KR101607705B1 - Green colored composition for color filter, and color filter - Google Patents

Abstract

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

(B) a pigment, a precursor thereof, or a mixture thereof,

(a) a basic resinous dispersant having an amine value of 35 to 100 mgKOH / g,

(b) a pigment derivative having a basic substituent, and

(c1) having 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 DEG C, (C2) having a boiling point of 8.0 to 10.0 (cal / cm < 3 >) ^1/2 and a boiling point of 760 mmHg at 160 to 200 DEG C,

At least one selected from the group consisting of

Lt; RTI ID = 0.0 > coloring < / RTI >

Description

A green coloring composition for a color filter, and a color filter for a color filter for a color filter,

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

A liquid crystal display device is a display device in which a liquid crystal layer sandwiched between two polarizing plates performs display by controlling the degree of polarization of light passing through the first polarizing plate and adjusting the amount of light passing through the second polarizing plate, (TN) type liquid crystal is used. The liquid crystal display device is capable of color display by providing a color filter between two polarizing plates, and has recently been used in televisions, PC monitors, and the like. Therefore, there is an increasing demand for high contrast and high definition for color filters.

The color filter is formed by arranging filter segments on two or more different colored fine strips (stripes) in parallel or crossing on the surface of a transparent substrate such as glass, or by arranging fine filter segments in a horizontal arrangement . The filter segments are fine from several microns to several hundreds of microns and are arranged in a predetermined arrangement in a color-coded manner.

In general, in a color liquid crystal display device, a transparent electrode for driving a liquid crystal is formed on a color filter by vapor deposition or sputtering, and an alignment film for orienting the liquid crystal in a certain direction is formed thereon. In order to sufficiently obtain the performance of these transparent electrodes and alignment films, it is generally necessary to carry out the formation at a high temperature of 200 DEG C or higher, preferably 230 DEG C or higher. For this reason, as a method of producing a color filter at present, a method called a pigment dispersion method using a pigment having excellent light resistance and heat resistance as a coloring agent has become mainstream.

However, in general, a color filter in which a pigment is dispersed has a problem that the degree of polarization controlled by the liquid crystal is disturbed by light scattering by the pigment or the like. That is, since the transmitted light is attenuated when the light should be blocked (OFF state) or when the light should be transmitted (ON state), the ratio of the luminance on the display device in the ON state and the OFF state (contrast ratio) Is low.

In order to realize high brightness and high contrast of a color filter, up to now, a pigment contained in a filter segment has been subjected to refinement treatment. However, a pigment (which is called a crude pigment having a particle size of 10 to 100 占 퐉 produced by a chemical reaction, is made into a mixture of primary particles and secondary particles aggregated by pigmentation treatment) Even if the fine particles are finely ground by various finishing methods, pigments in which primary particles or secondary particles are finely formed generally tend to agglomerate, and when the fineness is excessively advanced, a large mass of pigment solids is formed. In addition, it is very difficult to obtain a stable coloring composition even if it is intended to disperse the finely-faded pigment into a pigment carrier containing a resin or the like and to stabilize secondary particles of the pigment as close to primary particles as possible.

The coloring composition obtained by dispersing the finely-pigmented pigment in a pigment carrier occasionally becomes high in viscosity due to agglomeration of the pigment particles with time, and exhibits thixotropic properties. The increase in the viscosity and the poor flowability of such a coloring composition cause various problems in the manufacturing work problems and the product value. For example, the formation of the filter segment of the color filter is generally carried out by spin-coating a coloring composition having a pigment dispersed in a pigment carrier containing a monomer and a resin on a glass substrate. However, If it is used, it is not possible to obtain a coating film having a uniform film thickness due to defective spin coating, poor leveling, and the like, which is not preferable.

The color filter is produced by applying a coloring composition for a color filter (hereinafter also referred to as a coating liquid) onto a transparent substrate and drying the coating to form a coating film having a thickness of about 0.2 to 5 mu m. As a coating method, there are a spin coating method and a die coating method, and they are suitably used according to their characteristics.

The spin coating method is a widely used method for forming a thin film on a substrate of a relatively small size. The coating liquid is dripped to the center of the transparent substrate while rotating the transparent substrate at a constant rotation number, the coating liquid is diluted by the centrifugal force, And controlling the number of rotations and the rotation time of the transparent substrate suitable for the coating liquid to form a coating film having a desired film thickness on the surface of the transparent substrate. However, there is a disadvantage that the coating film thickness of the rotation center portion and the peripheral portion of the transparent substrate becomes excessively thick compared to the middle portion due to the principle that the coating film is thinned by the centrifugal force by the rotation. In Patent Document 1, a composition containing 50 wt% or more of a solvent having a boiling point or a vapor pressure within a specific range is described as a coating liquid for a spin coat system having excellent surface smoothness of a coating film.

When the size of the substrate is large, the die coating method is employed because the load on the apparatus is large in the method of rotating the substrate such as the spin coating method. 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 the transparent substrate on the substrate while moving the slit. However, streaky unevenness in the vertical direction with respect to the direction of the slit is likely to occur on the mechanism, and in the slit opening, the coating liquid spreads in the outside air to be dried and solidified to cause aggregation, resulting in uneven streaks in the coating advancing direction, The aggregate is incorporated into the coating material, resulting in coating film defects. Further, the outer peripheral portion of the coating film swells up, resulting in a problem that the coating film is thicker than the central portion of the substrate.

In order to solve the problem of non-uniformity of the coating film in the die coating method, attempts have been made in the following patent documents.

Patent Documents 2 and 3 disclose a method of preventing a coating liquid from drying and solidifying by containing a solvent having a high boiling point and not causing aggregates.

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

[Patent Document 2] Japanese Unexamined Patent Publication No. 2003-55566

[Patent Document 3] Japanese Patent Application Laid-Open No. 2004-346218

On the other hand, as described above, not only high contrast ratio but also high definition is required for color filters. Generally, in order to obtain a high brightness, a high brightness is obtained by bringing the pigment close to the primary particle when dispersed in the pigment carrier to increase the transparency of the dispersion and to have a high transmittance in the spectral spectrum of the dispersion.

However, the green of one of the three primary colors (red, green, blue, and RGB) of the color filter substrate is a coloring material containing a halogenated copper phthalocyanine pigment (for example, CI Pigment Green 36 or CI Pigment Green 7) However, as long as halogenated copper phthalocyanine can be used, it is difficult to make high contrast ratio compatible with high brightness.

In order to solve these problems, a halogenated zinc phthalocyanine pigment in which a center metal is replaced with zinc from a current halogenated copper phthalocyanine pigment has been used as a coloring material having a high tinting power by exhibiting a bright color tone and a wide color display region.

[Patent Document 4] JP-A-10-130547

[Patent Document 5] Japanese Patent Application Laid-Open No. 2001-141922

[Patent Document 6] Japanese Patent Application Laid-Open No. 2007-204658

However, the zinc halide phthalocyanine green pigment has a higher acidity than the halogenated copper phthalocyanine green pigment. Therefore, the zinc halide phthalocyanine green pigment is difficult to disperse as compared with the halogenated copper phthalocyanine green pigment. The coloring composition with poor dispersion sometimes becomes high in viscosity due to agglomeration of the pigment particles with time, and exhibits thixotropic properties. The increase in the viscosity and the poor flowability of such a coloring composition cause various problems in the manufacturing work problems and the product value. For example, the formation of the filter segment of the color filter is generally carried out by spin-coating a coloring composition having a pigment dispersed in a pigment carrier containing a monomer and a resin on a glass substrate. However, If it is used, it is not preferable because a coating film having a uniform film thickness can not be obtained due to defective spin coating, leveling defects, or the like.

It is also known that the zinc halide phthalocyanine pigments are pigments which are difficult to disperse because of their chemical properties different from those of the conventional halogenated copper phthalocyanine pigments. For this reason, it has been difficult to stably disperse a zinc halide phthalocyanine pigment while retaining its excellent color characteristics, only by using a conventional dispersant suitable for a copper phthalocyanine halide pigment or other pigment.

On the other hand, in order to obtain a highly homogeneous zinc phthalocyanine pigment dispersion, it is necessary to use a large amount of a dispersing agent which often adversely affects all resistance, and in order to maintain a high pigment concentration, the pigment carrier component which maintains all the resistance must be reduced As a result, it was difficult to make all of the resistance, fluidity and color characteristics compatible.

Further, unlike the conventional halogenated copper phthalocyanine pigments, the zinc halide phthalocyanine pigments differ in solubility of the pigments themselves, so that the zinc halide phthalocyanine pigments exhibit an excessively good affinity as a solvent optimal for the dispersion of the halogenated copper phthalocyanine pigments , And when these solvents are used for the dispersion of the zinc phthalocyanine pigment, there is a problem that the pigment itself is dissolved in the solvent and a dispersion having a high contrast ratio and high brightness can not be obtained.

Also, as described above, the coloring compositions of zinc halphthalocyanine pigments dispersed by using a solvent used for dispersing the copper phthalocyanine pigments of halide are not limited to the coating methods such as the spin coating method and the die coating method, Further, there is a disadvantage that unevenness of the film thickness and streaks are caused due to the property of the coating liquid used there.

Here, the term "film thickness unevenness" means that the uniformity of the film thickness is insufficient. The term "film thickness uniformity (end portion)", that is, the uniformity of the film thickness at the end face portion and the "film thickness uniformity And the uniformity from the front side to the front side. The term "stripe unevenness" means streaked streaks occurring in a direction perpendicular to the direction in which the slits travel in the die coating system and "streaked streaks" in the die coating system, that is, And stripe-like stains in the direction of the slit in the direction of travel of the slit.

Accordingly, an object of the present invention is to provide a stable green coloring composition for a color filter which is excellent in fluidity and all resistance, and a color filter using the same, which has high brightness and contrast ratio.

It is also an object of the present invention to provide a green coloring composition for a color filter which can reduce defects observed in a coating film of a coating material by a spin coating method or a die coating method and can form a color filter having a high brightness and a high contrast ratio Material), and a filter segment formed using the same.

The above-

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

(B) a pigment, a precursor thereof, or a mixture thereof,

(a) a basic resinous dispersant having an amine value of 35 to 100 mgKOH / g,

(b) a pigment derivative having a basic substituent, and

(c1) having 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 DEG C, A mixed organic solvent containing an organic solvent (c2) having a boiling point of 8.0 to 10.0 (cal / cm3) ^1/2 and a boiling point of 760 mmHg at 160 to 200 DEG C, Filter green coloring composition.

In a preferred embodiment of the green coloring composition for a color filter of the present invention, when the resin constituting the pigment carrier (B) has an acid value of X (mgKOH / g) and a weight average molecular weight of Y, (F), (G) and (H):

(F) Y> -750X + 51000

(G) Y> 940X - 79000

(H) Y> 8000.

In a preferred embodiment of the green coloring composition for a color filter according to the present invention, the content of the basic resinous dispersant (a) is less than the content of the pigment component (A) comprising the zinc halide phthalocyanine pigment [ By weight, based on the total weight of the composition.

In a preferred embodiment of the green coloring composition for a color filter of the present invention, the basic resinous dispersant (a) is a block copolymer resin (a2) comprising a basic copolymer block (a1) and a pigment carrier affinity copolymer block , For example, a block copolymer resin obtained by living radical polymerization.

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

In a preferred embodiment of the green coloring composition for a color filter according to the present invention, the organic solvent (c1) is at least one selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl Ether acetate and the like.

In a preferred embodiment of the green coloring composition for a color filter according to the present invention, the organic solvent (c2) is selected from the group consisting of cyclohexyl acetate, propylene glycol diacetate, diethylene glycol diethyl ether, and ethyl 3-ethoxypropionate Or more.

In a preferred embodiment of the green coloring composition for a color filter of the present invention, the amount of the organic solvent (c1) is 50 wt% to 95 wt% based on the total amount of the mixed organic solvent (c) ) Is 5 wt% to 50 wt%.

In a preferred embodiment of the green coloring composition for a color filter of the present invention, a photopolymerization initiator is further contained.

In a preferred embodiment of the green coloring composition for a color filter of the present invention, the basic resinous dispersant (a) and the pigment derivative (b) are contained.

In a preferred embodiment of the green coloring composition for a color filter of the present invention, the basic resinous dispersant (a) and the mixed organic solvent (c) are contained.

In a preferred embodiment of the green coloring composition for a color filter of the present invention, the coloring derivative (b) and the mixed organic solvent (c) are contained.

In a preferred embodiment of the green coloring composition for a color filter of the present invention, the basic resinous dispersant (a), the colorant derivative (b) and the mixed organic solvent (c) are contained.

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

The green coloring composition for a color filter of the present invention,

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

(B) a pigment, a precursor thereof, or a mixture thereof,

In addition, at least one selected from the group consisting of the basic resinous dispersant (a), the colorant derivative (b), and the mixed organic solvent (c)

It becomes a high-dynamic and stable pigment dispersion. By using this pigment dispersion, it becomes possible to form a color filter with high brightness and a high contrast ratio. Further, the conventional defects observed in the coating film of the coating material are reduced, and a color filter having a high contrast ratio and high brightness can be formed.

In particular, when the basic resinous dispersant (a) is a block copolymer resin comprising a basic copolymer block (a1) and a pigment carrier affinity copolymer block (a2), a color filter with a higher contrast ratio is formed Dispersible pigment.

Further, in the case of containing the basic resinous dispersant (a) and the pigment derivative (b) having a basic substituent, the initial contrast ratio is high and the stability with time is also good.

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

The term "(meth) acryloyl", "(meth) acryl", "(meth) acrylic acid", " Acrylate and / or methacrylate ", " acrylic acid and / or methacrylic acid ", " acrylate and / or methacrylate ", "Quot; and " acryloyloxy and / or methacryloyloxy ".

The green coloring composition for a color filter of the present invention,

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

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

, And in the first embodiment,

(a) a basic resinous dispersant having an amine value of 35 to 100 mgKOH / g

.

In the second embodiment, the basic resinous dispersant (a) and / or

(b) Pigment derivatives having a basic substituent

.

In the third embodiment, the basic resinous dispersant (a) and / or the colorant derivative (b) and / or

(c1) having 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 DEG C, (C2) having a boiling point of 8.0 to 10.0 (cal / cm < 3 >) ^1/2 and a boiling point of 760 mmHg at 160 to 200 DEG C,

.

That is, it is possible to simultaneously include any two or all three of the basic resinous dispersant (a), the colorant derivative (b), and the mixed organic solvent (c).

[Pigment Component (A)]

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

Representative halogenated zinc phthalocyanine pigments can be represented by the color index (C.I.) number, C.I. Pigment Green 58 and the like. By using a zinc halide phthalocyanine pigment as a main pigment, a high brightness which can not be obtained with other green pigments can be obtained. Further, those obtained by a known production method can be used. Especially, when the measurement is performed using n-hexylamine as a basic substance by the method described in Coloring Material, 67 [9], 547-554 (1994), the amount of the acidic functional group on the surface of the pigment is preferably 100 mu mol / g or more , And more preferably 200 mu mol / g or more.

As the pigment component (A), not only zinc phthalocyanine halide as a main pigment but also other green or yellow pigments can be used in combination for color adjustment or complementary coloring.

Examples of other green pigments that can be used in combination include green pigments such as C.I. Pigment Green 7, 10, 36, 37, and the like. Examples of yellow pigments which can be used in combination include CI 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, , 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139 , 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180 , 181, 182, 185, 187, 188, 193, 194, 198, 199, 213 and 214.

Among these, CI Pigment Yellow 138, 139, 150, 185 and the like are preferably used in combination in terms of broadening the chromaticity region.

The concentration of the pigment component (A) in the total nonvolatile component of the coloring composition according to the present invention is preferably from 10 to 90% by weight, more preferably from 15 to 80% by weight, By weight is 20 to 70% by weight. When the concentration of the pigment component (A) is less than 10% by weight, sufficient color reproducibility can not be obtained. When the concentration of the pigment component (A) is more than 90% by weight, the concentration of the pigment carrier is lowered and the stability of the coloring composition is deteriorated.

Particularly preferable examples of the proportion of the pigment include 50 to 100% by weight of the zinc phthalocyanine pigment, 0 to 50% by weight of the halogenated copper phthalocyanine pigment, 0 to 50% by weight of the yellow pigment, 50% by weight.

More preferably, the halogenated zinc phthalocyanine pigment is contained in an amount of 50 to 90% by weight, the halogenated copper phthalocyanine pigment is contained in an amount of 5 to 45% by weight, and the yellow pigment is contained in an amount of 5 to 45% by weight, based on the pigment component (A). The chromaticity region can be broadened by the composition ratio of the pigment.

The green coloring composition of the present invention using the zinc halide phthalocyanine pigment is coated on a glass substrate or the like so as to have the same chromaticity as the green coloring composition using the halogenated copper phthalocyanine to measure the transmittance of the coating film, Exhibits a higher transmittance than the coating film of the coloring composition using phthalocyanine. In particular, the transmittance peaks show a transmittance of about 5% and a value of about 90%. Therefore, high brightness can not be obtained with a coloring composition using a copper phthalocyanine pigment such as C.I. Pigment Green 36 or C.I. Pigment Green 7 by combining with a backlight generally used in a color liquid crystal display.

[Minification of Pigment]

The pigment to be used in the green coloring composition of the present invention may be finely ground by a salt milling treatment, and it is preferable to use finely divided pigments.

In the salt milling treatment, a mixture of a pigment, a water-soluble inorganic salt and a water-soluble organic solvent is mechanically kneaded while heating using a kneader such as a kneader, a twin roll mill, a three roll mill, a ball mill, an attritor, or a sand mill, And removing the water-soluble inorganic salt and the water-soluble organic solvent by washing with water. The water-soluble inorganic salt acts as a crushing aid, and it is considered that the pigment is broken by using the high hardness of the inorganic salt during salt milling, thereby generating an active surface to cause crystal growth. Therefore, at the time of kneading, fracture of the pigment and crystal growth occur at the same time, and the primary particle diameter of the pigment obtained by the kneading condition is different.

In order to accelerate the crystal growth by heating, the heating temperature is preferably 40 to 150 ° C. If the heating temperature is lower than 40 占 폚, crystal growth does not sufficiently take place, and the shape of the pigment particles becomes nearly amorphous, which is not preferable. On the other hand, when the heating temperature exceeds 150 캜, the crystal growth proceeds excessively and the primary particle diameter of the pigment becomes large, so that it is not preferable as a coloring agent for the coloring composition for a color filter. The kneading time of the salt milling treatment is preferably 2 to 24 hours in terms of balancing the particle size distribution of the primary particles of the salt milled pigment and the cost required for the salt milling treatment.

By optimizing the conditions under which the pigment is subjected to the salt milling treatment, it is possible to obtain a pigment having a very small primary particle diameter, a narrow distribution width and a sharp particle size distribution.

The primary particle diameter determined by TEM (transmission electron microscope) of the green pigment used in the green coloring composition of the present invention is preferably in the range of 20 to 100 nm. If it is smaller than 20 nm, dispersion into an organic solvent becomes difficult. Further, if it is larger than 100 nm, a sufficient contrast ratio can not be obtained. A particularly preferable range is 25 to 85 nm.

As the water-soluble inorganic salt to be used in the salt milling treatment, sodium chloride, barium chloride, potassium chloride, sodium sulfate or the like can be used, but it is preferable to use sodium chloride (salt) in view of cost. The water-soluble inorganic salt is preferably used in an amount of from 50 to 2000% by weight, more preferably from 300 to 1000% by weight, based on the total weight of the pigment component (A) from both the treatment efficiency and the production efficiency Do.

The water-soluble organic solvent is not particularly limited as long as it acts to wet the pigment and the water-soluble inorganic salt, dissolves in water (miscible) and does not substantially dissolve the inorganic salt to be used. However, in the case of salt milling, the temperature rises and the solvent is liable to evaporate. Therefore, from the viewpoint of safety, a high boiling point solvent having a boiling point of 120 캜 or higher is preferable. For example, there can be mentioned 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl Diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, diethylene glycol monomethyl ether, Monoethyl ether, or liquid polypropylene glycol. The water-soluble organic solvent is preferably used in an amount of 5 to 1000 wt%, most preferably 50 to 500 wt%, based on the total weight of the pigment component (A).

In the salt milling treatment, a resin may be added as needed. The kind of the resin to be used is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like can be used. The resin used is preferably a solid at room temperature, preferably water-insoluble, and further preferably partially soluble in the organic solvent. The amount of the resin to be 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)]

The green coloring composition of the present invention includes, in addition to the pigment component (A), a pigment carrier (B) comprising a resin, a precursor thereof, or a mixture thereof.

The pigment carrier (B) used in the green coloring composition of the present invention is preferably a resin having a spectral transmittance of preferably 80% or more, more preferably 95% or more, in the entire wavelength range of 400 to 700 nm in the visible light region, Or mixtures thereof. The resin includes a thermoplastic resin, a thermosetting resin, or an active energy ray-curable resin, and the precursor thereof includes a monomer or an oligomer which is cured by irradiation with active energy rays to produce a transparent resin, Or more. The pigment carrier (B) may be used in an amount of 30 to 500% by weight based on the total weight of the pigment component (A). When the amount is less than 30% by weight, the film formability and all the resistance are insufficient, and when it is more than 500% by weight, the pigment concentration is low and color characteristics can not be exhibited.

The resin constituting the pigment carrier (B) has the following formulas (F), (G) and (H) when the acid value is X (mgKOH / g) and the weight average molecular weight is Y It is preferable that the resin satisfy all the requirements at the same time:

(F) Y> -750X + 51000

(G) Y> 940X - 79000

(H) Y> 8000.

When the resin constituting the pigment carrier (B) satisfies all of the conditions of the formulas (F), (G) and (H), the resin dispersant having a good acid value range, Since the resin can maintain a proper interaction and has a good molecular weight range, the function as a steric hindrance of the carrier resin can be adequately attained and a favorable dispersion state can be maintained. In particular, the basic resinous dispersant (a) used in the first embodiment of the present invention to be described later and / or the dye derivative (b) used in the second embodiment of the present invention to be described later is favorably adsorbed on the surface of the pigment . On the other hand, when the resin constituting the pigment carrier (B) does not satisfy the condition of the formula (F), the interaction between the basic resinous dispersant (a) adsorbed on the pigment surface and the resin becomes too weak It is impossible to maintain a good dispersed state due to pigment aggregation or the like. When the condition of the above formula (G) is not satisfied, the interaction becomes excessively strong, so that the resinous dispersant adsorbed on the pigment is peeled off, and a good dispersion state can not be maintained due to pigment aggregation or the like . When the condition of the above formula (H) is not satisfied, the molecular weight is too small, the resin does not act as a steric hindrance, resulting in poor dispersion due to pigment aggregation or the like. It is more preferable that Y ≤ 60000 and Y ≤ 50000 are more preferable. If Y is more than 60,000, it is not preferable because the developing property may become defective if it is used as an alkali developing type colored resist to be described later.

Examples of the thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, (HDPE, LDPE), polybutadiene, polyimide resin, and the like can be given as examples of the resin composition, resin, alkyd resin, polystyrene resin, polyamide resin, rubber resin,

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

When used in the form of an alkali developing type colored resist to be described later, it is preferable to use an alkali-soluble resin having an acidic group such as a (meth) acrylic acid copolymer resin (alkali-soluble acrylic resin). In order to disperse the zinc halide phthalocyanine pigment well, the weight average molecular weight (Mw) of the alkali-soluble resin is preferably in the range of 10,000 to 100,000, more preferably 30,000 to 80,000. 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 the present invention, the molecular weight distribution (weight average molecular weight (Mw), number average molecular weight (Mn)) of the resin is measured by GPC under the following conditions.

Device: GPC-150C (Waters)

Column: GMH-HT30 cm 2 stations (manufactured by TOSOH CORPORATION)

Temperature: 135 ° C

Solvent: o-Dichlorobenzene (0.1% Ionol added)

Flow rate: 1.0 ml / min

Samples: 0.4 ml of 0.15% sample

The above conditions are used to calculate the molecular weight of the sample, and a molecular weight calibration curve prepared by using a single sample of a dispersed polystyrene standard is used. It is also calculated by converting the polyethylene into a conversion formula derived from the Mark-Houwink viscosity equation.

As the active energy ray curable resin, a (meth) acrylic compound or cinnamic acid having a reactive substituent such as an isocyanate group, an aldehyde group, or an epoxy group is reacted with a linear polymer having a reactive substituent such as a hydroxyl group, a carboxyl group, Acryloyl group, or a styryl group is introduced into the linear polymer. The linear polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an alpha -olefin-maleic anhydride copolymer may be copolymerized with a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) Esterification is also used.

As the monomer and oligomer which are precursors of the resin, for example,

Acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (Meth) acrylate, isoamyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (Meth) acrylate, isostearyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, isomyristyl (Meth) acrylates;

(Meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl Cyclic alkyl (meth) acrylates such as chloropentenyloxyethyl (meth) acrylate, or isobornyl (meth) acrylate;

(Meth) acrylate such as trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate or tetrafluoropropyl Rheology;

(Meth) acryloxy-modified polydimethylsiloxane (silicone macromer);

(Meth) acrylates having a heterocycle such as tetrahydrofurfuryl (meth) acrylate or 3-methyl-3-oxetanyl (meth) acrylate;

Benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, para-cumylphenoxyethyl (meth) acrylate, para-cumylphenoxypolyethylene glycol (Meth) acrylates having an aromatic ring such as nonylphenoxypolyethylene glycol (meth) acrylate;

(Meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 3-methoxybutyl (Meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, triethylene glycol monomethyl ether (meth) acrylate, triethylene glycol monoethyl ether (Meth) acrylate, dipropylene glycol monomethyl ether (meth) acrylate, tripropylene glycol mono (meth) acrylate, polyethylene glycol monolauryl ether (meth) acrylate, or polyethylene glycol monostearyl ether (Poly) alkylene glycol monoalkyl ether (meth) acrylates such as methyl (meth) acrylate;

(Meth) acrylic acid, acrylic acid dimer, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxypropyl phthalate, 2- (meth) acryloyloxyethylhexahydrophthalate, 2- (Meth) acrylate having a carboxyl group such as acryloyloxypropyl hexahydrophthalate, ethylene oxide modified succinic acid (meth) acrylate,? -Carboxyethyl (meth) acrylate or? -Carboxylic polycaprolactone ) Acrylates;

(Meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (Meth) acrylate, ethyleneglycol mono (meth) acrylate, propyleneglycol mono (meth) acrylate, ethyleneglycol mono Poly (ethylene glycol) mono (meth) acrylate, poly (ethylene glycol-tetramethylene glycol) mono (meth) acrylate, polytetramethylene glycol mono (Meth) acrylates having a hydroxyl group such as poly (propylene glycol-tetramethylene glycol) mono (meth) acrylate or glycerol (meth) acrylate;

Acrylates such as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di Acrylate, poly (ethylene glycol-propylene glycol) di (meth) acrylate, poly (ethylene glycol-tetramethylene (Meth) acrylate, 1,3-butanediol di (meth) acrylate, neopentyl (meth) acrylate, Propane diol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, Such as a relay agent (poly) alkylene glycol di (meth) acrylate;

(Meth) acrylate, ethylene oxide modified bisphenol A di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, stearic acid modified pentaerythritol di Modified bisphenol F di (meth) acrylate, propylene oxide modified bisphenol A di (meth) acrylate, tetramethylene oxide modified bisphenol A di (meth) acrylate, ethylene oxide modified bisphenol F di Di (meth) acrylates such as acrylate, tetramethylene oxide modified bisphenol F di (meth) acrylate, zinc diacrylate, ethylene oxide modified phosphoric triacrylate, or glycerol di (meth) acrylate;

(Meth) acrylate having a tertiary amino group such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate or diethylaminopropyl (meth) Ryu;

(Meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, Trifunctional or higher polyfunctional (meth) acrylates such as hexa (meth) acrylate;

(Meth) acrylic acid adduct, 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 (Meth) acrylic acid adduct, alkyl glycidyl ether- (meth) acrylic acid adduct, allyl glycidyl ether- (meth) acrylic acid adduct, phenylglycidyl ether- (meth) acrylic acid adduct, styrene (Meth) acrylic acid adduct, bisphenol A diglycidyl ether- (meth) acrylic acid adduct, propylene oxide-modified bisphenol A diglycidyl ether- (meth) acrylic acid adduct, bisphenol F diglycidyl (Meth) acrylic acid adduct, epichlorohydrin-modified phthalic acid- (meth) acrylic acid adduct, epichlorohydrin-modified hexahydrophthalic acid- (meth) acrylic acid adduct, ethylene glycol diglycidyl ether- (meth) Acrylic acid moiety Water, polyethylene glycol diglycidyl ether- (meth) acrylic acid adduct, propylene glycol diglycidyl ether- (meth) acrylic acid adduct, polypropylene glycol diglycidyl ether- (meth) acrylic acid adduct, phenol novolak Epoxy (meth) acrylates such as a cycloolefin type epoxy resin- (meth) acrylic acid adduct, cresol novolak type epoxy resin- (meth) acrylic acid adduct or other epoxy resin- (meth) acrylic acid adduct;

(Meth) acryloyl-modified isocyanurate, (meth) acryloyl-modified polyurethane, (meth) acryloyl-modified polyester, (meth) acryloyl-modified melamine, (Meth) acryloyl-modified polybutadiene such as (meth) acryloyl-modified polybutadiene or (meth) acryloyl-modified rosin;

Styrene,? -Methylstyrene, vinyl acetate, vinyl (meth) acrylate, and vinyl (meth) acrylate;

Vinyl ethers such as hydroxyethyl vinyl ether, ethylene glycol divinyl ether, and pentaerythritol trivinyl ether;

Amides such as (meth) acrylamide, N-hydroxymethyl (meth) acrylamide or N-vinylformamide; or,

Acrylonitrile and the like. These may be used alone or in combination of two or more, but the present invention is not limited thereto.

[Basic resinous dispersant (a)]

The green coloring composition of the present invention is characterized by using zinc phthalocyanine halide having zinc as a main metal as a main pigment of the pigment component (A), but the zinc halphthalocyanine halide is generally used in a halogenated Compared with copper phthalocyanine pigments, an acidic pigment having zinc in its central metal has a negative charge on its pigment surface. Therefore, in the first embodiment of the present invention, by using the basic resinous dispersant (a) having a relatively high amine value of 35 to 100 mgKOH / g as the resinous dispersant used for pigment dispersion, the acidic pigment The adsorption to the dispersion medium becomes sufficient and the dispersion body can obtain sufficient fluidity.

The number average molecular weight of the basic resinous dispersant (a) used in the present invention is usually preferably from 500 to 50,000, more preferably from 3,000 to 30,000. When the number average molecular weight is less than 500, the effect of steric repulsion by the pigment-affinity group, the effect of compatibility with the pigment carrier, the effect of compatibility with the pigment carrier and the solvent when the solvent is used is small, And the viscosity of the dispersion may be increased. On the other hand, if the number average molecular weight exceeds 50,000, the addition amount of the resin 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 resinous dispersant (a) having an amine value of 35 to 100 mgKOH / g is used. The amine value of the basic resinous dispersant (a) is more preferably 50 to 75 mgKOH / g. If the amine value is less than 35 mgKOH / g, it is not sufficiently adsorbed on the pigment, resulting in poor dispersion. When the amine value is more than 100 mgKOH / g, adsorption to the acidic component in the pigment carrier or reaction causes adsorption to the zinc halide phthalocyanine pigment The efficiency becomes poor, and dispersion becomes defective.

As the basic resinous dispersant (a) having an amine value of 35 to 100 mgKOH / g, resin systems of various types such as vinyl type, urethane type, polyester type, polyether type and polyamide type can be used. (Meth) acrylate monomer units and other vinyl monomer units are preferable, and more specifically, vinyl monomer units having N, N-disubstituted amino group, alkyl (meth) acrylate monomer units and other vinyl monomer units The resin binder is suitable.

Examples of the N, N-disubstituted amino group-containing vinyl monomer unit include N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N- Acrylate, N, N-diethylaminopropyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylamide or N, N-diethylaminoethyl (meth) acrylamide. But the present invention is not limited thereto. These monomer units are adsorbed as a halogenated zinc phthalocyanine pigment having a high acidity as a monomer unit containing a basic group.

Examples of the alkyl (meth) acrylate monomer unit include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, Unsaturated monocarboxylic acids such as isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, (Meth) acrylic esters obtained by the reaction of an alkyl alcohol having 1 to 18 carbon atoms, but the present invention is not limited thereto. These monomer units function as a pigment carrier-affinity group.

Examples of other vinyl monomer units include nitro group-containing vinyl monomers such as (meth) acrylonitrile, vinyl-based aromatic monomers such as styrene,? -Methylstyrene, or benzyl (meth) acrylate, 2-hydroxyethyl (Meth) acrylate, N, N-dimethylacrylamide, N-isopropyl (meth) acrylate, hydroxypropyl (meth) acrylate or polyethylene glycol Acrylamide or diacetone acrylamide, vinyl-based monomers such as N-methylol (meth) acrylamide or dimethylol (meth) acrylamide, vinyl monomers such as N-methoxymethyl (Meth) acrylamide or N-butoxymethyl (meth) acrylamide, olefins such as ethylene, propylene or isoprene, chloroprene or butadiene Vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether and isobutyl vinyl ether; vinyl esters such as vinyl acetate and vinyl propionate; And the like, and they are appropriately used depending on the purpose, but are not limited thereto.

(Aminomethylated) epoxy resin, or the like, with a polymer having a primary amino group-containing monomer unit such as a polyethyleneimine, a polyethyleneimine, a polyethyleneimine, a polyimide, , Or a polyether resin, or the like.

As commercial products of such basic resinous dispersants, for example, BYK-161, 163, 164, 167, 174, 184, 2000, 2050 of Big Chem Japan Co. or SOLSPERSE-34750, 56000 of Japan Rubris Co., And EFKA4300, 4330, 4046, 4060, 4080 of Japan Co., Ltd., and the like.

Particularly preferred as the basic resinous dispersant (a) of the green coloring composition for a color filter of the present invention is a block copolymer resin comprising a basic copolymer block (a1) and a pigment carrier affinity copolymer block (a2). Hereinafter, the basic resinous dispersant will be described.

(Basic resinous dispersant)

The basic resinous dispersant of the green coloring composition for a color filter according to the present invention is a basic resinous dispersant of a coloring composition for a color filter which has a region adsorbed on a pigment (hereinafter, abbreviated as an adsorbing portion), and a pigment which prevents agglomeration of pigments, (Hereinafter, referred to as an affinity part) having a high affinity for the pigment carrier. Since the zinc halide phthalocyanine halide has high acidity, if the affinity part and the adsorbing part are arranged at random, the adsorption to the pigment becomes insufficient and dispersion becomes defective. In the first embodiment of the present invention, the basic copolymer block (a1), which is an adsorbent for the zinc halide phthalocyanine pigment, and the pigment carrier affinity copolymer block (a2), which is an affinity for the pigment carrier, By using the present block copolymer resin as the resinous dispersant (a), it is possible to provide a zinc colored phthalocyanine halide pigment with a fine, low-viscosity, and stably dispersed green coloring composition without impairing its color characteristics have.

The basic copolymer block (a1) and the pigment carrier-affinity copolymer block (a2) constituting the block copolymer resin can be selected from various resin systems, but the vinyl copolymer .

Each copolymer block will be described below.

≪ Basic copolymer block (a1) >

Specific examples of the basic copolymer block (a1) include N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N- (Meth) acrylate such as N, N-diethylaminopropyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylamide, or N, A copolymer having a vinyl monomer unit having a substituted amino group, a polymer having a monomer unit containing a primary amino group such as allylamine, or a polymer having a monomer unit containing a primary amino group such as polyethyleneimine, polyethylene polyamine, poly (xylylene poly (hydroxypropylene) ) Epoxy resin, and the like, but are not limited thereto.

Among these, a copolymer having an N, N-disubstituted amino group-containing vinyl-based monomer unit which is easy to design a block copolymer and which is excellent in all resistance is preferable. In this case, The content of the N, N-disubstituted amino group-containing vinyl monomer unit is preferably 60 to 100% by weight, more preferably 80 to 100% by weight, and the content of the N, N-disubstituted amino group- The vinyl-based monomer unit is preferably a vinyl-based monomer unit described as the pigment carrier-affinity copolymer block (a2).

≪ Pigment carrier affinity copolymer block (a2) >

The pigment carrier affinity copolymer block (a2) is a vinyl monomer copolymer which is easy to design a block copolymer and which is excellent in all resistance, and further contains an alkyl (meth) acrylate as a vinyl monomer unit , Particularly preferably 60 to 100% by weight, and more preferably 80 to 100% by weight, in the pigment carrier-affinity copolymer block (a2). Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, Unsaturated monocarboxylic acid such as isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, or lauryl And (meth) acrylic esters obtained by the reaction of an alkyl alcohol having 1 to 18 carbon atoms. However, the present invention is not limited thereto.

In the pigment carrier affinity copolymer block (a2), the vinyl monomer unit containing an amino group is preferably 0% by weight, but it may be included if it is less than 10% by weight.

Examples of other vinyl monomer units that may be contained in the basic copolymer block (a1) and the pigment carrier affinity copolymer block (a2) include nitro group-containing vinyl monomers such as (meth) acrylonitrile, (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, or polyethylene glycol (meth) acrylate (Meth) acrylamide, N, N-dimethylacrylamide, N-isopropylacrylamide, or diacetone acrylamide, vinyl monomers having an amide group such as N-methylol (Meth) acrylamide, or dimethylol (meth) acrylamide, alkoxymethyl groups such as N-methoxymethyl (meth) acrylamide or N-butoxymethyl Olefins, such as vinyl monomers, ethylene, propylene, or isoprene;

Chloroprene, and butadiene; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether and isobutyl vinyl ether; And fatty acid vils such as vinyl propionate. However, the present invention is not limited thereto.

≪ Block copolymer resin >

The resinous dispersant (a) used in the first embodiment of the present invention can be produced by a known method, but in particular, (1) a method using living polymerization, or (2) a method in which a basic aromatic The polymer coupling method is preferable in which the precursor (a11) of the coalescing block (a1) is reacted with the precursor (a21) of the pigment carrier affinity copolymer block (a2) having a functional group at the terminal. Among these, a method using (1) living polymerization is particularly preferable.

(1) Living polymerization

The living polymerization method suppresses side reactions occurring in general radical polymerization and moreover causes uniform polymerization of the polymerization. Therefore, a block polymer and a resin having a uniform molecular weight can be easily synthesized. Among them, an atomic transfer radical polymerization method using an organic halide or a halogenated sulfonyl compound as an initiator and a transition metal complex as a catalyst can be applied to a wide range of monomers, and a polymerization temperature applicable to existing equipment is adopted It is preferable. The atom transfer radical polymerization can be carried out by the methods described in References 1 to 8 below.

(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

(Reference 5) International Publication No. 96/30421 Pamphlet

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

(Reference 7) Japanese Patent Application Laid-Open No. 9-208616

(Reference 8) Japanese Unexamined Patent Publication No. 8-41117

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

An organic ligand is used for the metal complex. The organic ligand is used to enable solubility in the polymerization solvent and reversible change of the redox conjugate complex. The coordination atom of the metal may be a nitrogen atom, an oxygen atom, a phosphorus atom, or a sulfur atom, but is preferably a nitrogen atom or phosphorus atom. Specific examples of the organic ligand include spitalene, or 2,2'-bipyridyl and derivatives thereof, 1,10-phenanthroline or derivatives thereof, tetramethylethylenediamine, pentamethyldiethylenetriamine, tris (dimethylamino Ethyl) amine, hexamethyl (2-aminoethyl) amine, triphenylphosphine, or tributylphosphine. Among the above catalysts, it is preferable to use a combination of copper halide and tetraethylenediamine for polymerization in terms of the polymerization rate and the molecular weight of the block resin.

The transition metal and the organic ligand may be added separately to form a metal complex in the polymer. Alternatively, a metal complex may be synthesized and added to the polymerization system in advance. Particularly, when the transition metal is copper, the former method is preferable, and the latter method is preferable for ruthenium, iron, or nickel. Specific examples of the ruthenium, iron, or nickel complex is synthesized previously, tris triphenyl phosphino dichloride ruthenium _{(Ru (Cl) 2 (PPh} 3) 3, Beast less diphenylphosphino the ferric _{(Fe (Cl) 2 (PPh} 3 ), and the _2), Beast less diphenylphosphino dichloride nickel _{(Ni (Cl) 2 (PPh} 3) 2), or bis tributyl phosphino nickel bromide _{(NiBr 2 (PBu 3) 2} ) or the like.

As the initiator used in the atom transfer radical polymerization method, a known one can be used, but an organic halide having a highly reactive carbon-halogen bond, a halogenated sulfonyl compound, or the like is used. Specific examples thereof include ethyl bromoisobutyrate, ethyl bromobutyrate, ethyl chloroisobutyrate, ethyl chlorobutyrate, para-toluenesulfonic chloride, bromoethylbenzene, and chloroethylbenzene. These may be used alone or in combination.

In the atom transfer radical polymerization, the atom transfer radical polymerization initiator is appropriately selected according to the molecular weight of the resin to be synthesized, but is preferably 0.001 to 10 mol%, more preferably 0.01 to 10 mol%, based on the total amount of the radical polymerizable monomer. 1 mol%. The amount of the transition metal to be used is preferably from 0.03 to 3 mol, more preferably from 0.1 to 2 mol, per mol of the initiator in the form of a halide or the like. The ligand is used in a proportion of usually 1 to 5 moles, preferably 1.2 to 3 moles, per 1 mole of the above transition metal (in the form of a halide or the like). When the initiator of the atom transfer radical polymerization, the transition metal and the ligand are used in such a ratio as described above, they are suitable in terms of the reactivity of the living radical polymerization and the molecular weight of the resulting polymer.

In addition, due to the nature of atom transfer radical polymerization, the resulting resin has an active carbon-halogen bond at the termination end thereof and can be modified by a known method to introduce the functional group. Further, polymerization can be carried out with a polymerization initiator having a functional group, and a functional group can be introduced at the terminal of the resin to be used for various reactions.

The atom transfer radical polymerization can be carried out in the absence of solvent and may be carried out in the presence of a solvent such as butyl acetate, toluene, xylene, anisole, methyl ethyl ketone, or cyclohexanone. Particularly, a ketone solvent is preferable in view of the polymerization rate, and methyl ethyl ketone is particularly preferable. In the case of using a solvent, it is preferable to use the amount of the solvent so that the concentration of the solvent after completion of the polymerization is 50% by weight or less in order to prevent the polymerization rate from lowering. There is no particular problem of safety regarding the control of the polymerization heat and the like even in the case of a solvent or a small amount of a solvent, and it is preferable from the viewpoints of economical efficiency and environmental measures by reducing the solvent.

Polymerization conditions may be a polymerization time of about 1 to 100 hours, depending on the final molecular weight or polymerization temperature at a polymerization temperature of 60 to 130 DEG C in terms of polymerization rate and inactivation of the catalyst. In the polymerization reaction, it is preferable to carry out the reaction in an inert gas atmosphere such as nitrogen or argon to prevent inactivation of the polymerization catalyst by oxygen.

After completion of the polymerization reaction, the polymerization reaction system is preferably cooled to 0 deg. C or lower, more preferably about -78 deg. C to terminate the reaction, and the remaining monomer and / or solvent may be removed in a suitable solvent The filtration of the precipitated polymer can be carried out by centrifugation, washing and drying of the polymer. The block resin used in the present invention can be obtained by removing the transition metal or the like contained in the polymerization system according to necessity and then evaporating the volatile matter. Examples of the removing method include a method of diluting the reaction mixture with an organic solvent such as tetrahydrofuran, toluene, or methyl ethyl ketone, washing with water or a dilute hydrochloric acid or an aqueous amine solution, contacting the resin solution with the cation exchange resin or the chelate resin, A method of passing through a column or pad of alumina, silica or clay, a method of adding an adsorbent such as a reducing agent or hydrotalcite, followed by filtration and centrifugation. From the viewpoint of simplicity of processing, it is preferable to add a cation exchange resin and an acid adsorbent such as hydrotalcite to the diluted resin solution and stir the solution, and then filtrate the ion exchange resin and acid adsorbent to obtain a resin solution.

When water is mixed into the resin solution by the refining treatment, the reaction between the block resin and the curing agent used in the present invention may be inhibited. In this case, a solvent that is miscible with water is added to the resin solution and treatment such as azeotropic dehydration It is preferable to remove moisture from the resin solution.

In the atom transfer radical polymerization used in the present invention, in order to suppress side reactions generated during general radical polymerization, depending on the addition ratio of the initiator of the atom transfer radical polymerization and the radical polymerizable monomer added at the time of polymerization, The ratio of the copolymer block (a1) or the pigment carrier affinity copolymer block (a2) can be freely adjusted.

(2) Polymer coupling method

Preferable examples of 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) include carboxyl group, primary amino group, hydroxyl group , Or an alkoxysilyl group.

As a method of introducing the terminal functional group into the precursor (a11) of the basic copolymer block (a1) and the precursor (a21) of the pigment carrier affinity copolymer block (a2), a chain transfer agent having the functional group and thiol group , A radical polymerization method is preferable. Examples of the chain transfer agent having a carboxyl group include mercaptopropionic acid, chain transfer agents having a primary amino group include cysteamine, mercaptoethanol as a chain transfer agent having a hydroxyl group, and chain transfer agents having an alkoxysilyl group include 3-mercaptopropylmethylmethoxysilane, Or 3-mercaptopropyltrimethoxysilane, respectively.

The reaction of the precursor (a11) and the precursor (a21) can be carried out by a known reaction using, for example, the combination of Table 1 below.

Examples of the polyisocyanate compound of the binder include aromatic polyisocyanates, aliphatic polyisocyanates, aromatic aliphatic polyisocyanates, and alicyclic polyisocyanates. Examples of the aromatic polyisocyanate include 1,3-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,6-tolylene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, 4,4'- Diphenyl ether diisocyanate, or 4,4 ', 4 " -triphenyl methane triisocyanate. Examples of the aliphatic polyisocyanate include aliphatic polyisocyanates such as trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, Isocyanate, dodecamethylene diisocyanate, or 2,4,4-trimethylhexamethylene diisocyanate. Examples of the aromatic aliphatic polyisocyanate include ω, ω'-diisocyanate-1,3-dimethylbenzene, ω'-diisocyanate-1,4-dimethylbenzene, ω, ω'-diisocyanate-1,4 -Diethylbenzene, 1,4-tetramethyl xylylene diisocyanate, or 1,3-tetramethyl xylylene diisocyanate. Examples of the alicyclic polyisocyanate include 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane di Cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4'-methylene bis (cyclohexyl isocyanate), 1,4-bis (isocyanate methyl) cyclohexane, or 1,4-bis (isocyanatomethyl) cyclohexane, and the like, but are not limited thereto. In addition, trimethylolpropane duct bodies of some of the above polyisocyanates, burettes reacted with water, trimer having an isocyanurate ring, and the like can also be used in combination.

As the polyepoxy compound of the binder, a polyepoxy compound having two or more glycidyl groups is preferable. Specific examples include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, trimethylol propane triglycidyl ether, trimethylol ethane triglycidyl ether Aliphatic polyepoxy compounds such as dibutyl ether, diester ether, sorbitol polyglycidyl ether, or pentaerythritol polyglycidyl ether, aromatic polyepoxy compounds such as bisphenol A or bisphenol F type, tetraglycidylaminophenylmethane, And glycidylamine type epoxy compounds such as 1,3-bis (N, N-glycidylaminomethyl) cyclohexane, but are not limited thereto.

The number average molecular weight of the block copolymer-type basic resinous dispersant used in the first embodiment of the present invention is usually preferably from 500 to 50000, more preferably from 3,000 to 30,000. When the number average molecular weight is less than 500, the effect of steric repulsion by the pigment-affinity copolymer block (a2), the compatibility effect with the pigment carrier, and the compatibility effect with the pigment carrier and the solvent when the solvent is used are small , It is difficult to prevent aggregation of the pigment, and the viscosity of the dispersion sometimes increases. On the other hand, if the number average molecular weight exceeds 50,000, the addition amount of the resin required for dispersion increases, resulting in a decrease in the pigment concentration in the coating film.

The amine copolymer of the block copolymer type basic resinous dispersant used in the first embodiment of the present invention has an amine value of 35 to 100 mgKOH / g, more preferably 50 to 75 mgKOH / g. If the amine value is less than 35 mgKOH / g, it is not sufficiently adsorbed on the pigment and dispersion is poor. When the amine value is more than 100 mgKOH / g, adsorption or reaction to the acidic component in the pigment carrier causes poor adsorption efficiency on the pigment , And dispersion failure occurs.

The constituent weight ratio of the basic copolymer block (a1) to the pigment carrier affinity copolymer block (a2) and the number average molecular weight of each block are such that the number average molecular weight and the amine value of the entire resinous dispersant are within the above- It is desirable that the device can be designed arbitrarily.

In the green coloring composition of the first embodiment of the present invention, the blending amount of the basic resinous dispersant (a) is preferably 0.001 to 50 wt%, more preferably 0.001 to 50 wt%, based on the total weight of the pigment component (A) Is 0.1 to 30% by weight, and most preferably 0.5 to 25% by weight. When the blending amount of the resinous dispersant (a) is less than 0.001% by weight based on the total weight of the pigment component (A), the dispersibility may deteriorate. When the blending amount exceeds 40% by weight, the heat resistance and the light resistance may be deteriorated .

[Coloring matter derivative (b) having basic substituent]

The green coloring composition of the present invention is characterized by using a zinc phthalocyanine halide having zinc as a main metal as a main pigment of the pigment component (A), but the zinc halide phthalocyanine is generally used in the form of copper halide Compared with phthalocyanine pigments, an acidic pigment having zinc in its central metal has a negative charge on its pigment surface. Therefore, when a dispersant having a basic substituent is used, the adsorption to an acidic pigment is sufficient, and the pigment dispersion can exhibit sufficient fluidity and color characteristics. In the second embodiment of the present invention, a suitable pigment dispersion can be obtained by using the pigment derivative (b) having a basic substituent as a dispersing agent.

As described above, in the second embodiment of the coloring composition for a color filter of the present invention, the coloring derivative (b) may be used for the purpose of improving the dispersibility of the pigment. Examples of the pigment derivative include organic pigments, anthraquinones, acridones, and compounds obtained by introducing a phthalimide methyl group, which may have a basic substituent, an acidic substituent or a substituent, in triazine.

In the present invention, a basic derivative is preferable, and a basic derivative is a compound represented by the following general formula (1), which is a derivative having a specific base skeleton having a basic group. The dye derivative having a basic group is not particularly limited, but a dye derivative having a triazine ring skeleton having a basic group represented by the following general formula (4) can be suitably used.

(1)

(Wherein, in formula (1)

P is an m-valence, an organic pigment residue, an anthraquinone skeleton, an acridone skeleton, a triazine skeleton,

m is an integer of 1 to 4,

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

(2)

(3)

(4)

[Wherein, in formulas (2) to (4)

A bond, or directly, - X is _{-SO 2 -, -CO-, -CH 2} -, -CH 2 NHCOCH 2 -, -CH 2 NHSO 2 CH 2

Y is -NH-, -O-, or a direct bond,

n is an integer of 1 to 10,

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

R ⁵⁸ and R ⁵⁹ are each independently a hydrogen bond, an alkyl group having 1 to 36 carbon atoms which may have a substituent, an alkenyl group having 2 to 36 carbon atoms which may have a substituent, or a phenyl group which may have a substituent,

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

R ⁵⁰ and R ⁵¹ each independently represent a hydrogen atom, an alkyl group having 1 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, or R ⁵⁰ and R ⁵¹ may be combined to form an additional nitrogen , Oxygen, or a sulfur atom, which may have a substituent,

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, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, An arylene group having 6 to 20 carbon atoms,

R ⁵⁶ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent,

R ⁵⁷ is a substituent represented by the formula (2) or a substituent represented by the formula (3)

Q is a hydroxyl group, an alkoxyl group, a substituent represented by the formula 2, or a substituent represented by the formula 3.

Examples of the amine component used for forming the substituent represented by the general formulas 2 to 4 include dimethylamine, diethylamine, methylethylamine, N, N-ethylisopropylamine, N, N-ethylpropylamine, N N, N-diethylamine, N, N-tert-butylethylamine, diisopropylamine, dipropylamine, N, N-sec- butyl Propylamine, diisobutylamine, diisobutylamine, N, N-isobutyl-sec-butylamine, diamylamine, diisooamylamine, dihexylamine, dicyclohexylamine, di (2-ethylhexyl) amine, dioctylamine, N, N-methyloctadecylamine, didecylamine, diallylamine, N, N-ethyl-1,2-dimethylpropylamine, N, N, N-dimethylaminoethylamine, N, N-dimethylaminobutylamine, N, N-dimethylaniline, N, Diethylaminoethylamine, N, N N, N-diethylaminobutylamine, N, N-dipropylaminobutylamine, N, N-diethylaminobutylamine, -Dibutylaminopropylamine, N, N-dibutylaminoethylamine, N, N-dibutylaminobutylamine, N, N-diisobutylaminopentylamine, N, N- But are not limited to, N, N-diethylaminoethylamine, N, N-ethylhexylaminoethylamine, N, N-distearylaminoethylamine, N, But are not limited to, choline, 3-piperolin, 4-piperolin, 2,4-lupetidine, 2,6-lupetidine, Aminoethylpiperidine, N-aminoethyl-4-piperazinecarboxylic acid, isonicotinic acid, isonicotinic acid, isonipecotic acid, isonipecotic acid methyl, isonipecotic acid ethyl, 2-piperidineethanol, pyrrolidine, , N-aminoethylmorpholine, N-aminopropylpiperidine, N-aminopropyl Aminopropylmorpholine, N-methylpiperazine, N-butylpiperazine, N-methyl homopiperazine, 1-cyclopentylpiperazine, 1 -Amino-4-methylpiperazine, 1-cyclopentylpiperazine, and the like.

The pigment derivative, anthraquinone derivative, and acridone derivative having a basic substituent group used in the second embodiment of the present invention can be synthesized by various synthetic routes. For example, after the introduction of a substituent represented by the formula (5) to (8) into an organic dye, anthraquinone, or acridone, the amine that forms a substituent represented by the formula N, N-dimethylaminopropylamine, N-methylpiperazine, diethylamine or 4- [4-hydroxy-6- [3- (dibutylamino) propylamino] , 5-triazin-2-ylamino] aniline, and the like.

Equation (5):

Equation (6):

Equation (7):

Equation (8):

In the reaction of the substituents of the formulas (5) to (8) with the amine component, some of the substituents of the formulas (5) to (8) may be hydrolyzed to replace the chlorine substituted by a hydroxyl group. In this case, the formulas (5) and (6) are respectively a sulfonic acid group and a carboxylic acid group, but they may be either free acid or a salt with a mono-trivalent metal or a monoamine.

When the organic dye is an azo dye, it is also possible to prepare an azo pigment derivative by introducing a substituent represented by the general formula (2) to (4) into a diazo component or a coupling component in advance and then conducting a coupling reaction .

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, an amine component, such as N, N-dimethylaminopropylamine or N, N-dimethylaminopropylamine, which forms cyanuric chloride as a starting material and forms substituents represented by formulas (2) to (4) in at least one chlorine atom of cyanuric chloride, Methylpiperazine, and the like, and then reacting the remaining chlorine of cyanuric chloride with various amines or alcohols.

In the pigment composition of the present invention, the amount of the pigment derivative having a base substituent is preferably from 1 to 50 parts by weight, more preferably from 3 to 30 parts by weight, and most preferably from 3 to 30 parts by weight, per 100 parts by weight of the pigment component (A) Is 5 to 25 parts by weight. When the amount of the basic derivative is less than 1 part by weight based on 100 parts by weight of the pigment, the dispersibility may be poor. When the amount is more than 50 parts by weight, the heat resistance and the light resistance may be deteriorated. Among them, it is preferable that the basic substituent has a triazine structure in terms of dispersion stability.

[Organic solvent (c)]

In the third embodiment of the green coloring composition of the present invention, the pigment component (A) is sufficiently dispersed in the pigment carrier (B) and coated on a substrate such as a glass substrate so that the dry film thickness becomes 0.2 to 5 탆, An organic solvent (c) is added to facilitate formation of the segment.

As the organic solvent (c), an organic solvent (c1) having a solubility parameter (SP value) of 8.0 to 10.0 (cal / cm3) ^1/2 and a boiling point at 760 mmHg of 140 to 159 ° C, (SP) of 8.0 to 10.0 (cal / cm < 3 >) ^1/2 and an organic solvent (c2) having a boiling point of 160 to 200 DEG C at 760 mmHg is used.

In the present specification, the solubility parameter (SP value) is a value obtained by a physical quantity (evaporation heat or the like) of an organic solvent and is a value described in various literatures.

More preferably, the organic solvent (c1) having a solubility parameter (SP value) of 8.0 to 10.0 (cal / cm3) ^1/2 and a boiling point of 144 to 157 占 폚 at 760 mmHg and a solubility parameter ) Of 8.0 to 10.0 (cal / cm 3) ^1/2 and an organic solvent (c2) having a boiling point of 164 to 192 ° C at 760 mmHg.

The organic solvent (c1) is preferably at least one solvent selected from propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate , And the organic solvent (c2) is preferably at least one solvent selected from, for example, cyclohexyl acetate, propylene glycol diacetate, diethylene glycol diethyl ether and ethyl 3-ethoxypropionate. Cyclohexyl acetate is also referred to as cyclohexanol acetate.

The green coloring composition for a color filter according to the third embodiment of the present invention blends the organic solvent (c1) and the organic solvent (c2) having a specific range of solubility parameter (SP value) It has rain and high accuracy. Further, the coating film coated with the colored composition has reduced film thickness unevenness and streaking unevenness, and has a uniform film thickness and excellent performance.

When the solubility parameter (SP value) is smaller than 8.0 (cal / cm 3) ^1/2 , the dispersion of the zinc halphthalocyanine pigment is deteriorated and when it is larger than 10.0 (cal / cm 3) ^1/2 , the zinc halphthalocyanine pigment dissolves in the organic solvent And the brightness and the contrast ratio are lowered.

If the boiling point of the solvent used as the organic solvent (c1) is less than 140 占 폚, film thickness unevenness and uneven streaks may occur, which is not preferable. Further, if the boiling point of the solvent used as the organic solvent (c2) becomes larger than 200 占 폚, tackness remains, which is not preferable.

The mixed organic solvent (c) may be used in an amount of 800 to 4,000 weight% based on the whole amount of the pigment component (A). The blending amount of the mixed organic solvent (c) is preferably 50 to 95% by weight of the organic solvent (c1) and 5 to 50% by weight of the organic solvent (c2). 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) is out of the range of 50 to 95%, there arises a problem that unevenness of the film thickness and uneven streaks occur as a coating liquid. The mixing of the organic solvent (c1) and the organic solvent (c2) is important for the preferable dispersion of the zinc halide phthalocyanine pigment.

As described above, the organic solvent (c1) used for dispersing the zinc halphthalocyanine pigment and the organic solvent (c2) added for improving the problems in the coating film coated with the green coloring composition for a color filter of the present invention ) Is limited to a specific one, but in order to facilitate formation of the coloring composition as a filter segment, the following organic solvent may be added as an auxiliary solvent.

1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl- 1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, 3- Methoxybutyl acetate, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichloro Benzene, N, N-dimethylacetamide, N, N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propylacetate, N-methylpyrrolidone, o-xylene, o-chlorotoluene, o Diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene,? -Butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, Ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl Ethylene glycol monoethyl ether, ethylene glycol mono tert-butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, diisobutyl ketone, diethylene glycol dimethyl Ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanone, di Propylene glycol dimethyl ether, propylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, Propylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether propionate, Methyl isobutyl ketone, methylcyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, or dibasic acid ester.

In order to obtain a preferable green coloring composition in the present invention, it is preferable that the total amount of the organic solvent (c1) and the organic solvent (c2) in the total mixed organic solvent (c) is 70 wt% or more. More preferably, the total amount is 80% by weight, particularly preferably the total amount is 85% by weight or more. Addition of a large amount of an auxiliary solvent other than the organic solvent (c1) and the organic solvent (c2) adversely affects the stability of the zinc halphthalocyanine pigment dispersion and the coatability of the coating film coated with the present colored composition.

[Dispersion]

The green coloring composition of the present invention is obtained by mixing a pigment component (A) containing at least a zinc phthalocyanine pigment with the basic resinous dispersant (a) or the basic resinous dispersant (a) and the pigment derivative having the basic substituent b) can be finely dispersed in the pigment carrier (B) using various dispersion means such as a three roll mill, a twill mill, a sand mill, a kneader or an attritor. The green coloring composition of the present invention can also be prepared by mixing several kinds of pigments separately dispersed in a pigment carrier (B).

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

[Photopolymerization initiator]

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

Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy- 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) Phenyl] -2-morpholinopropane-1-one, benzoin-based photopolymerization initiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether or benzyl dimethyl ketal Benzophenone-based photopolymerization initiators such as benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenyl benzophenone, hydroxybenzophenone, acrylated benzophenone, or 4-benzoyl- , 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, or 2,4-diisopropylthioxanthone, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4, Bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloromethyl) (Trichloromethyl) -6-styryl-s-triazine, 2- (naphtho-1-yl) -4,6-bis Methyl) -s-triazine, 2- (4-methoxy-naphtho-1-yl) -4,6-bis (trichloromethyl) (4'-methoxystyryl) -6-triazine and the like, a borate-based photopolymerization initiator, a carbazole-based photopolymerization initiator, or a triazine-based photopolymerization initiator such as 2,4-trichloromethyl An imidazole-based photopolymerization initiator, and the like are used, but the present invention is not limited thereto.

The photopolymerization initiator may be used singly or in admixture of two or more. As the sensitizer, for example,? -Acyloxyester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone , Ethyl anthraquinone, 4,4'-diethylisophthalophenone, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, or 4,4'-diethylaminobenzo Phenol and the like may be used in combination, but the present invention is not limited thereto.

The blending amount when the sensitizer is used is preferably 3 to 60% by weight, more preferably 5 to 50% by weight from the viewpoint of photocurability and developability, based on the combined weight of the photopolymerization initiator contained in the coloring composition Do.

[Dispersing aids]

When the pigment is dispersed in the pigment carrier (B), a dispersion auxiliary such as a resin-type pigment dispersant or a surfactant, which is separate from the basic resinous dispersant (a), may be suitably used. When the green coloring composition in which the pigment is dispersed in the pigment carrier (B) by using the dispersion auxiliary agent is used, the dispersion aid is excellent in the dispersion of the pigment A color filter having a high transmittance can be obtained.

A resin pigment dispersing system different from the basic resinous dispersant (a), a pigment affinity site having a property of adsorbing to the pigment, and a site compatible with the pigment carrier, and adsorbed on the pigment to form a pigment carrier B) to stabilize the dispersion. As the resinous pigment dispersant, known resinous pigment dispersants other than the above-mentioned basic resinous dispersant (a), specifically, polycarboxylic acid esters such as polyurethane or polyacrylate, unsaturated polyamides, polycarboxylic acids, A polycarboxylic acid (partial) amine salt, a polycarboxylic acid ammonium salt, a polycarboxylic acid alkylamine salt, a polysiloxane, a long chain polyaminoamide phosphate, a hydroxyl group-containing polycarboxylic acid ester, (Meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-butadiene copolymer and the like, Maleic acid copolymer, polyvinyl alcohol, or polyvinylpyrrolidone, water-soluble resins, water-soluble polymer compounds, Poly acrylate, ethylene oxide / propylene oxide addition compound, or a phosphoric acid ester and the like are used, and these may be used individually or in combination of two or more.

Examples of the surfactant include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salts of styrene-acrylic acid copolymer, sodium stearate, sodium alkylnaphthalene sulfonate, sodium alkyldiphenyl ether disulfonate, Anionic surfactants such as monoethanolamine laurylsulfate, triethanolamine laurylsulfate, ammonium laurylsulfate, stearic acid monoethanolamine, monoethanolamine of styrene-acrylic acid copolymer, and polyoxyethylene alkyl ether phosphate ester; Nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate, and polyethylene glycol monolaurate; Cationic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; Alkyl betaine such as alkyldimethylaminoacetic acid betaine, and alkyl imidazoline. These surfactants may be used singly or in combination of two or more. However, the present invention is not limited thereto.

In the green coloring composition for a color filter of the present invention, the pigment is sufficiently dispersed in the pigment carrier (B) and coated on a transparent substrate such as a glass substrate to a dry film thickness of 0.2 to 5 mu m to form a filter segment It may be used in the form of " green ink " or " green resist ink ".

In the first and second embodiments of the present invention, the organic solvent (c1), the organic solvent (c2) and the organic solvent (c2) are used in the third embodiment of the present invention, And an auxiliary solvent.

The green coloring composition of the present invention preferably has a viscosity immediately after dispersion (viscosity at 25 캜 of 60 rpm) of 2 to 100 mPa s, a thixotropic index immediately after dispersion (rotational speed of 6 rpm at 25 캜 (Ratio of viscosity to viscosity at 60 rpm) of not more than 1.4, and 3 months of storage at 10 캜 for 3 months. The viscosity increase rate at 60 rpm at 25 DEG C stored for 3 months under the condition of 10 DEG C) is preferably less than 20%. When the viscosity immediately after dispersion is less than 2 mPa.s or more than 100 mPa.s or when the thixotropic index immediately after dispersion exceeds 1.4 or when the viscosity increase rate with time is 20% or more, uniformity of application can be maintained No color filter having a uniform film thickness can be obtained. The viscosity and the thixotropic index can be measured by using, for example, an E-type viscometer ("ELD-type viscometer" manufactured by Toki Sangyo Co., Ltd.).

[Stabilizer]

Further, the green coloring composition of the present invention may contain a storage stabilizer to stabilize the viscosity of the composition over time.

As the storage stabilizer, for example,

Quaternary ammonium chlorides such as benzyltrimethylammonium chloride or diethylhydroxyamine;

Organic acids such as lactic acid and oxalic acid;

Methyl esters of the above organic acids;

catechols such as t-butyl pyrocatechol;

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

Phosphorous acid salts and the like.

[Removal of Coarse Particles and Dust]

The green coloring composition of the present invention can be obtained by coarse grains of 5 占 퐉 or more, preferably coarse grains of 1 占 퐉 or more, more preferably coarse grains of 0.5 占 퐉 or more and mixed grains of 0.5 占 퐉 or more by means of centrifugal separation, sintering filter, It is preferable to carry out the removal. When coarse particles are present, foreign matters remain in the color filter, causing a problem in practical use. In addition, foreign matters are clogged in piping or nozzles in the application step, and serious problems in production occur. Thus, it is preferable that the green coloring composition does not contain substantially 0.5 mu m or more of particles. More preferably, the particles contained in the green coloring composition are 0.3 m or less (particle diameter according to SEM).

The average dispersed particle diameter is preferably 0.05 to 0.2 占 퐉 in order to increase the lightness and the contrast ratio, and more preferably 0.06 to 0.15 占 퐉 because the brightness and the contrast ratio can be further increased.

[Production of color filter]

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

The formation of the filter segment by the printing method can be patterned only by repeating printing and drying of the coloring composition prepared as the printing ink, so that the mass production is excellent at low cost as a manufacturing method of the color filter. In addition, as printing technology is developed, it is possible to perform printing of a fine pattern having high dimensional accuracy and smoothness. In order to perform printing, it is preferable that the composition is such that the ink does not dry and solidify on a printing plate or on a blanket. In addition, it is also important to control the flowability of the ink on the printing machine, and it is also possible to adjust the viscosity of the ink by the dispersing agent and the extender pigment.

When the filter segment is formed by the photolithography method, the coloring composition prepared as the above solvent-developed or alkali-developed coloring resist is applied onto a transparent substrate by a coating method such as a spray coat, a spin coat, a slit coat, And a dry film thickness of 0.2 to 5 mu m. If necessary, the dried film is passed through a mask having a predetermined pattern provided in contact with or in contact with the film, and ultraviolet exposure is performed. Thereafter, the color filter can be produced by dipping in a solvent or an alkaline developing solution, spraying the developing solution by spraying or the like to remove un-hardened portions, forming a desired pattern, and repeating the same operation for different colors. Further, in order to accelerate the polymerization of the colored resist, it is also possible to carry out heating as required. According to the photolithography method, a color filter having a degree (accuracy) higher than that of the printing method described above can be manufactured.

At the time of development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as the alkali developing solution, and organic alkali such as dimethylbenzylamine or triethanolamine may be used. It is also possible to add a defoaming agent or a surfactant to the developer.

Further, in order to increase ultraviolet exposure sensitivity, the above-mentioned colored resist is applied and dried, and then a water-soluble or alkali-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin is applied and dried to form a film which prevents polymerization inhibition by oxygen , And ultraviolet exposure may be performed.

The color filter of the present invention can be produced by an electrodeposition method or a transfer method in addition to the above method, but the coloring composition of the present invention can be used by any method. The electrodeposition method is a method of manufacturing a color filter by electrodeposition of colloidal particles on a transparent conductive film formed on a substrate to electrodeposit the respective color filter segments on the transparent conductive film.

The transfer method is a method in which filter segments are formed in advance on the surface of a releasable transfer base sheet, and the filter segments are transferred onto a target substrate.

[Color Filter]

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

The red filter segments can be formed using conventional red coloring compositions. The red coloring composition may include, for example, CI Pigment Red 7, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 57: 1, 81, 81: Red pigments are used such as 1,1,2,3,4,12,14,14,122,146,168,177,178,184,185,187,202,208,202,246,254,255,264,270,272,279 and the like .

The red coloring composition may contain 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: , 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101 , 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153 , 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188 , 193, 194, 198, 199, 213 and 214 can be used in combination.

Further, the blue filter segment can be formed using a conventional 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 and 64 are used for the blue coloring composition. Further, purple pigments such as C. I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, and 50 can be used in combination with the purple coloring composition.

[Example]

Hereinafter, the present invention will be described on the basis of examples, but the present invention is not limited thereto. In Examples and Comparative Examples, "part" means "part by weight". Mn and Mw mean the number average molecular weight and the weight average molecular weight, respectively.

(1) Average molecular weight of basic resinous dispersant (a)

In the following Examples and Comparative Examples, the number average molecular weight (Mn) and the weight average molecular weight (Mw) of the basic resinous dispersant were measured by using HLC-8320GPC (manufactured by TOSOH CORPORATION) as a device and SUPER-AW3000 And the number average molecular weight (Mn) and the weight average molecular weight (Mw) of polystyrene measured using 30 mM triethylamine and 10 mM LiBr N, N-dimethylformamide as eluent.

(2) Amine

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

(3) Average molecular weight of the resin of the pigment carrier (B)

The number average molecular weight (Mn) and the weight average molecular weight (Mw) of the acrylic resin used as the resin of the pigment carrier (B) were measured by GPC (manufactured by TOHSOKU Co., Ltd., HLC-8120GPC ), And the number-average molecular weight (Mn) and the weight-average molecular weight (Mw) in terms of polystyrene measured using THF in the 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 acid value (mgKOH / g) measured in accordance with the potentiometric titration method of JIS K 0070 into a solid content.

(First embodiment)

The green coloring composition containing the basic resinous dispersant (a) as an essential component will be described with reference to Examples (Example I series) and Comparative Examples (Comparative Example I series).

First, the resin type dispersant, the solution, the commercially available resin type dispersant solution, the acrylic resin, and the solution thereof used in the Example I series and the comparative example I series will be described.

Synthesis Example I-1: Synthesis of resinous dispersant I-1 and preparation of its solution

70 parts of methyl ethyl ketone, 76.0 parts of n-butyl acrylate, 2.8 parts of sparteine and 1.9 parts of ethyl bromoisobutyrate were placed in four separable flasks equipped with a thermometer, a stirrer, a distillation tube and a condenser, The temperature was raised to 40 DEG C under an air stream. 1.1 parts of cuprous chloride was added, and the temperature was raised to 75 캜 to initiate polymerization. After 3 hours of polymerization, the polymerization solution was sampled, and it was confirmed that the polymerization yield was 95% or more from the solid content of the polymerization. 24.0 parts of N, N-dimethylaminoethyl methacrylate and 30.0 parts of MEK were added, Respectively. After 2 hours, it was confirmed that the polymerization yield was 97% or more from the solid content of the polymerization solution, and the polymerization was stopped by cooling to room temperature. 100 parts of the obtained resin solution was diluted with 100 parts of methyl ethyl ketone, 60 parts of a cation exchange resin " Daiion PK228LH " (manufactured by Mitsubishi Chemical Corporation) was added and stirred at room temperature for 1 hour. Further, hydrotalcite (Manufactured by Kyoei Kagaku Kogyo K.K.), and stirring was carried out for 30 minutes. The cation exchange resin and the adsorbent were removed by filtration to remove the residue of the polymerization catalyst. In addition, the resin solution was concentrated and ethylene glycol mono Methyl ether acetate to obtain a solution of a resinous dispersant I-1 (Mn = 10200, Mw = 12200, amine value of 86 mgKOH / g) having a nonvolatile fraction of 40% by weight.

Synthesis Example I-2: Synthesis of resinous dispersant I-2 and preparation of its solution

70 parts of methyl ethyl ketone, 75.0 parts of n-butyl acrylate, 10.0 parts of methyl methacrylate, 2.3 parts of sparte, and 1.6 parts of ethyl bromoisobutyrate were placed in the same manner as in Synthesis Example I-1, And 0.9 part of copper were added to initiate polymerization. After polymerization for 3 hours, 15.0 parts of N, N-dimethylaminoethyl methacrylate and 30.0 parts of MEK were added, and further polymerization was carried out for 2 hours. Thereafter, the same polymerization catalyst as in Synthesis Example I-1 was removed to obtain a resinous dispersant I-2 (Mn = 11900, Mw = 13200, amine value = 54 mgKOH / g) having a nonvolatile fraction of 40 wt% ≪ / RTI >

Synthesis Example I-3: Synthesis of resinous dispersant I-3 and preparation of its solution

In the same manner as in Synthesis Example I-1, 70 parts of methyl ethyl ketone, 45.0 parts of ethyl acrylate, 43.0 parts of methyl methacrylate, 3.3 parts of sparte, and 2.8 parts of ethyl bromoisobutyrate were charged, And polymerization was initiated. After polymerization for 3 hours, 12.0 parts of N, N-dimethylaminoethyl methacrylate and 30.0 parts of MEK were added, and further polymerization was carried out for 2 hours. Thereafter, the same polymerization catalyst as in Synthesis Example I-1 was removed to obtain a resinous dispersant I-3 (Mn = 7000, Mw = 8500, amine value 43 mgKOH / g) having a nonvolatile fraction of 40 wt% ≪ / RTI >

Synthesis Example I-4: Synthesis of resinous dispersant I-4 and preparation of its solution

70 parts of methyl ethyl ketone, 71.0 parts of n-butyl acrylate, 2.8 parts of sparte, and 1.9 parts of ethyl bromoisobutyrate were placed in the same manner as in Synthesis Example I-1, and 1.4 parts of cuprous chloride was added thereto. . After polymerization for 3 hours, 29.0 parts of N, N-dimethylaminoethyl methacrylate and 30.0 parts of MEK were added and polymerization was carried out for 2 hours. Thereafter, the same polymerization catalyst as in Synthesis Example I-1 was removed to obtain a resinous dispersant I-4 (Mn = 10000, Mw = 12000, amine value = 105 mgKOH / g) having a nonvolatile fraction of 40 wt% ≪ / RTI >

Synthesis Example I-5: Synthesis of resinous dispersant I-5 and preparation of its solution

70 parts of methyl ethyl ketone, 66.0 parts of n-butyl acrylate, 2.8 parts of sparte, and 1.9 parts of ethyl bromoisobutyrate were placed in the same manner as in Synthesis Example I-1, and 1.4 parts of cuprous chloride was added thereto. . After 3 hours of polymerization, 34.0 parts of N, N-dimethylaminoethyl methacrylate and 30.0 parts of MEK were added and polymerization was further carried out for 2 hours. Thereafter, the same polymerization catalyst as in Synthesis Example I-1 was removed to obtain a resinous dispersant I-5 (Mn = 9800, Mw = 12000, amine value of 121 mgKOH / g) having a nonvolatile fraction of 40 wt% ≪ / RTI >

Synthesis Example I-6: Preparation of commercially available resin-type dispersant solution

163, 164, 167, 174, 184, 2000, 2050 manufactured by Big Chem Japan Co., Ltd., commercially available resinous dispersant, SOLSPERSE-34750, 56000 manufactured by Lubrizol Japan, EFKA 4330, 4046, 4060 , And 4080 were each prepared into a 40% by weight non-volatile fraction by using ethylene glycol monomethyl ether acetate after reducing the non-volatile content to 60% or more by reduced-pressure drying for those having a non-volatile content of less than 40% Was used as a solution.

Synthesis Example I-A: Synthesis of acrylic resin I-A and preparation of its solution

800 parts of cyclohexanone was placed in a reaction vessel, and 80.0 parts of styrene, 40.0 parts of methacrylic acid, 85.0 parts of N, N-methylmethacrylate, n-butyl 95.0 parts of methacrylate, and 10.0 parts of azobisisobutyronitrile was added dropwise over 1 hour to carry out a polymerization reaction.

After dropwise addition, the mixture was further reacted at 100 ° C for 3 hours, and then azobisisobutyronitrile (2.0 parts) was dissolved in cyclohexanone (50 parts). The reaction was further continued at 100 ° C for 1 hour, To obtain a cyclohexanone solution of acrylic resin IA having an acid value of 87 mgKOH / g.

After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180 캜 for 20 minutes to measure the nonvolatile content. Ethylene glycol monomethyl ether acetate was added to the resin solution so that the nonvolatile content became 20% by weight To prepare a solution of acrylic resin IA.

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

Synthesis of acrylic resins I-B to I-P was carried out in the same manner as in the synthesis of acrylic resin I-A by the monomer composition and amount of initiator (azobisisobutyronitrile amount) shown in Table 2 below to prepare solutions thereof. The acid value and the weight average molecular weight of the synthesized resin are shown in 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

[Example I-1]

2.5 parts of SOLSPERSE-56000 solution prepared according to the method for preparing a solution of a commercially available resinous dispersant, 40.0 parts of the solution of the acrylic resin IA and 40.0 parts of a solution of the ethylene glycol monomethyl (meth) acrylate And 46.5 parts of ether acetate were homogeneously mixed and stirred. Thereafter, zirconia beads having a diameter of 0.5 mm were dispersed for 5 hours using Eiger mill ("Minimodel M-250 MKII" manufactured by Eiger Japan Co.) Followed by filtration to prepare a green pigment dispersion.

Then, 60.0 parts of the green pigment dispersion, 11.0 parts of the solution of the acrylic resin IA, 4.2 parts of trimethylolpropane triacrylate ("NK Ester ATMPT" manufactured by Shin-Nakamura Chemical Co., Ltd.), 10 parts of a photopolymerization initiator 907 "), 0.4 part of a sensitizer (" EAB-F "manufactured by Hodogaya Chemical Co., Ltd.), and 23.2 parts of ethylene glycol monomethyl ether acetate was stirred and mixed to homogeneity and then filtered with a filter of 1.0 μm to obtain an alkali Thereby obtaining a development type green resist material I-1.

[Examples I-2 to I-24]

2 to I-24 were obtained in the same manner as in the method shown in Example I-1 by using the solution of the resinous dispersant, the dye derivative, and the solution of the acrylic resin shown in Table 3 . Table 4 shows the type of resinous dispersant (either block type or non-block type).

[Example I-25]

10 parts of zinc halophthalocyanine green pigment (C. I. pigment green 58), 2.5 parts of a resin solution (nonvolatile matter 40% by weight) of SOLSPERSE-56000,

1.0 part of a pigment derivative having a basic functional group represented by the following formula, 40.0 parts of the solution of the acrylic resin IA, and 46.5 parts of ethylene glycol monomethyl ether acetate was uniformly stirred and mixed. Then, using zirconia beads having a diameter of 0.5 mm, The mixture was dispersed with wheat (Mini Model M-250 MKII, manufactured by Eiger Japan Co., Ltd.) for 5 hours, and then filtered through a 5.0 탆 filter to prepare a green pigment dispersion.

Then, 60.0 parts of the green pigment dispersion, 11.0 parts of the solution of the acrylic resin IA, 4.2 parts of trimethylolpropane triacrylate ("NK Ester ATMPT" manufactured by Shin-Nakamura Chemical Co., Ltd.), 10 parts of a photopolymerization initiator 907 "), 0.4 part of a sensitizer (" EAB-F "manufactured by Hodogaya Chemical Co., Ltd.), and 23.2 parts of ethylene glycol monomethyl ether acetate was stirred and mixed to homogeneity and then filtered with a filter of 1.0 μm to obtain an alkali A development type green resist material I-25 was obtained.

[Examples I-26 to I-48]

I-26 to I-25 were prepared in the same manner as in Example I-25, except that the solution of the resinous dispersant, the dye derivative, and the solution of the alkenyl resin shown in Table 5 were used, 48.

[Example I-49]

10 parts of zinc halophthalocyanine green pigment (C.I. pigment green 58), 2.5 parts of SOLSPERSE-56000 solution (nonvolatile matter 40% by weight), the following formula I-10:

, 1.0 part of a pigment derivative having a triazine ring skeleton having a basic functional group having an anchor portion benzimidazolone, 40.0 parts of the solution of the acrylic resin IA and 46.5 parts of ethylene glycol monomethyl ether acetate was uniformly stirred Thereafter, zirconia beads having a diameter of 0.5 mm were dispersed for 5 hours by Eiger mill (Mini Model M-250 MKII, manufactured by Eiger Japan Co.), and then filtered with a 5.0 탆 filter to prepare a green pigment dispersion.

Then, 60.0 parts of the green pigment dispersion, 11.0 parts of the solution of the acrylic resin IA, 4.2 parts of trimethylolpropane triacrylate ("NK Ester ATMPT" manufactured by Shin-Nakamura Chemical Co., Ltd.), 10 parts of a photopolymerization initiator 907 "), 0.4 part of a sensitizer (" EAB-F "manufactured by Hodogaya Chemical Co., Ltd.), and 23.2 parts of ethylene glycol monomethyl ether acetate was stirred and mixed to homogeneity and then filtered with a filter of 1.0 μm to obtain an alkali A development type green resist material I-49 was obtained.

[Examples I-50 to I-72]

50 to I-72 were prepared in the same manner as in Example 1-49, except that the solution of the resinous dispersant, the dye derivative, and the solution of the acrylic resin shown in Table 6 were used. .

[Comparative Examples I-1 to I-15]

The same procedures as in Example I-1 were carried out except that the dispersant solution (non-volatile matter content of 40% by weight) shown in Table 7 was used instead of the SOLSPERSE-56000 solution used in Example I-1, I-87 was obtained.

[Comparative Example I-16]

An alkali development type resist material I-88 was obtained in the same manner as in Example I-3 except that halogenated copper phthalocyanine green pigment (C.I. pigment green 36) was used instead of zinc halphthalocyanine green pigment (C.I. pigment green 58).

(Assessment Methods)

Using the thus obtained alkali-developable resist materials I-1 to I-88, the viscosity characteristics were measured in order to evaluate the fluidity in the following manner, and the brightness and contrast ratio were measured to evaluate the brightness and contrast ratio (CR) , And the change ratio of the contrast ratio at the time of aging and the rate of increase in the viscosity at the time of aging were measured to evaluate the stability.

(1) Measurement method of viscosity characteristics

The viscosity of the resulting alkali-developable resist material was measured using an E-type viscometer ("ELD-type viscometer" available from Toki Sangyo Co., Ltd.) at a rotational speed of 20 rpm. Further, the ratio of the viscosity at 6 rpm and 60 rpm (referred to as the thixotropic index and the higher the value of the thixotropic property) was determined, and the thixotropic property was evaluated.

(2) Measurement method of viscosity increase rate with time

The initial viscosity of the obtained next day alkali-developable resist material and the viscosity at 40 占 폚 for one week and the aging accelerated viscosity were measured at 25 占 폚 at 20 rpm using an E-type viscometer ("ELD type viscometer" . The initial viscosity measured in this manner and the viscosity at the elapsed time were applied to the following equations to measure the viscosity increase rate with time.

[Aging Viscosity Increase Rate] = (Aging Viscosity / Initial Viscosity) x 100

(3) Measurement of brightness

The obtained alkali-developable resist material was changed in the number of revolutions using a spin coater to prepare three coated substrates so that the dry film thickness was 0.62, 0.6 and 0.58 in the CIE colorimetric system. After coating, the film was dried at 80 DEG C for 30 minutes in a hot air oven, and then the film thickness was measured. From the data of the three points, the brightness at the chromaticity y of 0.6 was determined by the first correlation method. The chromaticity was determined by using a brown spectrophotometer ("OSP-SP100" manufactured by Olympus Optics).

(4) Method of measuring the contrast ratio of the coating film

The contrast ratio of the chromaticity y of 0.6 was obtained from the data of three points by the substrate used for the measurement of the brightness by a first-order correlation method. The chromaticity was determined by using a brown spectrophotometer ("OSP-SP100" manufactured by Olympus Optics).

An apparatus for measuring a contrast ratio of a coating film and a method for calculating a value will be described with reference to Fig.

Light emitted from the backlight unit 7 for the liquid crystal display passes through the polarizing plate 6 and is polarized and passes through the dried coating film 4 of the colored composition applied on the glass substrate 5 to be polarized on the polarizing plate 3 . When the polarizing planes of the polarizing plate 6 and the polarizing plate 3 are parallel, light passes through the polarizing plate 3, but when the polarizing plane is straight, the light is blocked by the polarizing plate 3. However, when light polarized by the polarizing plate 6 passes through the dried coating film 4 of the colored composition, scattering due to the pigment particles occurs, and when a part of the polarizing plane deviates, when the polarizing plate is parallel, The amount of light passing through the polarizing plate 3 decreases, and when the polarizing plate is directly passed, some light is transmitted through the polarizing plate 3. The transmitted light was measured as the brightness on the polarizing plate to calculate the brightness when the polarizing plate was parallel and the ratio of brightness when not directly used (contrast ratio).

(Contrast ratio) = (luminance in parallel) / (luminance in direct)

Therefore, when scattering is caused by the pigment of the dried coating film 4 of the coloring composition, the brightness at the time of paralleling decreases and the brightness at the time of directing increases, so that the contrast ratio is lowered.

A color luminance meter (BM-5A) was used as the luminance meter 1, and a polarizing plate (NPF-G1220DUN manufactured by Nitto Denko Co., Ltd.) was used as the polarizer. In addition, in order to shield unnecessary light during measurement, a black mask (2) having a hole of 1 cm in length and width was put on the measurement part.

(5) Measurement method of the change rate of the contrast ratio over time

The obtained alkali-developable resist material was allowed to stand at 40 占 폚 for 7 days, and the rate of change of CR (contrast ratio) after standing at 7 days with respect to the initial CR (contrast ratio) was obtained from the following formula.

CR change rate at the time of elapsed time = (CR after 7 days of elapsed time) / (initial CR)

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

The results of the thixotropic index, viscosity, time-dependent viscosity increase rate, contrast ratio (CR), rate of change of the ratio of the contrast ratio (CR) with time and brightness are shown in Tables 8 to 11.

As shown in Example I series, when a basic resinous dispersant having an amine value of 35 to 100 mgKOH / g is used, it is possible to provide a colorant which is excellent in fluidity, excellent in storage stability over time, A composition can be obtained.

When the resinous dispersant is a block copolymer resin comprising a basic copolymer block (a1) and a pigment carrier affinity copolymer block (a2), a higher contrast ratio is obtained.

In addition, when the pigment derivative having a basic functional group is used in combination with the resinous dispersant, the initial contrast ratio is increased, and viscosity characteristics and stability with time are generally improved. (F) Y> -750X + 51000, and (G) Y> 940X-79000 and (H) Y> 8000, when X is an acid value and Y is an average molecular weight. The most favorable green coloring composition can be obtained.

On the other hand, in Comparative Examples I-1 to I-15, fluidity and storage stability were all poor, and a green coloring composition having a low contrast ratio was obtained. Further, in Comparative Example I-16, since a halogenated copper phthalocyanine green is used, a green coloring composition with low brightness is obtained.

(Second Embodiment)

Next, a green coloring composition containing the above-described colorant derivative (b) as an essential component will be described with reference to Examples (Example II series) and Comparative Examples (Comparative Example II series).

First, the acrylic resin solution used in the Example II series and the Comparative Example II series will be described.

Synthesis Example II-A: Synthesis of acrylic resin II-A and preparation of its solution

800 parts of cyclohexanone was placed in a reaction vessel, and heated to 100 占 폚 while introducing nitrogen gas into the vessel. At the same temperature, 80.0 parts of styrene, 40.0 parts of methacrylic acid, 85.0 parts of methyl methacrylate, 95.0 parts of n-butyl methacrylate , And 2.0 parts of azobisisobutyronitrile was added dropwise over 1 hour to carry out a polymerization reaction.

After addition, the mixture was further reacted at 100 ° C for 3 hours, and then azobisisobutyronitrile (2.0 parts) was dissolved in cyclohexanone (50 parts). The reaction was further continued at 100 ° C for 1 hour to give a weight average molecular weight of about 30000 To obtain a cyclohexane solution of an acrylic resin II-A having an acid value of 87 mgKOH / g.

After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180 캜 for 20 minutes to measure the nonvolatile content. Ethylene glycol monomethyl ether acetate was added to the resin solution so that the nonvolatile content became 20% by weight To prepare a solution of the acrylic resin II-A.

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

Synthesis of acrylic resins II-B to II-P was carried out in the same manner as in the synthesis of acrylic resin II-A by the monomer composition and amount of initiator (azobisisobutyronitrile amount) shown in Table 12 below, Lt; / RTI > The acid value and the weight average molecular weight of the synthesized resin are shown in 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 halophthalocyanine green pigment (C.I. pigment green 58), the following formula II-9:

, 1.0 part of a pigment derivative having a triazine ring skeleton having a basic substituent group having an anchor portion of benzimidazolone, 40.0 parts of a solution of the acrylic resin II-A, and 48.0 parts of ethylene glycol monomethyl ether acetate was uniformly stirred After mixing, zirconia beads having a diameter of 0.5 mm were dispersed for 5 hours by Eiger mill (Mini Model M-250 MKII made by Eiger Japan Co., Ltd.) and then filtered with a 5.0 탆 filter to prepare a green pigment dispersion .

Then, 60.0 parts of the green pigment dispersion, 11.0 parts of the solution of the acrylic resin II-A, 4.2 parts of trimethylolpropane triacrylate ("NK Ester ATMPT" manufactured by Shin-Nakamura Chemical Co., Ltd.), a photopolymerization initiator (manufactured by Ciba Specialty Chemicals , 1.2 parts of "Irgacure 907"), 0.4 parts of a sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) and 23.2 parts of ethylene glycol monomethyl ether acetate was stirred and mixed, And filtered to obtain an alkali development type green resist material II-1.

[Example II-2]

(EFK 4300, amine value 56 mgKOH / g) prepared by adding 37.0 parts of a solution of the acrylic resin II-A and ethylene glycol monomethyl ether acetate so as to have a nonvolatile content of 20% by weight Except that 3 parts of the resist solution was added, to thereby obtain an alkali development type resist material II-2.

[Example II-3]

(BYK-163, amine value 10 mgKOH / g) prepared by adding 37.0 parts of a solution of the acrylic resin II-A and ethylene glycol monomethyl ether acetate so as to have a nonvolatile content of 20% by weight Except that 3 parts of the resist solution was added, to thereby obtain an alkali development type resist material II-3.

[Example II-4]

A dye derivative having a triazine ring skeleton having a basic substituent group in which the anchor portion is benzimidazolone is represented by the following Formula II-10:

4 was obtained in the same manner as in Example II-1, except that the dye derivative having a triazine ring skeleton having a basic substituent having an anthraquinone anchor portion represented by the following formula (II-1) was changed.

[Example II-5]

, 11.0 parts of zinc halophthalocyanine green pigment (CI pigment green 58) was changed to 9.0 parts of zinc halophthalocyanine green pigment (CI pigment green 58) and 2.0 parts of a yellow pigment of metal complex system (CI pigment yellow 150, Yellow Pigment E4GN manufactured by Lancet) , An alkali developing type resist material II-5 was obtained in the same manner as in Example II-1.

[Example II-6]

1.0 part of a colorant derivative having a triazine skeleton having a basic substituent group in which the anchor portion is benzimidazolone,

6 was obtained in the same manner as in Example II-1, except that the anchor portion represented by the formula (II) was changed to 1.0 part of a pigment derivative having a basic substituent group of benzimidazolone.

[Example II-7]

1.0 part of a colorant derivative having a triazine skeleton having a basic substituent group in which the anchor portion is benzimidazolone,

7 was obtained in the same manner as in II-1, except that 1.0 part of the dye derivative having an anthraquinone basic substituent represented by the formula (II-1) was replaced with 1.0 part of the dye derivative having a basic substituent.

[Examples II-8 to II-15]

An alkali development type resist material II-8 was obtained in the same manner as in Example II-1 except that the solution of the acrylic resin II-A was changed to the solution of the acrylic resin II-B. In the following, alkali developing type resist materials II-9 to II-15 were obtained in the same manner as in Example II-1 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.

[Comparative Example II-1]

An alkali development 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 changed to 41.0 parts and the dye derivative was removed.

[Comparative Example II-2]

Except that 11.0 parts of zinc halophthalocyanine green pigment (CI pigment green 58) was changed to 11.0 parts of halogenated copper phthalocyanine green pigment (CI pigment green 36, "Lionol Green 6YK" manufactured by Toyo Ink & Chemicals Inc.) In the same manner, an alkali developing type resist material II-17 was obtained.

[Comparative Example II-3]

Except that 11.0 parts of zinc halphthalocyanine green pigment (CI pigment green 58) was changed to 11.0 parts of halogenated copper phthalocyanine green pigment (CI pigment green 7, "Lionol Green YS-07" manufactured by Toyo Ink SEISO Co., Ltd.) 1, an alkali developing type resist material II-18 was obtained.

[Examples II-16 to II-22]

An alkali development type resist material II-19 was obtained in the same manner as in Example II-1 except that the solution of the acrylic resin II-A was changed to a solution of the acrylic resin II-J. Then, alkali developing type resist materials II-20 to II-25 were obtained in the same manner as in Example II-1 except that only the solution of acrylic resin II-A was changed to a solution of acrylic resins II-K to II-P.

(Assessment Methods)

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

As shown in Example II series, when a pigment derivative having a basic substituent group was used when dispersing a zinc halphthalocyanine pigment, a colored composition excellent in fluidity was obtained, and a coating film which achieved high brightness and high contrast ratio at the same time was obtained. Particularly, when a dye derivative having a triazine skeleton was used, the lightness and the contrast ratio showed good values. In addition, the case where Y> -750X + 51000, Y> 940X-79000, and Y> 8000 resin solutions were used in combination was also preferable particularly when X was an acid value and Y was an average molecular weight. On the other hand, the resist material using the coloring composition of Comparative Example II-1 was much higher in viscosity than the resist material obtained in Examples, and the brightness and contrast ratio of the coating film were also low. In the resist materials using the coloring compositions of Comparative Examples II-2 and II-3, the viscosity was at the same level as that of the resist material obtained in the examples, and the contrast ratio of the coating film was almost the same level. However, Value.

(Third Embodiment)

The green coloring composition containing the above mixed organic solvent (c) as an essential component will be described with reference to Examples (Example III series) and Comparative Examples (Comparative Example III series).

First, a method of evaluating the coating property of a resist, and an acrylic resin solution used in the series of Example III and Comparative Example III will be described.

[Evaluation method of coating property]

Evaluation of coating properties will be described.

A coating method using a die coating method and a spin coating method was applied to a glass substrate having a size of 360 mm x 465 mm so as to have an average film thickness of 2.0 m and the obtained coated substrate was prebaked at 70 캜 for 20 minutes Thereby obtaining a dried coating film. The following describes how to describe evaluation items, contents and results.

<Spin coat method only>

(Film thickness uniformity)

&Quot; Film thickness uniformity (end) &quot;: The film thickness was measured at intervals of 5 mm from the center of the short edge of the coated substrate to 5 cm from the center of the substrate. The film thickness uniformity (end) was calculated by the following formula (A) with the maximum film thickness T ₁ , the minimum film thickness T ₂ , and the average film thickness T.

&Quot; Film thickness uniformity (except for end portions) &quot;: The film thickness was measured at intervals of 2 cm from the center of the substrate of the application substrate to 26 cm in the diagonal direction. The film thickness uniformity (other than the end portion) was calculated by the following equation (A).

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

The film thickness uniformity [%] is preferably small, and less than 4% is rated as?, 4% to less than 10%?, And 10% or more as x.

&Lt; Die coat method only &

(Vertical stripes stain)

&Quot; Vertical stripe unevenness &quot;: On the die coating application substrate, &quot; vertical stripe unevenness &quot; which is stripe-shaped unevenness in the advancing direction of the slit due to agglomeration of the slit opening was evaluated as white transmitted light. When no vertical stripe unevenness was observed on the naked eye, it was indicated by o, and when vertical stripe unevenness was observed, it was indicated by x.

(Maximum transmittance)

The number of revolutions of the thus-obtained alkali-developable resist material was changed by a spin coater to prepare three coated substrates so that the dry film thicknesses were 0.62, 0.6 and 0.58 in the CIE colorimetric system. After the coating, the film was dried at 80 캜 for 30 minutes in a hot air oven, and then the film thickness was measured. From the data of the three points, the maximum transmittance at a chromaticity y of 0.6 was determined by a first-order correlation method. The chromaticity was measured using a brown spectrophotometer ("OSP-SP100" manufactured by Olympus Optics).

Next, the acrylic resin solution and the pigment used in the Example III series and the Comparative Example III series will be described.

Synthesis Example III-A: Preparation of a solution of acrylic resin III-A

800 parts of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMAC) was placed in a reaction vessel, and heated to 100 DEG C while introducing nitrogen gas into the vessel. 60.0 parts of styrene, 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 added dropwise over 1 hour to carry out a polymerization reaction.

After dropwise addition, the mixture was further reacted at 100 ° C for 3 hours, and then azobisisobutyronitrile (2.0 parts) was dissolved in 50 parts of PGMAC. Further, the reaction was further continued at 100 ° C for 1 hour to obtain an acrylic resin having a weight average molecular weight (Mw) A solution of resin III-A was obtained.

After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180 DEG C for 20 minutes to measure the non-volatile content. PGMAC was added to the resin solution so that the non-volatile content was 20 wt% A solution was prepared.

Pigment Preparation example

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

(Primary particle size measurement method)

The average primary particle diameter of the pigment was measured by a method of directly measuring the size of primary particles from an electron microscope photograph of a transmission electron microscope (TEM). Specifically, the minor axis diameter and the major axis diameter of the primary particles of each pigment were measured, and the average was determined as the particle diameter of the pigment particles. Next, for 100 pigment particles, the volume (weight) of each particle was determined to approximate the obtained cubic grain, and the volume average particle diameter was determined as the average primary particle diameter.

(Preparation of Green Pigment III-1)

, 200 parts of zinc halphthalocyanine green pigment (CI Pigment Green 58), 1400 parts of sodium chloride and 360 parts of diethylene glycol were placed in a stainless steel first gaillon kneader (manufactured by INOUE KK) and kneaded at 80 DEG C for 6 hours. Next, this kneaded product was charged into 8 liters of warm water and stirred for 2 hours while being heated to 80 DEG C to form a slurry, followed by filtration and washing with water to remove sodium chloride and diethylene glycol, followed by drying at 85 DEG C for one day , 190 parts of a green pigment III-1 was obtained. The primary particle diameter determined by TEM (transmission electron microscope) was 50 nm.

(Preparation of Green Pigment III-2)

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

(Preparation of Green Pigment III-3)

Green pigment III-3 was obtained in the same manner as in the preparation of green pigment III-1 except that zinc halphthalocyanine green pigment (C.I. Pigment Green 58) was replaced with halogenated copper 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 in the preparation of Green Pigment III-1, except that the zinc halide phthalocyanine green pigment (C.I. Pigment Green 58) was replaced with a metal complex system yellow pigment (C.I. pigment yellow 150). The primary particle diameter determined by TEM (transmission electron microscope) was 70 nm.

Pigment Dispersant Preparation example

Next, a method for preparing a green coloring composition (green pigment dispersion) for a color filter will be described.

(Preparation of green pigment dispersion III-1)

A mixture of 11.0 parts of Green Pigment III-1 (CI Pigment Green 58), 40 parts of a solution of acrylic resin III-A, 48.0 parts of propylene glycol monomethyl ether acetate (PGMAC) and 1.0 part of a resinous dispersant (EFKA4300) After mixing, zirconia beads having a diameter of 0.5 mm were dispersed for 5 hours by Eiger mill ("Minimodel M-250 MKII" manufactured by Eiger Japan Co.) and then filtered with a 5.0 μm filter to obtain green pigment dispersion III- Respectively.

Green pigment dispersions III-2 to III-8 were obtained in the same manner as in the preparation of green pigment dispersion III-1 by using the materials shown in Table 14 below. In the pigment dispersion III-5, two kinds of green pigment III-1 and 2 parts of yellow pigment were used to prepare a pigment dispersion.

[Resist remanufacturing example]

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

(Dispersion particle size measurement)

The microtrack UPA-EX150 of Nikkiso Co., Ltd. employing the dynamic light scattering method (FFT power spectrum method) was used to set the particle permeability to the absorption mode and the particle shape to be non-spherical, and the average particle diameter was D50. The dilution solvent for measurement was measured with respect to the sample treated with the ultrasonic wave by using each of the solvents used in the dispersion.

(Particle size by SEM)

The particle size of the pigment by SEM was measured by a direct measurement of the maximum particle size from an electron microscope photograph of a scanning electron microscope (SEM). Specifically, 50 pigment particles are photographed, and the minor axis diameter and the major axis diameter of the primary particles of each pigment are measured. The average particle diameter is determined as the particle diameter of the pigment particles. Significant figures are indicated.

(Green resist material III-1)

Green pigment dispersion III-1 60.0 parts

Acrylic resin solution 11.0 parts

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

Photopolymerization initiator ("Irugacure 907" manufactured by Ciba Specialty Chemicals) 1.2 parts

(EAB-F manufactured by Hodogaya Chemical Co., Ltd.) 0.4 part

PGMAC 15.0 part

Cyclohexyl acetate 8.2 parts

The mixture was stirred and mixed so as to be uniform, and then filtered with a filter of 1.0 mu m to obtain an alkali development type green resist material III-1. The proportion of PGMAC in the whole solvent is 89.8% and the proportion of cyclohexyl acetate is 10.2%. The particle size of the green pigment particles dispersed by SEM was 0.2 탆.

(Green resist material III-2)

Green pigment dispersion III-1 60.0 parts

Acrylic resin solution 11.0 parts

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

Photopolymerization initiator ("Irugacure 907" manufactured by Ciba Specialty Chemicals) 1.2 parts

(EAB-F manufactured by Hodogaya Chemical Co., Ltd.) 0.4 part

Cyclohexyl acetate 23.2 parts

The mixture was stirred and mixed so as to be uniform, and then filtered with a filter of 1.0 탆 to obtain an alkali development type green resist material III-2. Of the total solvents, the blending ratio of PGMAC is 71.0% and the blending ratio of cyclohexyl acetate is 29.0%. The particle size of the green pigment particles dispersed by SEM was 0.2 탆.

Green resist materials III-3 to III-11 were obtained in the same manner as in the preparation of green resist material III-1 using the materials shown in Table 15 below. Table 15 also shows the particle diameters of the respective resist materials measured by SEM.

[Comparative Example]

A green resist material was prepared in the same manner as in the preparation of the green resist material III-1 by using the materials shown in Table 16. In the green resist materials III-12 and III-19, 23.2 parts of one type of solvent was added. Table 16 also shows the particle diameters of the respective resist materials measured by SEM.

Table 17 shows the values of the characteristics of the organic solvents used in the Example III series and the Comparative Example III series.

(Evaluation results)

The evaluation results of the viscosity, thixotropic index, brightness and contrast ratio of the resist obtained as described above in the same manner as in the first embodiment and evaluation results of dispersed particle diameter, maximum transmittance and coatability are shown in Tables 18 and 19.

(Preparation of Red Pigment Dispersion)

Next, a color filter was prepared and evaluated using a red resist material and a green resist material. First, the red resist material used for manufacturing the color filter will be described.

A mixture of 1778.0 parts of CI Pigment Red, 40 parts of an acrylic resin solution, 48.0 parts of propylene glycol monomethyl ether acetate (PGMAC) and 1.0 part of a resin type dispersant (EFKA 4300) was uniformly stirred and mixed with 0.5 mm diameter zirconia beads , Dispersed with Eiger mill (Mini Model M-250 MKII, manufactured by Eiger Japan) for 5 hours, and then filtered with a 5.0 占 퐉 filter to prepare a red pigment dispersion.

(Preparation of red resist material)

, 4.2 parts of a red pigment dispersion, 11.0 parts of an acrylic resin solution, 4.2 parts of trimethylolpropane triacrylate ("NK Ester ATMPT" manufactured by Shin Nakamura Chemical Co., Ltd.), 1.2 parts of a photopolymerization initiator ("Irgacure 907" 0.4 parts of a sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) and 23.2 parts of PGMAC were stirred and mixed to homogeneity, and then filtered with a filter of 1.0 μm to obtain an alkali development type red resist material.

(Fabrication of color filter)

The red resist material was coated on the glass substrate of 10 cm x 10 cm with a spin coater to a thickness of about 2 mu m and allowed to stand in an oven at 70 deg. C for 15 minutes to remove excess solvent and dry. Then, stripe pattern exposure was performed using an exposure apparatus. The exposure dose was 100 mJ / cm 2. Further, the unexposed portions were removed by a developer with a 2% aqueous solution of sodium carbonate to remove unexposed portions, washed with ion-exchanged water, and the substrate was heated at 230 占 폚 for 30 minutes to form red filter segments having a line width of about 50 占 퐉 Respectively. Then, in the same manner, filter segments were formed next to the red filter segments using the green resist material of Example III-1 to prepare color filters having filter segments of two colors.

(C1) and the solvent (c2) were used in the resist using the zinc halphthalocyanine pigment dispersion prepared using the solvent (c1) as in the green resist materials III-1 to III-11 shown in the Example III series , A coloring composition having excellent fluidity and coating properties was obtained, and a coating film which achieved high brightness, high transmittance and high contrast ratio at the same time was obtained. On the other hand, in the green resist materials III-12 to III-21 shown in the comparative example III series, a satisfactory coating film at the same time in terms of brightness, contrast ratio, transmittance and coatability was not obtained.

1 is a schematic explanatory diagram of a measuring apparatus for measuring a contrast ratio.

Explanation of symbols

(1) The luminance meter

(2) Mask

(3) Polarizer

(4) Coloring composition Dry film

(5) Glass substrate

(6) Polarizing plate

(7) Backlight unit

Claims (15)

(A) a pigment component comprising at least a zinc halide phthalocyanine pigment, (B) a pigment, a precursor thereof, or a mixture thereof,   (A) a block copolymer resin comprising a basic copolymer block (a1) and a pigment carrier-affinity copolymer block (a2) and having an amine value of 35 to 100 mgKOH / g, and   (2) at least one organic solvent (c1) selected from propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate, and at least one organic solvent selected from cyclohexyl acetate, propylene glycol (C) containing at least one organic solvent (c2) selected from diethyl ether, diethylene glycol diethyl ether, diethylene glycol diethyl ether, diethylene glycol diacetate, diethylene glycol diethyl ether, At least one selected from the group consisting of A green coloring composition for a color filter, (F), (G) and (H) in the case where the resin constituting the pigment carrier (B) has an acid value of X (mgKOH / g) and a weight average molecular weight of Y A green coloring composition for a color filter, which is a resin satisfying all at the same time: (F) Y> -750X + 51000 (G) Y> 940X - 79000 (H) Y> 8000. The method according to claim 1, Wherein the content of the basic resinous dispersant (a) is 0.001 to 50% by weight based on the total weight of the pigment component (A). The method according to claim 1, Wherein the block copolymer resin is a block copolymer resin obtained by living radical polymerization. The method according to claim 1, Further, a green coloring composition for a color filter containing a coloring derivative (b) having a basic substituent. 5. The method of claim 4, Wherein the content of the dye derivative (b) is 0.001 to 40% by weight based on the total weight of the pigment component (A). The method according to claim 1, Wherein the organic solvent (c1) is 50 wt% to 95 wt% and the organic solvent (c2) is 5 wt% to 50 wt% based on the total amount of the mixed organic solvent (c) Composition. The method according to claim 1, A green coloring composition for a color filter, which further comprises a photopolymerization initiator. 5. The method of claim 4, A green coloring composition for a color filter comprising the basic resinous dispersant (a) and the pigment derivative (b). The method according to claim 1, A green coloring composition for a color filter, comprising the basic resinous dispersant (a) and the mixed organic solvent (c). 5. The method of claim 4, A green coloring composition for a color filter, comprising the dye derivative (b) and the mixed organic solvent (c). 11. The method of claim 10, In addition, a green coloring composition for a color filter containing the basic resinous dispersant (a). A color filter comprising a green filter segment formed of a green coloring composition for a color filter according to any one of claims 1 to 11. delete delete delete

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