine green pigment (C.I. Pigment Green 58), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were added to a 1-gallon kneader made of stainless steel (Garon Ni-da) (manufactured by Inoue Seisakusho). It kneaded at 80 degreeC for 6 hours. Next, this kneaded product was added to 8 liters of warm water, and stirred for 2 hours while heating to 80°C to form a slurry, which was repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 85°C. One day and one night, 190 parts of green pigment III-1 were obtained. The primary particle diameter determined by TEM (transmission electron microscope) was 50 nm.

(modulation of green pigment III-2)

Green Pigment III-2 was obtained in the same way as Green Pigment III-1, except that the zinc halide phthalocyanine green pigment (C.I. Pigment Green 58) was replaced with the copper halide phthalocyanine green pigment (C.I. Pigment Green 36). The primary particle diameter determined by TEM (transmission electron microscope) was 60 nm.

(modulation of green pigment III-3)

Green Pigment III-3 was obtained in the same manner as Green Pigment III-1, except that the zinc halide phthalocyanine green pigment (C.I. Pigment Green 58) was replaced with the copper halide phthalocyanine green pigment (C.I. Pigment Green 7). The primary particle diameter determined by TEM (transmission electron microscope) was 60 nm.

(Preparation of yellow pigment)

A yellow pigment was obtained in the same manner as Green Pigment III-1, except that the zinc halide phthalocyanine green pigment (C.I. Pigment Green 58) was replaced with a metal complex yellow pigment (C.I. Pigment Yellow 150). The primary particle diameter determined by TEM (transmission electron microscope) was 70 nm.

Example of Pigment Dispersion Preparation

Next, the preparation method of the green coloring composition (green pigment dispersion) for color filters is demonstrated.

(Preparation of Green Pigment Dispersion III-1)

A mixture of 11.0 parts of green pigment III-1 (C.I. Pigment Green 58), 40 parts of acrylic resin III-A solution, 48.0 parts of propylene glycol monomethyl ether acetate (PGMAC), and 1.0 parts of resin-type dispersant (EFKA4300) After uniform stirring and mixing, zirconia beads with a diameter of 0.5 mm were dispersed in an Egger mill ("Minimodel M-250MKII" manufactured by Aiga Japan Co., Ltd.) for 5 hours, and filtered through a 5.0 μm filter. Preparation of Green Pigment Dispersion III-1.

Hereinafter, green pigment dispersions III-2 to III-8 were obtained in the same manner as the preparation of green pigment dispersion III-1 using the materials shown in Table 14. In addition, the pigment dispersion III-5 prepared a pigment dispersion using 9 parts of green pigment III-1 and 2 parts of yellow pigments.

[Table 14]

〔Resist material manufacturing example〕

Next, the method of measuring and preparing the dispersed particle size of the green resist material will be described.

(Measurement of dispersed particle size)

Microtrac UPA-EX150 from Nikkiso Co., Ltd. using the dynamic light scattering method (FFT power spectrum method) was used. The particle permeability was used as the absorption mode, the particle shape was non-spherical, and D50 was used as the average diameter. As the dilution solvent for the measurement, the solvent used for the dispersion was used, and the measurement was performed on the sample treated with ultrasonic waves.

(Particle size measured by SEM)

The particle size of the pigment measured by SEM is measured by a method of directly measuring the size of the largest particle from an electron micrograph of a scanning electron microscope (SEM). Specifically, take 50 pigment particles in the photo, measure the minor-axis diameter and major-axis diameter of the primary particle of each pigment, and use the average value as the particle diameter of the pigment particle, and retain 1 significant figure after the decimal point Indicates its largest particle size.

(Green resist material III-1)

60.0 parts of green pigment dispersion III-1

11.0 parts acrylic resin solution

4.2 parts of trimethylolpropane triacrylate ("NK Ester ATMPT" manufactured by Shin-Nakamura Chemical Co., Ltd.)

1.2 parts of photopolymerization initiator ("Irugakiyua-907" manufactured by Chiba Specialty Technology Chemical Co., Ltd.)

0.4 parts of sensitizer ("EAB-F" manufactured by Hodo Ketani Chemical Co., Ltd.)

15.0 PGMACs

8.2 parts cyclohexyl acetate

Stirring and mixing were performed so that the above-mentioned mixture was uniformly formed, and then filtered through a 1.0 μm filter to obtain an alkali-developing type green resist material III-1. The compounding ratio of PGMAC in all solvents is 89.8%, and the compounding ratio of cyclohexyl acetate is 10.2%. In addition, the particle size of the dispersed green pigment particles measured by SEM was 0.2 μm.

(Green resist material III-2)

60.0 parts of green pigment dispersion III-1

11.0 parts acrylic resin solution

4.2 parts of trimethylolpropane triacrylate ("NK Ester ATMPT" manufactured by Shin-Nakamura Chemical Co., Ltd.)

1.2 parts of photopolymerization initiator ("Irugakiyua-907" manufactured by Chiba Specialty Technology Chemical Co., Ltd.)

0.4 parts of sensitizer ("EAB-F" manufactured by Hodo Ketani Chemical Co., Ltd.)

23.2 parts cyclohexyl acetate

Stirring and mixing were performed so that the above-mentioned mixture was uniformly formed, and then filtered through a 1.0 μm filter to obtain an alkali-developing type green resist material III-2. The compounding ratio of PGMAC in all solvents is 71.0%, and the compounding ratio of cyclohexyl acetate is 29.0%. In addition, the particle size of the dispersed green pigment particles measured by SEM was 0.2 μm.

Hereinafter, using the materials shown in Table 15, green resist materials III-3 to III-11 were obtained in the same manner as the preparation of green resist material III-1. In addition, Table 15 also shows the particle size measured by SEM of each resist material.

[Table 15]

[comparative example]

Using the materials shown in Table 16, a green resist material was prepared in the same manner as the preparation of the green resist material III-1. Also, 23.2 parts of one solvent was added to the green resist materials III-12 and III-19. In addition, Table 16 also shows the particle size measured by SEM of each resist material.

In addition, the characteristic values of the organic solvents used in the Example III series and the Comparative Example III series are shown in Table 17.

[Table 17]

(Evaluation results)

The viscosity, thixotropic index, brightness of the coating film, and contrast ratio of the resist obtained above were evaluated in the same manner as in the first embodiment, and the results are shown in Table 1. 18 and Table 19.

(Preparation of Red Pigment Dispersion)

Next, color filters were fabricated and evaluated using the red resist material and the green resist material. First, a red resist material used for producing a color filter will be described.

After uniformly stirring and mixing 8.0 parts of C.I. Pigment Red 177, 40 parts of acrylic resin solution, 48.0 parts of propylene glycol monomethyl ether acetate (PGMAC), and 1.0 parts of resin-type dispersant (EFKA4300), use a diameter of 0.5 mm zirconia beads were dispersed in an Egger mill ("Minimodel M-250MKII" manufactured by Aiga Japan Co., Ltd.) for 5 hours, and filtered through a 5.0 μm filter to prepare a red pigment dispersion.

(modulation of red resist material)

Stir and mix to make 60.0 parts of red pigment dispersion, 11.0 parts of acrylic resin solution, 4.2 parts of trimethylolpropane triacrylate (manufactured by Shin Nakamura Chemical Co., Ltd. "NK Ester ATMPT"), photopolymerization initiator (Chiba Japan A mixture of 1.2 parts of "Irugakuyua-907" manufactured by Hodo Ketani Chemical Co., Ltd.), 0.4 parts of a sensitizer ("EAB-F" manufactured by Hodo Keya Chemical Co., Ltd.), and 23.2 parts of PGMAC was uniformly formed, and then filtered through a 1.0 μm filter to obtain Alkali-developable red resist material.

(production of color filter)

The above-mentioned red resist material was coated with a thickness of about 2 μm on a 10 cm×10 cm glass substrate with a spinner, and left to stand in an oven at 70° C. for 15 minutes to remove and dry the remaining solvent. Next, stripe pattern exposure is performed using an exposure device. The exposure amount was 100 mJ/cm ² . Furthermore, spray development was performed with a developer containing 2% sodium carbonate aqueous solution to remove unexposed parts, and then washed with ion-exchanged water, and the substrate was heated at 230° C. for 30 minutes to form a red color filter with a line width of about 50 μm. Festival. Next, by the same operation, the green resist material of Example III-1 was used to form a color filter segment adjacent to the red color filter segment, thereby producing a color filter having two color filter segments.

[Table 18]

[Table 19]

When the green resist materials III-1 to III-11 shown in the series of Examples III are prepared using solvent (c1) and using a zinc halide phthalocyanine pigment dispersion, use at least When the mixed organic solvent of the solvent (c1) and the solvent (c2) is included, a colored composition having excellent fluidity and coatability can be obtained, and a coating film capable of simultaneously achieving high brightness, high transmittance, and high contrast ratio can be formed. On the other hand, with the green resist materials III-12 to III-21 shown in the comparative example III series, coating films satisfying brightness, contrast ratio, transmittance, and coatability at the same time could not be obtained.

Claims (15)

1. A green coloring composition for color filters, comprising: (A) a pigment component containing at least a zinc halide phthalocyanine pigment, and (B) a pigment vehicle comprising a resin, a precursor thereof, or a mixture thereof, and Contains selected from: (b) pigment derivatives having basic substituents, and (c) mixed organic solvent at least 1 of the The mixed organic solvent contains an organic solvent (c1) having a solubility parameter, that is, an SP value of 8.0 to 10.0 (cal/cm ³ ) ^1/2 , and a boiling point of 140 to 159°C at 760 mmHg; and a solubility parameter, that is, an SP value of 8.0 to 10.0 (cal/cm ³ ) ^1/2 , an organic solvent (c2) having a boiling point of 160 to 200°C at 760 mmHg, and in all organic solvents, the total of the above organic solvent (c1) and the above organic solvent (c2) It is 85% by weight or more. 2. The green coloring composition for color filters according to claim 1, wherein when the acid value is represented as X (mg KOH/g) and the weight average molecular weight is represented as Y, the resin constituting the pigment carrier (B) It is a resin that satisfies the conditions of the following formulas (F), (G) and (H) simultaneously: (F)Y＞-750X+51000 (G)Y＞940X-79000 (H)Y>8000. 3. The green coloring composition for color filters according to claim 1, further comprising a yellow pigment as a pigment component. 4. The green coloring composition for color filters according to claim 3, further comprising a copper halide phthalocyanine pigment as a pigment component. 5. The green coloring composition for color filters according to claim 3, wherein the content of the pigment is 50 to 90% by weight of the zinc halide phthalocyanine pigment based on the total weight of the pigment component (A). , The yellow pigment is 5 to 45% by weight. 6. The green coloring composition for color filters according to claim 4, wherein the content of the pigment is 50 to 90% by weight of the zinc halide phthalocyanine pigment based on the total weight of the pigment component (A). , copper halide phthalocyanine pigment is 5-45% by weight, yellow pigment is 5-45% by weight 7. The green coloring composition for color filters according to claim 1, wherein the content of the pigment derivative (b) is 0.001 to 40% by weight based on the total weight of the pigment component (A) . 8. The green coloring composition for color filters according to claim 1, wherein the organic solvent (c1) is selected from propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol mono At least one or more solvents of methyl ether acetate and ethylene glycol monoethyl ether acetate. 9. The green coloring composition for color filters according to claim 1, wherein the organic solvent (c2) is selected from the group consisting of cyclohexyl acetate, propylene glycol diacetate, diethylene glycol diethyl ether, and 3- At least one or more solvents of ethyl ethoxypropionate. 10. The green coloring composition for color filters according to claim 1, wherein, based on the total amount of the mixed organic solvent (c), the organic solvent (c1) is 50% by weight to 95% by weight, and the above-mentioned The organic solvent (c2) is 5% by weight to 50% by weight. 11. The green coloring composition for color filters according to claim 1, further comprising a photopolymerization initiator. 12. The green coloring composition for color filters according to claim 1, comprising the above-mentioned dye derivative (b) and the above-mentioned mixed organic solvent (c). The green coloring composition for color filters of Claim 1 which further contains the said basic resin type dispersant (a). 14. The green coloring composition for color filters according to claim 1, which has an average dispersed particle diameter of 0.05 to 0.2 μm. 15. A color filter comprising green color filter segments formed from the green coloring composition for color filters according to any one of claims 1 to 14.