TWI506306B - Green colored composition for color filter, and color filter - Google Patents

Description

Color filter with green coloring composition, and color filter

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

The liquid crystal display device is a display device that controls the degree of polarization of light passing through the first polarizing plate and controls the amount of light passing through the second polarizing plate through a liquid crystal layer sandwiched between two polarizing plates, and uses a twisted nematic ( The type of TN) type liquid crystal is becoming the mainstream. The liquid crystal display device can perform color display by providing a color filter between two polarizing plates. In recent years, since it has been applied to a television or a personal computer display, high contrast and high brightness of the color filter have been achieved. The requirements for the improvement have increased.

The color filter is a filter in which fine or thin (striped) filter segments of two or more different hue are arranged in parallel or in a cross on a surface of a transparent substrate such as glass, or a fine A filter in which the filter segments are arranged in a vertical and horizontal arrangement. The filter fragments are finely arranged in a range of several micrometers to several hundreds of micrometers and arranged neatly in a manner to arrange each color phase.

Generally, in a color liquid crystal display device, a transparent filter for driving a liquid crystal is formed on a color filter by vapor deposition or sputtering, and further, an alignment for aligning the liquid crystal in a certain direction is formed thereon. membrane. In order to sufficiently obtain the properties of the transparent electrode and the alignment film, the formation thereof generally needs to be carried out at a high temperature of 200 ° C or higher (preferably 230 ° C or higher). For this reason, as a method of producing a color filter, a method in which a pigment having excellent light resistance and heat resistance is used as a colorant is known as a method of a pigment dispersion method.

However, the color filter in which the pigment is generally dispersed has a problem that the degree of polarization of the liquid crystal control is disturbed due to light scattering due to the pigment or the like. In other words, when it is necessary to shield the light (OFF state), the light leaks, and when the light must be transmitted (ON state), the transmitted light is attenuated, so that the luminance ratio (contrast ratio) on the display device in the ON state and the OFF state is low. .

In order to achieve high luminance and high contrast of the color filter, the pigment contained in the filter segment has been miniaturized. However, even a pigment (a particle called a crude product having a particle diameter of 10 to 100 μm produced by a chemical reaction is passed through a pigmentation treatment until it becomes a mixture of primary particles and secondary particles obtained by agglomeration thereof) By refining by various microfabrication methods, pigments in which primary particles or secondary particles are refined are generally easily aggregated, and when they are excessively refined, a large block of pigment solids is formed. Further, the pigment which has been miniaturized is dispersed in a pigment carrier containing a resin or the like, and the secondary particles of the pigment are again brought close to the primary particles as much as possible to stabilize them, and a stable color composition is obtained. Things are also very difficult.

The colored composition in which the finely divided pigment is dispersed in the pigment carrier tends to cause aggregation of the pigment particles over time, resulting in high viscosity and thixotropy. The increased viscosity of the colored composition and poor fluidity cause problems in manufacturing operations or various problems in product value. For example, the formation of a filter segment of a color filter is generally performed by spin coating a pigmented composition in a pigment carrier containing a monomer and a resin onto a glass substrate, if high viscosity and poor fluidity are used. The colored composition is poor in spin coating property, poor in leveling property, and the like, and a coating film having a uniform film thickness cannot be obtained, which is not preferable.

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

The spin coating method is widely used for forming a thin film on a substrate having a small size, and the coating liquid is dripped at the center of the transparent substrate while rotating the transparent substrate at a constant number of rotations, and the coating liquid is thin by centrifugal force. The film is spread thin, and a coating film having a desired film thickness is formed on the surface of the transparent substrate by controlling the number of rotations or the rotation time of the transparent substrate suitable for the coating liquid. However, the principle of thinning the coating film by the centrifugal force caused by the rotation is that the coating film thickness of the center portion and the peripheral portion of the transparent substrate is too thick compared with the intermediate portion. Patent Document 1 describes a coating liquid for a spin coating method in which a composition containing a solvent having a boiling point of 50% by weight or more and a vapor pressure in a specific range is formed into a coating film with excellent surface smoothness.

When the size of the substrate is large, the method of rotating the substrate by the spin coating method has a large load on the device, and therefore a die coating method is employed. 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 a surface of a transparent substrate on a substrate while moving the slit. However, with this structure, stripe unevenness in the vertical direction is likely to occur with respect to the advance direction of the slit, and in the slit opening portion, the coating liquid is exposed to the atmosphere to be dried and solidified, thereby generating aggregates. The strip shape unevenness occurs in the coating advancing direction, and the aggregate is mixed into the coating to form a coating film defect. Further, the outer peripheral portion of the coating film is raised, and there is a problem that the coating film becomes thicker than the center portion of the substrate.

In order to eliminate such a problem of coating film unevenness in the die coating method, an attempt is made in the following patent documents.

Patent Documents 2 and 3 disclose a method of preventing drying and solidification of a coating liquid by a solvent containing a high boiling point without causing aggregation.

[Patent Document 1] Japanese Patent Laid-Open No. Hei 6-3521

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

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

On the other hand, for the color filter described above, not only high contrast but also high brightness is required. Generally, in order to obtain high brightness, when the pigment is dispersed in the pigment carrier, it is made close to the primary particles, and the transparency of the dispersion is increased, so that the dispersion has high transmittance in the spectroscopic spectrum, thereby obtaining high brightness.

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

In order to solve such problems, a zinc halide phthalocyanine pigment in which a central metal is substituted with zinc from a conventional copper phthalocyanine pigment has been used as a bright color tone and a wide color display region, and has high coloring power. Color material.

[Patent Document 4] Japanese Patent Laid-Open No. Hei 10-130547

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

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

However, the zinc halide phthalocyanine green pigment has a higher acidity than the copper halide phthalocyanine green pigment. Therefore, the zinc halide phthalocyanine green pigment is more difficult to disperse than the copper halide phthalocyanine green pigment. The coloring composition having poor dispersion tends to cause aggregation of pigment particles and the like over time, resulting in high viscosity and thixotropy. The increased viscosity of the colored composition and poor fluidity cause problems in manufacturing operations or various problems in product value. For example, the formation of a filter segment of a color filter is generally performed by spin coating a pigmented composition in a pigment carrier containing a monomer and a resin onto a glass substrate, if high viscosity and poor fluidity are used. The colored composition is poor in spin coating property, poor in leveling property, and the like, and a coating film having a uniform film thickness cannot be obtained, which is not preferable.

Further, it is known that a zinc halide phthalocyanine pigment is different from a conventional copper halide phthalocyanine pigment in chemical properties, and is a pigment which is difficult to disperse. Therefore, it is difficult to stably disperse the zinc halide phthalocyanine pigment in a state in which its excellent color characteristics are maintained, using only a dispersant suitable for a conventional copper phthalocyanine pigment or other pigment.

On the other hand, in order to obtain a highly fluidized zinc halide phthalocyanine pigment dispersion, it is necessary to use a large amount of a dispersant which adversely affects each resistance, and in order to maintain a high pigment concentration, it is necessary to reduce the pigment carrier component which maintains each resistance. The amount, the result is difficult to balance the resistance, fluidity and color characteristics.

In addition, the zinc halide phthalocyanine pigment is different from the conventional copper halide phthalocyanine pigment in that the solubility of the pigment itself is different, so that the zinc halide phthalocyanine pigment has a good affinity with respect to the solvent most suitable for dispersing the copper halide phthalocyanine pigment. When these solvents are used for dispersing a zinc phthalocyanine pigment, the pigment itself is dissolved in a solvent, and there is a problem that a dispersion having a high contrast ratio and high brightness cannot be obtained.

In addition, the coloring composition of the zinc halide phthalocyanine pigment which is dispersed by the solvent used for the dispersion of the copper phthalocyanine pigment (Patent Documents 1 to 3) is as described above, and is applied by a spin coating method or a die coating method. The manner and the properties of the coating liquid used therein have the disadvantages of uneven film thickness or unevenness of the strip.

Here, the film thickness unevenness means that the uniformity of the film thickness is insufficient, and can be classified into "thickness uniformity (end portion)" (that is, film thickness uniformity of the end surface portion) and "film thickness uniformity (end) There are two types other than the part (ie, uniformity from the center of the substrate to the end surface). Moreover, the stripe unevenness can be divided into two types: "horizontal stripe unevenness" (that is, in the die coating method, the strip shape is uneven in the direction perpendicular to the advance direction of the slit) and the "longitudinal strip shape" "Inhomogeneity" (i.e., in the die coating method, the stripe originating from the opening of the slit is uneven in the strip advance direction.

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

Further, an object of the present invention is to provide a green coloring composition for a color filter (a green resist material), and a color filter having a filter segment formed using the color filter, wherein the color filter is green The coloring composition can reduce the defects observed in the coating film of the coating formed by the spin coating method and the die coating method, and can further form a color filter having high brightness and contrast ratio.

The above problem can be solved by using a green coloring composition for a color filter, and the green coloring composition for the color filter includes:

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

(B) a pigment carrier comprising a resin, a precursor thereof or a mixture thereof, and comprising a selected from the group consisting of:

(a) an alkaline resin type dispersant having an amine price of 35 to 100 mg KOH/g;

(b) a pigment derivative having a basic substituent;

(c) at least one of the group consisting of mixed organic solvents containing a solubility parameter (SP value) of 8.0 to 10.0 (cal/cm ³ ) ^1/2 and a boiling point of 760 mmHg of 140 to 159 ° C The organic solvent (c1); and the solubility parameter (SP value) are 8.0 to 10.0 (cal/cm ³ ) ^1/2 , and the organic solvent (c2) having a boiling point of 160 to 200 ° C at 760 mmHg.

In a preferred embodiment of the green coloring composition for a color filter of the present invention, when the acid value is referred to as X (mg KOH/g) and the weight average molecular weight is referred to as Y, the resin constituting the above pigment carrier (B) A resin which simultaneously satisfies the conditions of the following formulas (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 of the present invention, the total weight of the pigment component (A) containing the above-mentioned zinc halide phthalocyanine pigment (hereinafter referred to as only the pigment component (A)) In the case of the above, the content of the above basic resin type dispersant (a) is 0.001 to 50% by weight.

In a preferred embodiment of the green coloring composition for a color filter of the present invention, the basic resin type dispersing agent (a) comprises a basic copolymer block (a1) and a pigment carrier affinity copolymer block ( The block copolymer resin of a2), for example, a block copolymer resin obtained by living 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 of the present invention, the organic solvent (c1) is selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and ethylene glycol single At least one or more solvents of methyl ether acetate and ethylene glycol monoethyl ether acetate.

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

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

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 resin type dispersing agent (a) and the coloring matter derivative (b) are contained.

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

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

Further, the present invention relates to a color filter comprising a green filter segment formed of the green coloring composition of the color filter.

The green coloring composition for a color filter of the present invention is a pigment carrier containing (A) a pigment component containing at least a zinc halide phthalocyanine pigment; and (B) a pigment carrier comprising a resin, a precursor thereof or a mixture thereof, and further comprising a pigment carrier selected from the group consisting of At least one of the group consisting of the basic resin type dispersant (a), the dye derivative (b), and the mixed organic solvent (c) can form a high-flow and stable pigment dispersion, and can be used by using the same. The composition can form a color filter of high brightness and high contrast ratio. In addition, it is possible to form a color filter having a reduced conventional drawback observed in a coating film of a coating material and having a high contrast ratio and high brightness.

In particular, when the above basic resin type dispersant (a) is a block copolymer resin comprising a basic copolymer block (a1) and a pigment carrier affinity copolymer block (a2), it is further possible to form a high A pigment dispersion of a contrast color filter.

Further, when the above-mentioned basic resin type dispersant (a) and the pigment derivative (b) having a basic substituent are contained, the initial contrast ratio is high and the stability with time is also good.

First, a preferred embodiment will be described in detail, and a green coloring composition for a color filter of the present invention will be described in detail.

In addition, in the present specification, it is indicated as "(meth)acrylylene group, "(meth)acrylic group", "(meth)acrylic acid", "(meth)acrylic acid ester", and "(methyl group). In the case of propylene oxy group, unless otherwise specified, it means "acryloyl fluorenyl group and/or methacryl fluorenyl group", "acrylic group and/or methacrylic group", "acrylic acid and/or methyl group". Acrylic acid, "acrylate and/or methacrylate" and "propylene oxy and/or methacryloxy".

The green coloring composition for a color filter of the present invention contains (A) a pigment component containing at least a zinc halide phthalocyanine pigment; and (B) a pigment carrier comprising a resin, a precursor thereof or a mixture thereof, in the first embodiment Further, (a) a basic resin type dispersant having an amine price of 35 to 100 mg KOH/g; and in the second embodiment, the basic resin type dispersant (a) and/or (b) In the third embodiment, the basic resin type dispersant (a) and/or the dye derivative (b) and/or (c) contain a solubility parameter (SP value). The organic solvent (c1) having a boiling point of 140 to 159 ° C at 8.0 to 10.0 (cal/cm ³ ) ^1/2 and 760 mmHg and the solubility parameter (SP value) are 8.0 to 10.0 (cal/cm ³ ) ^1/2 . A mixed organic solvent having an organic solvent (c2) having a boiling point of 160 to 200 ° C at 760 mmHg.

In other words, any two or all of the above-described basic resin type dispersant (a), the above dye derivative (b), and the above mixed organic solvent (c) may be contained.

[Pigment ingredient (A)]

The green coloring composition for a color filter of the present invention is characterized in that a pigment component (A) containing at least a zinc halide phthalocyanine pigment as a main pigment is used. When a typical zinc halide phthalocyanine pigment is represented by a color index (C.I) number, C.I. Pigment Green 58 or the like can be cited. By using a zinc halide phthalocyanine pigment as a main pigment, high brightness which cannot be obtained with other green pigments can be obtained. Further, those obtained by a known manufacturing method can be used. In particular, it is possible to use a pigment which is an acidic functional group on the surface of the pigment when it is measured by a color material, 67 [9], 547-554 (1994), and using n-hexylamine as a basic substance. The amount is preferably 100 μmol/g or more, more preferably 200 μmol/g or more.

The pigment component (A) contains not only a zinc halide phthalocyanine as a main pigment but also other green pigments or yellow pigments for the purpose of color adjustment or complementary color.

As other green pigments which can be used together, a green pigment such as C.I. Pigment Green 7, 10, 36, 37 can be cited. Further, as the yellow pigment which can be used in combination, 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, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, Yellow pigments such as 180, 181, 182, 185, 187, 188, 193, 194, 198, 199, 213, 214.

Among them, from the viewpoint of expanding the chromaticity region, it is preferred to use C.I. Pigment Yellow 138, 139, 150, 185 and the like in combination.

Among all the nonvolatile components of the colored composition of the present invention, the concentration of the preferred pigment component (A) is from 10 to 90% by weight, more preferably from 15 to 80% by weight, from the viewpoint of obtaining sufficient color reproducibility. The best 20~70% by weight. When the concentration of the pigment component (A) is less than 10% by weight, sufficient color reproducibility cannot be obtained, and when it exceeds 90% by weight, the concentration of the pigment carrier becomes low, and the stability of the colored composition is deteriorated.

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

More preferably, the zinc halide phthalocyanine pigment is 50 to 90% by weight, the copper halide phthalocyanine pigment is 5 to 45% by weight, and the yellow pigment is 5 to 45% by weight based on the pigment component (A). By using the composition ratio of such pigments, the chromaticity region can be enlarged.

The green coloring composition of the present invention using a zinc halide phthalocyanine pigment is coated on a glass substrate or the like to form the same color as the green coloring composition using the copper halide phthalocyanine, and the penetration of the coating film is measured. At the time of the ratio, the transmittance higher than that of the coating film using the colored composition of copper phthalocyanine was exhibited from around 450 nm to around 530 nm. In particular, the peak value of the transmittance is about 5%, and the high transmittance is about 90%. Therefore, by combining with a backlight which is generally used in a color liquid crystal display device, high brightness which cannot be obtained by using a coloring composition of a copper phthalocyanine pigment such as C.I. Pigment Green 36 or C.I. Pigment Green 7 can be obtained.

[Micronization of pigments]

The pigment used in the green coloring composition of the present invention can be subjected to a salt milling treatment, and a finer one can be used, and it is preferred to use a finer one.

The salt grinding treatment refers to a mixture of a pigment and a water-soluble inorganic salt and a water-soluble organic solvent using a kneader such as a kneader, a two-roll mill, a three-roll mill, a ball mill, a vertical ball mill or a sand mill. After mechanically kneading while heating, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt acts as a crushing aid. When the salt is polished, the pigment is crushed by the high hardness of the inorganic salt, thereby generating an active surface and causing crystal growth. Therefore, at the time of kneading, the crushing of the pigment and the crystal growth are simultaneously caused, and the primary particle diameter of the pigment obtained according to the kneading conditions is different.

In order to promote crystal growth by heating, the heating temperature is preferably 40 to 150 °C. When the heating temperature is less than 40 ° C, crystal growth cannot be sufficiently caused, and the shape of the pigment particles is close to an irregular shape, which is not preferable. On the other hand, when the heating temperature exceeds 150 ° C, the crystal growth proceeds too much, and the primary particle diameter of the pigment becomes large, so that the coloring material which is a coloring composition for a color filter is not preferable. Further, the kneading time of the salt polishing treatment is preferably from 2 to 24 hours from the viewpoint of the particle size distribution of the primary particles of the salt-polishing treatment pigment and the cost of the salt polishing treatment.

By optimizing the conditions for the salt polishing treatment of the pigment, it is possible to obtain a pigment having a very fine particle diameter and a narrow distribution range and having a sharp particle size distribution.

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

As the water-soluble inorganic salt used in the salt polishing treatment, sodium chloride, cesium chloride, potassium chloride or sodium sulfate can be used, and from the viewpoint of price, sodium chloride (salt) is preferably used. In terms of both the treatment efficiency and the production efficiency, the water-soluble inorganic salt is preferably used in an amount of 50 to 2000% by weight, preferably 300 to 1000% by weight, based on the total weight of the pigment component (A).

The water-soluble organic solvent has a function of a wet pigment and a water-soluble inorganic salt, and is not particularly limited as long as it is dissolved (mixed) in water and does not substantially dissolve the inorganic salt used. However, since the solvent is in a state of being easily evaporated due to an increase in temperature during salt polishing, a high boiling point solvent having a boiling point of 120 ° C or higher is preferred from the viewpoint of safety. For example, 2-methoxyethanol, 2-butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol, diethylene glycol monoethyl ether can be used. , diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2- Propyl alcohol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether or liquid polypropylene glycol. When the total weight of the pigment component (A) is used as a standard, the water-soluble organic solvent is preferably used in an amount of 5 to 1000% by weight, and more preferably 50 to 500% by weight.

When the salt polishing treatment is performed, a resin may be added as needed. The type of the resin to be used is not particularly limited, and a natural resin, a modified natural resin, a synthetic resin, or a synthetic resin modified with a natural resin can be used. The resin to be used is a solid at room temperature, preferably water-insoluble, and more preferably partially soluble in the above organic solvent. When the total weight of the pigment component (A) is used as a standard, the amount of the resin used is preferably in the range of 5 to 200% by weight.

[Pigment Carrier (B)]

In the green coloring composition of the present invention, in addition to the pigment component (A), a pigment carrier (B) containing a resin, a precursor thereof or a mixture thereof is contained.

The pigment carrier (B) used in the green coloring composition of the present invention has 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. Resin, its precursor or a mixture thereof. The resin contains a thermoplastic resin, a thermosetting resin, or an active energy ray-curable resin, and the precursor includes a monomer or an oligomer which is cured by irradiation with an active energy ray to form a transparent resin, and these may be used alone or in combination of two or more kinds. To use. When the total weight of the pigment component (A) is used as a standard, the pigment carrier (B) can be used in an amount of 30 to 500% by weight. When the amount is less than 30% by weight, the film formability and the respective resistances are insufficient. When the amount is more than 500% by weight, the pigment concentration is low and the color characteristics are not exhibited.

When the acid value is referred to as X (mg KOH/g) and the weight average molecular weight is referred to as Y, the resin constituting the above pigment carrier (B) satisfies all of the following formulas (F), (G) and (H) at the same time. The resin of the condition is better:

(F)Y>-750X+51000

(G)Y>940X-79000

(H) Y>8000.

When the resin constituting the above pigment carrier (B) satisfies all the conditions of the above formulas (F), (G) and (H), the resin type dispersant adsorbed on the pigment and the above resin are in the range of good acid value. Since it is possible to maintain an appropriate interaction, and because of a good molecular weight range, it is possible to appropriately exhibit a function as a steric barrier of the carrier resin, and it is preferable to maintain a good dispersion state. In particular, the basic resin type dispersant (a) used in the first embodiment of the present invention and/or the dye derivative (b) used in the second embodiment of the present invention described below can be satisfactorily Adsorbed on the surface of the pigment. On the contrary, when the resin constituting the pigment carrier (B) does not satisfy the condition of the above formula (F), the interaction of the above-mentioned basic resin type dispersant (a) adsorbed on the surface of the pigment with the above resin is too weak, so The dispersion state cannot be maintained due to the aggregation of the pigment or the like. When the conditions of the above formula (G) are not satisfied, the above interaction is too strong, so that the resin-type dispersant adsorbed on the pigment is peeled off, and a good dispersion state cannot be maintained due to aggregation of the pigment or the like. In addition, when the condition of the above formula (H) is not satisfied, since the molecular weight is too small, the above-mentioned resin does not function as a steric hindrance, and thus dispersion failure occurs due to aggregation of the pigment or the like. Further, it is preferably Y≦60000, more preferably Y≦50000. When Y is more than 60,000, it may be inferior in developability when it is used as the alkali-developing type coloring resist described below, which is not preferable.

The thermoplastic resin may, for example, be butyraldehyde resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyamine. Carbamate-based resin, polyester resin, acrylic resin, alkyd resin, polystyrene resin, polyamide resin, rubber resin, cyclized rubber resin, cellulose, polyethylene (HDPE, LDPE) , polybutadiene, polyimine resin, and the like.

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

When it is used in the form of the following alkali-developing type coloring resist, an alkali-soluble resin having an acidic group such as a (meth)acrylic copolymer resin (alkali-soluble acrylic resin) is preferably used. 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 in the range of 30,000 to 80,000. Further, 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.

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

Device: GPC-150C (Waters)

Pipe column: GMH-HT 30cm 2 company (made by Tosoh Corporation)

Temperature: 135 ° C

Solvent: o-dichlorobenzene (addition of 0.1% 2,6-di-t-butyl-4-methylphenol (IONOL))

Flow rate: 1.0ml/min

Sample: Inject 0.4ml 0.15% of the sample

The measurement was carried out under the above conditions, and when calculating the molecular weight of the sample, a molecular weight calibration curve prepared using a monodisperse polystyrene standard sample was used. Further, it is calculated by using a conversion formula derived from the Mark-Houwink viscosity type using a polyethylene conversion.

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, and a hydroxyl group, a carboxyl group or an amine group can be used. The linear polymer of the reactive substituent is reacted, and a photocrosslinkable group such as a (meth)acrylonyl group or a styryl group is introduced into the linear polymer. Further, a resin containing a hydroxy group-containing (meth)acrylic acid compound such as a hydroxyalkyl (meth)acrylate to contain a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer may be used. The linear polymer of the acid anhydride is semi-esterified.

Examples of the monomer and oligomer of the resin precursor include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and isopropyl (meth)acrylate. Butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, isoamyl (meth)acrylate, octyl (meth)acrylate, (meth)acrylic acid Octyl ester, 2-ethylhexyl (meth)acrylate, cetyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, ( a linear or branched chain of tridecyl (meth) acrylate, isomyristyl (meth) acrylate, stearyl (meth) acrylate or isostearyl (meth) acrylate (A) Alkyl acrylates; cyclohexyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentyl (meth)acrylate Ethyl ester, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate or (meth)acrylic acid a cycloalkyl (meth)acrylate such as an ester; trifluoroethyl (meth)acrylate, octafluoropentyl (meth)acrylate, perfluorooctyl (meth)acrylate or (methyl) a fluoroalkyl (meth)acrylate such as tetrafluoropropyl acrylate; a (meth) propylene oxime modified polydimethyl siloxane (polyoxyl macromonomer); (methyl) a (meth) acrylate having a heterocyclic ring such as tetrahydrofurfuryl acrylate or 3-methyl-3-oxetanyl (meth) acrylate; benzyl (meth) acrylate; Phenyloxyethyl acrylate, phenoxy polyethylene glycol (meth) acrylate, (meth)acrylic acid Phenoxyethyl ester, pair a (meth) acrylate having an aromatic ring such as a phenoxy polyethylene glycol (meth) acrylate or a nonyl phenoxy polyethylene glycol (meth) acrylate; (meth) acrylate 2-methoxyethyl ester, 2-ethoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, 2-methoxypropyl (meth)acrylate, diethylene Alcohol monomethyl ether (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, triethylene glycol monomethyl ether (meth) acrylate, triethylene glycol monoethyl ether (Meth) acrylate, diethylene glycol mono 2-ethylhexyl ether (meth) acrylate, dipropylene glycol monomethyl ether (meth) acrylate, tripropylene glycol mono (meth) acrylate (poly)alkylene glycol monoalkyl ether (meth)acrylic acid, such as polyethylene glycol monolauryl ether (meth) acrylate or polyethylene glycol monostearyl ether (meth) acrylate Ester; (meth)acrylic acid, acrylic acid dimer, 2-(methyl) propylene methoxyethyl phthalate, 2-(methyl) propylene methoxy propyl phthalate, hexahydrogenation 2-(methyl)propenyloxyethyl phthalate, hexahydrophthalic acid 2-(Methyl)propenyl propyl acrylate, ethylene oxide modified succinic acid (meth) acrylate, β-carboxyethyl (meth) acrylate or ω-carboxy polycaprolactone (methyl a (meth) acrylate having a carboxyl group such as an acrylate; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate Ester, 4-hydroxybutyl (meth)acrylate, 2-propenyloxyethyl-2-hydroxyethyl (methyl) phthalate, diethylene glycol mono(meth)acrylate , dipropylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, propylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polybutylene glycol mono (methyl Acrylate, poly(ethylene glycol-propylene glycol) mono(meth)acrylate, poly(ethylene glycol-butanediol) mono(meth)acrylate, poly(propylene glycol-butanediol) mono(methyl) a (meth) acrylate having a hydroxyl group such as acrylate or glycerol (meth) acrylate; ethylene glycol di(meth) acrylate, diethylene glycol di (meth) acrylate, three Ethylene glycol di(meth)acrylate, polyethylene glycol di(methyl)propyl Ethacrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, poly(ethylene) Alcohol-propylene glycol) di(meth)acrylate, poly(ethylene glycol-butanediol) di(meth)acrylate, poly(propylene glycol-butanediol) di(meth)acrylate, polytetramethylene glycol Di(meth)acrylate, 1,3-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, (poly)alkylene glycol di(meth)acrylate such as 1,9-nonanediol di(meth)acrylate or 2-ethyl or 2-butyl-propylene glycol di(meth)acrylate Dimethylol dicyclopentane di(meth)acrylate, hydroxytrimethylacetic acid neopentyl glycol di(meth)acrylate, stearic acid modified pentaerythritol di(meth)acrylate, ring Oxygen ethane modified bisphenol A di(meth) acrylate, propylene oxide modified bisphenol A di(meth) acrylate, butylene oxide modified bisphenol A di(meth) acrylate, ring Oxygen ethane modified bisphenol F di(meth) acrylate, propylene oxide modification Phenol F di(meth)acrylate, butylene oxide modified bisphenol F di(meth)acrylate, zinc diacrylate, ethylene oxide modified phosphoric acid triacrylate or glycerol di(methyl) Di(meth)acrylates such as acrylates; dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate or ( a (meth) acrylate having a third amine group such as diethylaminopropyl methacrylate; glycerol tri(meth) acrylate, trimethylolpropane tri(meth) acrylate, a trifunctional or higher polyfunctional (meth)acrylic acid such as pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate or dipentaerythritol hexa(meth)acrylate Ester; glycerol triglycidyl ether-(meth)acrylic acid adduct, glycerol diglycidyl ether-(meth)acrylic acid adduct, polyglycerol polyglycidyl ether-(meth)acrylic acid Adduct, 1,6-butanediol diglycidyl ether-(meth)acrylic acid adduct, alkyl glycidyl ether-(meth)acrylic acid adduct, allyl Glycidyl ether-(meth)acrylic acid adduct, phenyl glycidyl ether-(meth)acrylic acid adduct, styrene oxide-(meth)acrylic acid adduct, bisphenol A diglycidyl ether-( Methyl)acrylic acid adduct, propylene oxide modified bisphenol A diglycidyl ether-(meth)acrylic acid adduct, bisphenol F diglycidyl ether-(meth)acrylic acid adduct, epichlorohydrin Modified phthalic acid-(meth)acrylic acid adduct, epichlorohydrin-modified hexahydrophthalic acid-(meth)acrylic acid adduct, ethylene glycol diglycidyl ether-(meth)acrylic acid Adduct, polyethylene glycol diglycidyl ether-(meth)acrylic acid adduct, propylene glycol diglycidyl ether-(meth)acrylic acid adduct, polypropylene glycol diglycidyl ether-(meth)acrylic acid Form, phenol novolac type epoxy resin-(meth)acrylic acid adduct, cresol novolac type epoxy resin-(meth)acrylic acid addition or other epoxy resin-(meth)acrylic acid addition Epoxy (meth) acrylates, etc.; (meth) propylene oxime modified isocyanurate, (meth) propylene oxime modified polyurethane, (meth) propylene hydrazine Polyester, (meth) propylene ruthenium modified melamine, (meth) propylene oxime modified poly oxime, (meth) propylene ruthenium modified polybutadiene, or (meth) propylene ruthenium modified rosin (Methyl) propylene hydrazine modified resin oligomers; ethylene such as styrene, α-methylstyrene, vinyl acetate, vinyl (meth)acrylate, or allyl (meth)acrylate a vinyl ether such as hydroxyethyl vinyl ether, ethylene glycol divinyl ether, or pentaerythritol trivinyl ether; (meth) acrylamide, N-hydroxymethyl (meth) acrylamide Or a guanamine such as N-vinylformamide; or acrylonitrile. These systems may be used singly or in combination of two or more kinds, but are not limited thereto.

[Basic Resin Type Dispersant (a)]

The green colored composition of the present invention is characterized in that a zinc halide of zinc phthalocyanine is used as a main pigment of the pigment component (A), and the above-mentioned zinc halide phthalocyanine and a copper halide ruthenium which is generally used in a green coloring composition. In contrast to cyanine pigments, the center metal has an acidic acid of zinc with a negative charge on the surface. Therefore, in the first embodiment of the present invention, the basic resin type dispersant (a) having a high amine value of 35 to 100 mg KOH/g is used as the resin type dispersant used for pigment dispersion. The adsorption to the acidic pigment is made sufficient, and the dispersion can obtain sufficient fluidity.

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

In the first embodiment of the present invention, a basic resin type dispersant (a) having an amine price of 35 to 100 mg KOH/g is used. The amine resin type dispersant (a) preferably has an amine value of 50 to 75 mg KOH/g. When the amine price is less than 35 mg KOH/g, it is not sufficiently adsorbed on the pigment to form a poor dispersion. When it exceeds 100 mg KOH/g, the zinc halide is used for the adsorption or reaction of the acidic component in the pigment carrier. The adsorption efficiency of the cyanine pigment deteriorates, resulting in poor dispersion.

The basic resin type dispersing agent (a) having an amine price of 35 to 100 mg KOH/g can be used in various types of resins such as a vinyl type, an urethane type, a polyester type, a polyether type, or a polyamidamide type. A vinyl-based monomer copolymer type which is easy to design and has excellent resistance to each other, and specifically, a vinyl monomer unit containing an N,N-disubstituted amine group and (a) a copolymer resin of an alkyl acrylate monomer unit and other vinyl monomer units.

The vinyl monomer unit containing an N,N-disubstituted amine group may, for example, be N,N-dimethylaminoethyl (meth)acrylate or N,N-diethylaminoethyl (meth)acrylate. N,N-dimethylaminopropyl (meth)acrylate, N,N-diethylaminopropyl (meth)acrylate, N,N-dimethylaminoethyl(meth)acrylamide, Or N,N-diethylaminoethyl (meth) acrylamide or the like, but is not limited thereto. These monomer units are adsorbed on a zinc halide phthalocyanine pigment having a high acidity as a monomer unit containing a basic group.

Examples of the (meth)acrylic acid alkyl ester monomer unit include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and isopropyl (meth)acrylate. Base) n-butyl acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, or (a) The (meth) acrylate obtained by reacting an unsaturated monocarboxylic acid such as lauryl acrylate with an alkyl alcohol having 1 to 18 carbon atoms is not limited thereto. These monomer units function as a pigment carrier affinity group.

Examples of the other vinyl monomer unit include vinyl groups containing a nitro group such as (meth)acrylonitrile, and vinyl groups such as styrene, α-methylstyrene, or benzyl (meth)acrylate. An aromatic monomer; a hydroxyl group-containing vinyl monomer such as 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, or polyethylene glycol (meth)acrylate; A vinyl group-containing vinyl monomer such as methacrylamide, N,N-dimethylpropenylamine, N-isopropylacrylamide or diacetone acrylamide; N-hydroxyl a vinyl monomer such as a (meth) acrylamide or a dimethylol (meth) acrylamide; N-methoxymethyl (meth) acrylamide or N-butoxymethyl ( a vinyl-based monomer containing an alkoxymethyl group such as methyl acrylamide; an olefin such as ethylene, propylene or isoprene; a diene such as chloroprene or butadiene; methylethylene; Vinyl ethers such as ethyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether; vinyl acetate or propyl acetate Acid vinyl ester, etc. The fatty acid vinyl esters and the like may be used according to the purpose, but are not limited to the compounds.

Further, a polymer having a monomer unit containing a primary amine group such as an allylamine, or a polyethyleneimine, a polyethylene polyamine, or a parylene may be used, such as a polyester resin, an acrylic resin, or a polyether resin. A comb-shaped basic resin type dispersant modified by a poly(hydroxyl-propyl)polyamine or a poly(amine methylated) epoxy resin.

Commercial products of such basic resin type dispersing agents can be exemplified by BYK-161, 163, 164, 167, 174, 184, 2000, 2050 of BYK, or SOLSPERSE-34750, 56000, Ciba Japan of Lubrizol Corporation of Japan. EFKA4300, 4330, 4046, 4060, 4080, etc. of K.K.

The basic resin type dispersant (a) which is a green coloring composition for a color filter of the present invention contains a basic copolymer block (a1) and a pigment carrier affinity copolymer block (a2). Block copolymer resin. Hereinafter, the basic resin type dispersant will be described.

(Basic Resin Type Dispersant)

The basic resin type dispersant for a green coloring composition of the color filter of the present invention has a site to be adsorbed on the pigment (hereinafter referred to as an adsorption portion); and prevents aggregation between the pigments and improves dispersibility. A portion having a high affinity for a pigment carrier (hereinafter referred to simply as an affinity portion). Since the zinc halide phthalocyanine has a high acidity, when the affinity portion and the adsorption portion are randomly arranged, the adsorption of the pigment becomes insufficient, resulting in poor dispersion. In the first embodiment of the present invention, by using the following block copolymer resin as the resin type dispersant (a), it is possible to provide a zinc halide phthalocyanine pigment without impairing its color characteristics, fineness and low viscosity, and a highly dispersed green coloring composition which is a basic copolymer block (a1) for an adsorption portion of a zinc halide phthalocyanine pigment and a pigment carrier affinity copolymerization as an affinity portion for a pigment carrier The block (a2) is present separately on the same molecule.

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, and it is preferred that the resin is easy to design and excellent in resistance. 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 and N,N-diethylaminoethyl (meth)acrylate. , N,N-dimethylaminopropyl (meth)acrylate, N,N-diethylaminopropyl (meth)acrylate, N,N-dimethylaminoethyl(meth)acrylamide Or a copolymer of a vinyl monomer unit containing an N,N-disubstituted amine group such as N,N-diethylaminoethyl (meth) acrylamide; or a monomer having a primary amine group such as allylamine a polymer of a unit, or a polyethyleneimine, a polyethylidene polyamine, a poly(p-hydroxypropene) polyamine, or a poly(amine methylated) epoxy resin, but is not limited to the compounds .

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

(Pigment Carrier Affinity Copolymer Block (a2)>

The pigment carrier affinity copolymer block (a2) is a resin of a block copolymer which is easy to design and has excellent resistance to each other, and more preferably contains a vinyl monomer unit (methyl). The alkyl acrylate, particularly in the pigment carrier affinity copolymer block (a2), is preferably contained in an amount of from 60 to 100% by weight, more preferably from 80 to 100% by weight. The (meth)acrylic acid alkyl ester may, for example, be methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate or isopropyl (meth)acrylate, ( N-butyl methacrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate or (a) The (meth) acrylate obtained by reacting an unsaturated monocarboxylic acid such as lauryl acrylate with an alkyl alcohol having 1 to 18 carbon atoms is not limited to these compounds.

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

The other vinyl monomer unit which may be contained in the basic copolymer block (a1) and the pigment carrier affinity copolymer block (a2) may, for example, be a nitro group such as (meth)acrylonitrile. Vinyl monomers; vinyl aromatic monomers such as styrene, α-methylstyrene or benzyl (meth)acrylate; 2-hydroxyethyl (meth)acrylate, (methyl) a hydroxyl group-containing vinyl monomer such as hydroxypropyl acrylate or polyethylene glycol (meth) acrylate; (meth) acrylamide, N, N-dimethyl decylamine, N-isopropyl a vinyl monomer containing a guanamine group such as a acrylamide or a diacetone acrylamide; an ethylene such as N-hydroxymethyl (meth) acrylamide or dimethylol (meth) acrylamide Base monomer, vinyl group containing alkoxymethyl group such as N-methoxymethyl (meth) acrylamide or N-butoxymethyl (meth) acrylamide; ethylene, propylene Or an isomer such as isoprene; a diene such as chloroprene or butadiene; methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether N-butyl vinyl ether Isobutyl vinyl ether, vinyl ether, etc.; or vinyl propionate, or vinyl acetate fatty acid esters, vinyl esters, etc. and the like, but are not limited to such compounds.

(Block copolymer resin)

The resin-type dispersant (a) used in the first embodiment of the present invention can be produced by a known method, and particularly preferably (1) using a living polymerization method or (2) having a functional group at the terminal. A polymer coupling method in which the body (a1) of the basic copolymer block (a1) is reacted with the body (a21) before the pigment carrier affinity copolymer block (a2) having a functional group at the terminal. Among them, the special system (1) uses a method of living polymerization.

(1) Living polymerization method

The living polymerization method can suppress the side reaction which occurs in general radical polymerization, and further, since the growth of the polymerization can be performed uniformly, the block polymer or the resin having the same molecular weight can be easily synthesized. Among them, from the viewpoints of being applicable to a wide range of monomers, and being able to adopt a polymerization temperature which is suitable for the existing equipment, it is preferred to use an organic halide or a sulfonium halide compound as a starting agent and a transition metal The atom acts as a catalyst for mobile radical polymerization. The atomic mobile radical polymerization method can be carried out by the methods described in the following References 1 to 8 and the like.

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

(Reference 2) Matyjaszewski et al., Chem. 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

(Reference 6) International Publication No. 97/18247

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

(Reference 8) Japanese Patent Laid-Open No. Hei 8-41117

The atomic mobile radical polymerization method is carried out by using a transition metal complex such as copper, ruthenium, iron or nickel as a redox catalyst. Specific examples of the transition metal complex compound include a halogenated transition metal having a low valence such as copper (I) chloride or copper (I) bromide. However, in order to control the polymerization rate, it may be added to the polymerization system according to a known method. A high valence transition metal such as copper (II) chloride or copper (II) bromide.

An organic ligand can be used in the above metal complex. In order to have a reversible change in the solubility of the polymerization solvent and the redox conjugated complex, an organic ligand is used. As the coordination atom of the metal, a nitrogen atom, an oxygen atom, a phosphorus atom or a sulfur atom can be used, and a nitrogen atom or a phosphorus atom is preferable. Specific examples of the organic ligand include sparteine, 2,2'-bipyridyl and derivatives thereof, 1,10-morpholine or a derivative thereof, tetramethylethylenediamine, Pentamethyldiethylamine, tris(dimethylaminoethyl)amine, hexamethyl(2-aminoethyl)amine, triphenylphosphine, or tributylphosphine. Among the above catalysts, copper halide and butadiamine are used in combination to carry out polymerization, and it is preferable from the viewpoint of controlling the polymerization rate and the molecular weight of the block resin.

The above transition metal and organic ligand may be separately added to form a metal complex in the polymer, or a metal complex may be synthesized in advance and added to the polymerization system. Particularly when the transition metal is copper, the former method is preferred, and when the transition metal is ruthenium, iron or nickel, the latter method is preferred. Specific examples of the previously synthesized ruthenium, iron or nickel complex may be exemplified by tris(triphenylphosphine)ruthenium dichloride (Ru(Cl) ₂ (PPh ₃ ) ₃ , bis(triphenylphosphine) dichloride. Iron (Fe(Cl) ₂ (PPh ₃ ) ₂ ), bis(triphenylphosphine) nickel dichloride (Ni(Cl) ₂ (PPh ₃ ) ₂ ) or bis(tributylphosphine) nickel dibromide (NiBr ₂ (PBu ₃ ) ₂ ) and the like.

As the initiator used in the atomic mobile radical polymerization method, a known compound can be used, and an organic halide having a highly reactive carbon-halogen bond, or a sulfonium halide compound or the like can be mainly used. Specific examples thereof include ethyl bromoisobutyrate, ethyl bromobutyrate, ethyl chloroisobutyrate, ethyl chlorobutyrate, p-toluenesulfonium chloride, bromoethylbenzene, or chloroethyl. Benzene, etc. These compounds may be used singly or in combination.

In the above atomic mobile radical polymerization, the initiator of the atomic mobile radical polymerization may be appropriately selected depending on the molecular weight of the synthesized resin, and is preferably 0.001 to 10 mol% based on the total amount of the radical polymerizable monomer. More preferably used in a ratio of 0.01 to 1 mol%. Further, the amount of the transition metal used is, as a form of a halide, preferably used in a ratio of 0.03 to 3 mol, more preferably 0.1 to 2 mol, per mol of the initiator. Further, the ligand is used in a ratio of 1 to 5 moles, preferably 1.2 to 3 moles, per mole of the transition metal (form of a halide or the like). When the above-mentioned atomic mobile radical polymerization initiator, transition metal and ligand are used in such a ratio, it is preferable in terms of the reactivity of living radical polymerization, the molecular weight of the resulting polymer, and the like.

Further, in the characteristics of atomic mobile radical polymerization, an activated carbon-halogen bond is formed at the terminal end of the obtained resin, and it can be modified into a functional group by a known method. Further, polymerization can be carried out using a polymerization initiator having a functional group, and a functional group can be introduced at the end of the resin and used for various reactions.

The atomic mobile radical polymerization system can be carried out in the absence of a solvent, or can be carried out in the presence of a solvent such as butyl acetate, toluene, xylene, anisole, methyl ethyl ketone or cyclohexanone. Particularly, from the viewpoint of the polymerization rate, a ketone-based solvent is preferred, and methyl ethyl ketone is particularly preferred. When a solvent is used, in order to prevent a decrease in the polymerization rate, the amount used is such that the solvent concentration after completion of the polymerization is 50% by weight or less. Even in the case of no solvent or a small amount of solvent, there is no safety problem particularly related to the control of polymerization heat, and the like, thereby reducing the solvent, and thus it is also preferable in terms of economy and environmental countermeasures.

As the polymerization conditions, from the viewpoint of polymerization rate or catalyst deactivation, the polymerization temperature is carried out at a polymerization temperature of 60 to 130 ° C, and the polymerization time depends on the final molecular weight or the polymerization temperature, but it is in the polymerization time range of about 1 to 100 hours. Just inside. Further, in the polymerization reaction, in order to prevent deactivation of the polymerization catalyst by oxygen, it is preferably carried out in an inert gas atmosphere such as nitrogen or argon.

Further, after completion of the polymerization reaction, it is preferred to cool the polymerization reaction system to 0 ° C or lower, more preferably about -78 ° C, to terminate the reaction, and to remove residual monomers and/or solvents according to a known method. Reprecipitation in a suitable solvent, filtration of the precipitated polymer by centrifugation, washing and drying of the polymer. After removing the transition metal or the like contained in the polymerization system by a known method, the block resin used in the present invention can be obtained by evaporating the volatile component. The removal method is carried out by diluting the reaction mixture with an organic solvent such as tetrahydrofuran, toluene or methyl ethyl ketone, washing with water, dilute hydrochloric acid or an aqueous ammonia solution, and contacting the resin solution with a cation exchange resin or a chelating resin. After adding an adsorbent such as a reducing agent or a hydrotalcite to a column or a filler of aluminum or cerium oxide or clay, the method of filtration, centrifugation, and the like are carried out. From the viewpoint of the simplicity of the treatment, it is preferred to add a cation exchange resin, an acid adsorbent such as hydrotalcite, or the like to the diluted resin solution and stir, and filter the ion exchange resin and the acid adsorbent to obtain a resin solution. .

When water is mixed in the resin solution by the refining treatment, there is a case where the block resin used in the present invention is inhibited from reacting with the curing agent, and it is preferred to carry out azeotropic dehydration by adding a solvent mixed with water to the resin solution. The treatment is carried out to remove moisture from the resin solution.

For the atomic mobile radical polymerization used in the present invention, since the side reaction occurring in the general radical polymerization can be suppressed, the initiator of the atomic mobile radical polymerization added during the polymerization and the radical polymerizable monomer are used. In proportion, the molecular weight of the resin or the ratio of the basic copolymer block (a1) or the pigment carrier affinity copolymer block (a2) can be freely controlled.

(2) Polymer coupling law

Preferred examples of the functional group of the terminal body (a11) before the basic copolymer block (a1) and the front end of the body (a21) of the pigment carrier affinity copolymer block (a2) of the polymer coupling method are exemplified. A carboxyl group, a primary amino group, a hydroxyl group, or an alkoxyalkyl group. As a method of introducing a terminal functional group into the body (a11) before the basic copolymer block (a1) and the body (a2) before the pigment carrier affinity copolymer block (a2), it is preferred to use the above-mentioned enumeration. A method of radical polymerization using a functional group and a thiol chain transfer agent. The chain transfer agent having a carboxyl group may, for example, be mercaptopropionic acid, the chain transfer agent having a primary amine group may be exemplified by cysteamine, the chain transfer agent having a hydroxyl group may be mercaptoethanol, and the chain transfer agent having an alkoxycarbenyl group may be exemplified by 3 - Mercaptopropyl methyl methoxy decane or 3-mercaptopropyl trimethoxy decane.

The reaction between the precursor (a11) and the precursor (a21) is, for example, a known reaction which can be carried out in combination with the following Table 1.

The polyisocyanate compound of the binder may, for example, be an aromatic polyisocyanate, an aliphatic polyisocyanate, an aromatic aliphatic polyisocyanate or an alicyclic polyisocyanate. The aromatic polyisocyanate may, for example, be 1,3-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,4-phenylene diisocyanate or 4,4'-diphenylmethane. Isocyanate, 2,4-methylphenylene diisocyanate, 2,6-phenylene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-three Isocyanate benzene, dimethoxyaniline diisocyanate, 4,4'-diphenyl ether diisocyanate, or 4,4',4''-triphenylmethane triisocyanate. The aliphatic polyisocyanate may, for example, be trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene isocyanate, pentamethyl diisocyanate or diisocyanate 1,2 Propyl propyl ester, diisocyanato 2,3-butyl butyl ester, 1,3-butylene diisocyanate, 12-methylene methyl diisocyanate or 2,4,4-trimethyl diisocyanate Methyl hexamethyl ester and the like. The aromatic aliphatic polyisocyanate may, for example, be ω,ω'-diisocyanate-1,3-dimethylbenzene, ω,ω'-diisocyanate-1,4-dimethylbenzene, ω,ω'-two Isocyanate-1,4-diethylbenzene, 1,4-tetramethylxylene diisocyanate, or 1,3-tetramethylxylene diisocyanate. The alicyclic polyisocyanate may, for example, be 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate, 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4 - cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), 1, 4-bis(isocyanatemethyl)cyclohexane or 1,4-bis(isocyanatemethyl)cyclohexane, etc., but is not limited thereto. Further, a biuret compound in which a part of the above polyisocyanate trimethylolpropane adduct is reacted with water, a trimer having an isocyanurate ring, or the like may be used in combination.

The polyepoxide of the binder is preferably a polyepoxide having at least 2 glycidyl groups. Specific examples thereof include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, and trimethylol An aliphatic polyepoxide such as ethane triglycidyl ether, sorbitol polyglycidyl ether or pentaerythritol polyglycidyl ether, an aromatic polyepoxy compound of the bisphenol A or bisphenol F type, tetraglycidyl group a glycidylamine type epoxy compound such as aminophenylmethane, triglycidyl isocyanurate or 1,3-bis(N,N-glycidylaminomethyl)cyclohexane, but not Limited to these compounds.

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

In addition, the block copolymer type basic resin type dispersant used in the first embodiment of the present invention has an amine value of 35 to 100 mg KOH/g, more preferably 50 to 75 mg KOH/g. When the amine price is less than 35 mg KOH/g, it is not sufficiently adsorbed on the pigment to form a poor dispersion. When it exceeds 100 mg KOH/g, the adsorption to the pigment is caused by adsorption or reaction to the acidic component in the pigment carrier. The efficiency is deteriorated, resulting in poor dispersion.

The constituent weight ratio of the basic copolymer block (a1) or the pigment carrier affinity copolymer block (a2) and the number average molecular weight of each block can be arbitrarily designed so that the number average molecular weight of the resin type dispersant as a whole And the amine price is within the above preferred range.

In the green coloring composition of the first embodiment of the present invention, the amount of the basic resin type dispersant (a) is preferably 0.001 to 50% by weight based on the total weight of the pigment component (A). Preferably, it is 0.1 to 30% by weight, preferably 0.5 to 25% by weight. When the amount of the resin-type dispersant (a) is less than 0.001% by weight based on the total weight of the pigment component (A), the dispersibility may be deteriorated, and if it exceeds 40% by weight, the heat resistance may be Light resistance is worse.

[Pigment Derivative (b) having a basic substituent]

The green colored composition of the present invention is characterized in that a zinc halide phthalocyanine having a central metal having zinc is used as a main pigment of the pigment component (A), and the above-mentioned zinc halide phthalocyanine and a copper halide phthalocyanine generally used in a green coloring composition are used. In contrast to the pigment, the center metal has an acidic zinc pigment which has a negative charge on the surface. Therefore, when a dispersing agent having a basic substituent is used, adsorption to an acidic pigment becomes 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 a 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 dye derivative (b) can be used for the purpose of improving the dispersibility of the pigment. The pigment derivative can be exemplified by an organic pigment, hydrazine, acridone or three. A compound obtained by introducing a basic substituent, an acidic substituent, or a phthalimidomethyl group which may have a substituent.

In the present invention, a basic derivative is preferred, and the basic derivative is a compound represented by the following formula (1) which is a derivative having a specific parent skeleton having a basic group. It is not particularly limited as long as it is a pigment derivative having a basic group, and preferably has three a pigment derivative of a ring skeleton, the above three The ring skeleton has a basic group represented by the following formula (4).

Formula (1): P-Lm (wherein, in the formula (1), P is an m-valent organic pigment residue, an anthracene skeleton, an acridone skeleton, and three The skeleton or the like, m is an integer of 1 to 4, and L is a substituent selected from the group represented by the general formulae (2), (3), and (4). )

General formula (3):

(In the formulae (2) to (4), X-type -SO ₂ -, -CO-, -CH ₂ -, -CH ₂ NHCOCH ₂ -, -CH ₂ NHSO ₂ CH ₂ -, or direct bonding , Y--NH-, -O-, or direct bonding, n is an integer from 1 to 10, Y ¹ is -NH-, -NR ⁵⁸ -Z-NR ⁵⁹ -, or directly bonded, R ⁵⁸ and R ⁵⁹ independently represents a hydrogen atom, 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 benzene which may have a substituent a group, Z represents an alkylene group which may have a substituent, or an extended aromatic group which may have a substituent, and R ⁵⁰ and R ⁵¹ each independently represent a hydrogen atom, and may have a substituent having 1 to 30 carbon atoms. An alkyl group, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, and a heterocyclic ring which may have a substituent of R ⁵⁰ and R ⁵¹ and further contain a nitrogen, oxygen or sulfur atom, R ⁵² , R ⁵³ , R ⁵⁴ and R ⁵⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and an alkenyl group having 2 to 20 carbon atoms which may have a substituent. , which may be substituted for the number of carbon atoms of the extension of the aromatic group having 6 to 20, R ⁵⁶ hydrogen-based An 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, and R ⁵⁷ is a substituent represented by the formula (2) Or a substituent represented by the formula (3), a Q-based hydroxyl group, an alkoxy group, a substituent represented by the above formula (2), or a substituent represented by the above formula (3).

The amine component for forming the substituents represented by the general formulae (2) to (4) may, for example, be dimethylamine, diethylamine, methylethylamine, N,N-ethylisopropylamine or N. , N-ethylpropylamine, N,N-methylbutylamine, N,N-methylisobutylamine, N,N-butylethylamine, N,N-tert-butylethylamine, diisopropylamine, Dipropylamine, N,N-second butyl propylamine, dibutylamine, di-second butylamine, diisobutylamine, N,N-isobutyl second butylamine, diamylamine, diisoamylamine, two Hexylamine, dicyclohexylamine, di(2-ethylhexyl)amine, dioctylamine, N,N-methyloctadecylamine, diamine, diallylamine, N,N-ethyl-1 ,2-dimethylpropylamine, N,N-methylhexylamine, dioleylamine, distearylamine, N,N-dimethylaminomethylamine, N,N-dimethylaminoethylamine , N,N-dimethylaminopentylamine, N,N-dimethylaminobutylamine, N,N-diethylaminoethylamine, N,N-diethylaminopropylamine, N, N-diethylaminohexylamine, N,N-diethylaminobutylamine, N,N-diethylaminopentylamine, N,N-dipropylaminobutylamine, N,N- Dibutylaminopropylamine, N,N-dibutylaminoethylamine, N,N-dibutylaminobutylamine, N,N-diisobutylaminopentylamine, N,N-A - lauryl propylamine, N,N-ethyl-hexylaminoethylamine, N,N-distearate aminoethylamine, N,N-dioleylaminoethylamine, N,N-di Stearylamine butylamine, piperidine, 2-methylpiperidine (pipecoline), 3-methylpiperidine, 4-methylpiperidine, 2,4-dimethylpiperidine (lupetidine), 2, 6-Dimethylpiperidine, 3,5-dimethylpiperidine, 3-piperidinemethanol, methylpipecolic acid, isohexahydronicotinic acid, isohexahydronicotinic acid methyl ester, isohexahydrobutanic acid Ethyl alkaliate, 2-piperidineethanol, pyrrolidine, 3-hydroxypyrrolidine, N-aminoethylpiperidine, N-aminoethyl-4-methylpiperidine, N-aminoethyl Porphyrin, N-aminopropyl piperidine, N-aminopropyl-2-methylpiperidine, N-aminopropyl-4-methylpiperidine, N-aminopropyl Porphyrin, N-methyl pipe N-butylperidazole N-methyl homopolypiperidine, 1-cyclopentylperidine 1-amino-4-methylper 1-cyclopentylperidazole Wait.

The pigment derivative, the anthracene derivative and the acridone derivative having a basic substituent used in the second embodiment of the present invention can be synthesized by various synthetic routes. For example, by introducing a substituent represented by the formula (5) to (8) into an organic dye, hydrazine or acridone, it is possible to react with the above substituent to form a formula (2) to (4). The above-mentioned amine component of the substituent shown is reacted, and the above amine component is, for example, N,N-dimethylaminopropylamine or N-methylpiperidone. , diethylamine, or 4-[4-hydroxy-6-[3-(dibutylamino)propylamino]-1,3,5-three -2-amino] aniline and the like.

Formula (5): -SO ₂ Cl

Formula (6): -COCl

Formula (7): -CH ₂ NHCOCH ₂ Cl

Formula (8): -CH ₂ Cl

When the substituent of the formula (5) to (8) is reacted with the above amine component, one of the substituents of the formulae (5) to (8) is partially hydrolyzed, and a substance in which chlorine is substituted with a hydroxyl group may be mixed. At this time, the formula (5) and the formula (6) respectively become a sulfonic acid group and a carboxylic acid group, and both of them may be in a state of maintaining a free acid, or may be a salt formed of a metal having a valence of 1 to 3 or the above monoamine. .

In addition, when the organic dye is an azo dye, the substituents represented by the general formulae (2) to (4) are introduced into a diazo component or an even component in advance, and then a coupling reaction is carried out, whereby an azo can also be produced. A pigment derivative.

The third basic base used in the second embodiment of the present invention Derivatives can be synthesized using a variety of synthetic routes. For example, cyanuric chloride is used as a starting material to pass through an amine component which forms a substituent represented by the general formulae (2) to (4), for example, N,N-dimethylaminopropylamine or N-methylpiperidin. The reaction is carried out by reacting at least one chlorine with cyanuric chloride, followed by 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 basic substituent is preferably from 1 to 50 parts by weight, more preferably from 3 to 30 parts by weight, per 100 parts by weight of the pigment component (A). The best is 5 to 25 parts by weight. When the basic derivative is less than 1 part by weight based on 100 parts by weight of the pigment, the dispersibility may be deteriorated, and when it exceeds 50 parts by weight, heat resistance and light resistance may be deteriorated. Wherein, there are three in the basic substituent The compound of the structure is preferred in terms of dispersion stability.

[Organic solvent (c)]

In the third embodiment of the green coloring composition of the present invention, in order to sufficiently disperse the pigment component (A) in the pigment carrier (B), it is easy to have a dry film thickness of 0.2 to 5 μm on a substrate such as a glass substrate. The coating is carried out in such a manner as to form a filter segment, and contains an organic solvent (c).

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

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

Preferably, the organic solvent (c) is an organic solvent (c1) having a solubility parameter (SP value) of 8.0 to 10.0 (cal/cm ³ ) ^1/2 and a boiling point of 144 to 157 ° C at 760 mmHg; and a solubility parameter. (SP value) is a mixed organic solvent 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.

Here, the organic solvent (c1) is preferably selected, for example, from propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate. More preferably, the organic solvent (c2) is selected, for example, from cyclohexyl acetate, propylene glycol diacetate, diethylene glycol diethyl ether, and ethyl 3-ethoxypropionate. More than one solvent. Further, 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 has an organic solvent (c1) and an organic solvent (c2) having a specific range of solubility parameter (SP value) and boiling point in a specific ratio. High contrast ratio and high brightness. Further, with respect to the coating film coated with the colored composition, the film thickness unevenness and the stripe unevenness are reduced, the film thickness is uniform, and the film has excellent properties.

When the solubility parameter (SP value) is ^1/2 (cal/cm ³ ) ^1/2 hour, the dispersion of the zinc halide phthalocyanine pigment deteriorates, and when the ratio is larger than 10.0 (cal/cm ³ ) ^1/2 , the zinc halide phthalocyanine The pigment dissolves in an organic solvent, resulting in a decrease in brightness and contrast ratio.

When the boiling point of the solvent used as the organic solvent (c1) is less than 140 ° C, unevenness in film thickness or unevenness in strip shape occurs, which is not preferable. Further, when the boiling point of the solvent used as the organic solvent (c2) is more than 200 ° C, the adhesiveness remains, which is not preferable.

When the total amount of the pigment component (A) is used as a reference, the mixed organic solvent (c) may be used in an amount of from 800 to 4,000% by weight. Further, in the total amount of the mixed organic solvent (c), the organic solvent (c1) is preferably 50 to 95% by weight, and the organic solvent (c2) is 5 to 50% by weight. More preferably, the organic solvent (c1) is 65 to 95% by weight, and the organic solvent (c2) is 5 to 35% by weight. If the ratio of the organic solvent (c1) exceeds the range of 50 to 95%, the coating liquid may have a problem of uneven film thickness or unevenness of the strip. Thus, in order to perform preferred dispersion of the zinc halide phthalocyanine pigment, the coordination of the organic solvent (c1) and the organic solvent (c2) is important.

Further, as described above, the organic solvent (c1) used in dispersing the zinc halide phthalocyanine pigment and the organic substance added in order to improve the coating film in the green coloring composition coated with the color filter of the present invention are added. The solvent (c2) is not limited to a specific solvent, and in order to easily form the colored composition into a filter segment, the following organic solvent may be added as an auxiliary solvent.

1,2,3-trichloropropane, 1,3-butandiol, 1,3-butylene glycol, 1,3-butane can be used. Alcohol diacetate, 1,4-two Alkane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexane-1-one, 3,3,5-trimethylcyclohexanone , 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methyl Oxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N,N-dimethylacetamide, N,N - dimethylformamide, n-butanol, n-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene , p-diethylbenzene, t-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutanol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, Ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-telebutyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol single Propyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, diisobutyl ketone, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl Ethyl acetate, diethylene glycol monobutyl ether, Ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether , dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol Phenyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methyl ring Hexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, or a dibasic acid ester.

In order to obtain a preferred green coloring composition of the present invention, the total amount of the organic solvent (c1) and the organic solvent (c2) is preferably 70% by weight or more in the total mixed organic solvent (c). Further, it is more preferably 80% by weight in total. The total amount is particularly 85% by weight or more. When the auxiliary solvent other than the organic solvent (c1) and the organic solvent (c2) is added in a large amount, the stability of the dispersion of the zinc halide phthalocyanine pigment and the coating property of the coating film coated with the colored composition are adversely affected. It is not good.

[dispersion]

The green coloring composition of the present invention may contain a pigment component containing at least a zinc halide phthalocyanine pigment by using various dispersion means such as the above-described three-roll mill, two-roll mill, sand mill, kneader, or vertical ball mill. And finely dispersing in the pigment carrier (B) together with the basic resin type dispersant (a) or the basic resin type dispersant (a) and the above-mentioned dye derivative (b) having a basic substituent. Made for manufacturing. Further, the green colored composition of the present invention may be produced by mixing a substance obtained by dispersing a plurality of kinds of pigments in the pigment carrier (B).

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

[Photopolymerization initiator]

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

As the photopolymerization initiator, 4-phenoxydichloroacetophenone, 4-tert-butyldichloroacetophenone, diethoxyacetophenone, 1-(4-isopropyl group) can be used. Phenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1-(4- Olefinophenyl)-butan-1-one or 2-methyl-1-[4-(methylthio)phenyl]-2- An acetophenone photopolymerization initiator such as phenylpropan-1-one; benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether or benzyl dimethyl condensate Benzoin-based photopolymerization initiator; diphenyl ketone, benzhydryl benzoic acid, methyl benzyl benzoyl benzoate, 4-phenyl diphenyl ketone, hydroxy diphenyl ketone, acrylate Diphenyl ketone photopolymerization initiator such as diphenyl ketone or 4-benzylidene-4'-methyldiphenyl sulfide; 9-oxygen sulphur 2-chloro 9-oxosulfur 2-methyl 9-oxosulfur Isopropyl 9-oxosulfur Or 2,4-diisopropyl 9-oxosulfur 9-oxosulfur Photopolymerization initiator; 2,4,6-trichloro-s-three 2-phenyl-4,6-bis(trichloromethyl)-s-three , 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-three , 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-three , 2-piperonyl-4,6-bis(trichloromethyl)-s-three 2,4-bis(trichloromethyl)-6-styryl-s-three ,2-(naphthalen-1-yl)-4,6-bis(trichloromethyl)-s-three , 2-(4-methoxy-naphthalen-1-yl)-4,6-bis(trichloromethyl)-s-three 2,4-trichloromethyl-(piperidinyl)-6-three Or 2,4-trichloromethyl (4'-methoxystyryl)-6-three Wait three The photopolymerization initiator; a borate photopolymerization initiator; an oxazole photopolymerization initiator or an imidazole photopolymerization initiator, etc., but is not limited thereto.

The photopolymerization initiator may be used singly or in combination of two or more kinds, and may also be used in combination as a sensitizer such as α-oxime oxy ester, decylphosphine oxide, methyl phenyl glyoxylate, benzyl, 9 , 10-phenanthrenequinone, camphorquinone, ethylhydrazine, 4,4'-diethylm-xylylenebenzene, 3,3',4,4'-tetra(t-butylperoxycarbonyl) A compound such as diphenyl ketone or 4,4'-diethylaminodiphenyl ketone is not limited to these compounds.

When the sensitizer is used as a standard, the amount of the sensitizer is preferably from 3 to 60% by weight, more preferably from the viewpoint of photocurability and developability. It is 5 to 50% by weight.

[Dispersing aid]

When the pigment is dispersed in the pigment carrier (B), a dispersion auxiliary agent such as another resin type pigment dispersant or a surfactant different from the above basic resin type dispersant (a) can be suitably used. The dispersing aid is excellent in dispersion of the pigment and has a large effect of preventing re-agglomeration of the pigment after dispersion. Therefore, when a green coloring composition obtained by dispersing a pigment in a pigment carrier (B) with a dispersing aid is used, A color filter having a high spectral transmittance can be obtained.

The other resin type pigment dispersant different from the above basic resin type dispersant (a) also has a pigment affinity portion and a portion compatible with the pigment carrier, and the pigment affinity portion has a property of adsorbing on the pigment. The dispersant adsorbs on the pigment to function as a dispersion of the pigment in the pigment carrier (B). As the resin type pigment dispersant, another known resin type pigment dispersant different from the above basic resin type dispersant (a) can be used. Specifically, a polyurethane or a polyacrylate can be used. Polycarboxylate, unsaturated polyamine, polycarboxylic acid, polycarboxylic acid (partial) amine salt, polycarboxylate ammonium salt, polycarboxylic acid alkylamine salt, polyoxyalkylene oxide, long chain polyamine decylamine a phosphate, a hydroxyl group-containing polycarboxylate, or a modified substance thereof, or an oily dispersant such as a guanamine or a salt thereof formed by reacting a poly(lower alkyleneimine) with a polyester having a free carboxyl group, (A) Water-soluble resin such as acrylic acid-styrene copolymer, (meth)acrylic acid-(meth)acrylate copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, or polyvinylpyrrolidone or high water solubility A molecular compound, a polyester type, a modified polyacrylate type, an ethylene oxide / a propylene oxide addition compound, or a phosphate type, etc., These may be used individually or in mixture of 2 or more types.

The surfactant may, for example, be sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, an alkali metal salt of a styrene-acrylic acid copolymer, sodium stearate or alkylnaphthalenesulfonic acid. Sodium, sodium alkyl diphenyl ether disulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene oxide Anionic surfactant such as ether ether phosphate; polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitol a nonionic surfactant such as monostearate or polyethylene glycol monolaurate; a cationic surfactant such as an alkyl 4-grade ammonium salt or an ethylene oxide adduct thereof; An amphoteric surfactant such as an alkylbetaine or an alkylimidazoline, which may be used alone or in combination of two or more, is not limited thereto.

Further, in the green coloring composition for a color filter of the present invention, in order to sufficiently disperse the pigment in the pigment carrier (B), it is easy to have a dry film thickness of 0.2 to 5 μm on a transparent substrate such as a glass substrate. The coating is carried out to form a filter segment, and the solvent is contained, and it can be used as a "green ink" or a "green resist ink".

In the third embodiment of the present invention, the mixed organic solvent (c) is used as the solvent. However, in the first and second embodiments of the present invention, the organic solvent (c1), the organic solvent (c2), and the auxiliary solvent may be used. Choose to use.

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

[Storage Stabilizer]

Further, in order to stabilize the time-dependent viscosity of the composition, the green coloring composition of the present invention may contain a storage stabilizer.

The storage stabilizer may, for example, be a quaternary ammonium chloride such as benzyltrimethylammonium chloride or diethylhydroxylamine; an organic acid such as lactic acid or oxalic acid; or a methyl ester of the above organic acid; a catechol such as a third butyl catechol; an organic phosphine such as triphenylphosphine, tetraethylphosphine or tetraphenylphosphine; or a phosphite.

[Removal of coarse particles or dust]

The green coloring composition of the present invention preferably removes coarse particles of 5 μm or more (preferably coarse particles of 1 μm or more, more preferably coarse particles of 0.5 μm or more) by means of centrifugation, a sintered filter, or a membrane filter. Mixed with dust. When coarse particles are present, impurities remain in the color filter, which not only causes practical problems, but also clogging impurities in the piping or the nozzle during the coating step, causing a major manufacturing problem. Such a green coloring composition is preferably substantially free of particles of 0.5 μm or more. More preferably, the particles contained in the green coloring composition are 0.3 μm or less (particle diameter measured by SEM).

Further, in order to increase the brightness or the contrast ratio, the average dispersed particle diameter is preferably 0.05 to 0.2 μm, and when it is 0.06 to 0.15 μm, the brightness or the contrast ratio can be further improved, which is more preferable.

[Manufacture of color filters]

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

Since the formation of the filter segment by the printing method can be performed by merely printing and drying the coloring composition prepared as the printing ink, the color filter can be produced at a low cost. Excellent in terms of mass production. In addition, the development of printing technology enables fine pattern printing with high dimensional accuracy and smoothness. For printing, it is preferred to form a composition on the printing plate or on the outer cover that the ink does not dry or solidify. In addition, the control of the fluidity of the ink on the printing press is also important, and the viscosity of the ink can also be adjusted by using a dispersing agent or a filling pigment.

When the filter segment is formed by photolithography, it can be applied as a solvent developing type or an alkali developing type coloring resist by a coating method such as a spray coating method, a spin coating method, a slit coating method, or a roll coating method. The prepared coloring composition was applied onto a transparent substrate so as to have a dry film thickness of 0.2 to 5 μm. If necessary, the dried film is exposed to ultraviolet light by a mask having a predetermined pattern provided in contact with or in contact with the film. Thereafter, the developing solution is sprayed in a solvent or an alkali developing solution or sprayed with a sprayer or the like to remove the uncured portion to form a desired pattern, and then the same operation can be repeated for the other colors to manufacture a color filter. Further, in order to promote polymerization of the coloring resist, heating may be performed as needed. According to the photolithography method, a color filter having high precision can be manufactured by the above printing method.

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

Further, in order to increase the ultraviolet exposure sensitivity, a water-soluble or alkali-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin may be applied and dried after application and drying of the colored resist, and formation of oxygen may be prevented. The film that causes the polymerization to hinder is then exposed to ultraviolet light.

The color filter of the present invention can be produced by an electrodeposition method, a transfer method or the like other than the above method, and the colored composition of the present invention can be used in any of the methods. In addition, the electrodeposition method utilizes a transparent conductive film formed on a substrate, and electrophoretically forms a plurality of color filter segments on the transparent conductive film by electrophoresis of the colloidal particles, thereby producing a color filter.

Further, the transfer method is a method in which a filter segment is formed in advance on the surface of a peelable transfer substrate, and the filter segment is transferred onto a desired substrate.

[Color Filter]

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

The red filter segments can be formed using a common red coloring composition. Regarding the red coloring composition, for example, CI Pigment Red 7, 14, 41, 48:1, 48:2, 48:3, 48:4, 57:1, 81, 81:1, 81:2, 81 can be used. : 3, 81: 4, 122, 146, 168, 177, 178, 184, 185, 187, 200, 202, 208, 210, 246, 254, 255, 264, 270, 272, 279, etc. red pigment.

Regarding the red coloring composition, it is possible to use an orange pigment such as CI Pigment Orange 43, 71, 73, and/or 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, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, Yellow pigments of 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 198, 199, 213, 214.

Further, the blue filter segment can be formed using a usual blue coloring composition. As the blue coloring composition, a blue pigment such as C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 60, 64 can be used. Further, as for the purple coloring composition, a violet pigment such as C.I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50 may be used in combination.

[Examples]

Hereinafter, the present invention will be described based on examples, but the present invention is not limited to the examples. Further, in the examples and comparative examples, "parts" means "parts by weight". Further, Mn and Mw represent a number average molecular weight and a weight average molecular weight, respectively.

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

In the following examples and comparative examples, the number average molecular weight (Mn) and the weight average molecular weight (Mw) of the basic resin type dispersant were HLC-8320GPC (manufactured by Tosoh Corporation) as a device, and SUPER-AW3000 was used. The number average molecular weight (Mn) and weight average molecular weight (Mw) in terms of polystyrene measured as a column and N,N-dimethylformamide as 30 mM triethylamine and 10 mM LiBr as an eluent .

(2) Amine price

The amine valence of the basic resin type dispersant is a value obtained by solid-state conversion of the measured total amine value (mgKOH/g) according to the method of ASTM D 2074.

(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) are TSKge1 column (manufactured by Tosoh Corporation), and GPC equipped with an RI detector (Dongsuo) Co., Ltd., HLC-8120GPC), a polystyrene-equivalent number average molecular weight (Mn) and a weight average molecular weight (Mw) measured by using THF in a developing solvent.

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

The acid value of the acrylic resin used as the resin of the pigment carrier (B) is a value obtained by solid-state conversion of the measured acid value (mgKOH/g) according to the potential difference titration method of JIS K 0070.

(First embodiment)

The green coloring composition containing the above-mentioned basic resin type dispersing agent (a) as an essential component will be described using the examples (Example I series) and the comparative examples (Comparative Example I series).

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

Synthesis Example I-1: Synthesis of Resin Dispersant I-1 and Modulation of Its Solution

In a four-necked flask equipped with a thermometer, a stirrer, a distillation tube and a cooler, 70 parts of methyl ethyl ketone, 76.0 parts of n-butyl acrylate, 2.8 parts of oleolin, and ethyl bromoisobutyrate 1.9 were added. The temperature was raised to 40 ° C under a nitrogen gas stream. 1.1 parts of cuprous chloride was added, and the temperature was raised to 75 ° C to start polymerization. After the polymerization for 3 hours, the polymerization solution was sampled, and the polymerization yield was confirmed to be 95% or more from the solid content of the polymerization, and 24.0 parts of N,N-dimethylaminoethyl methacrylate and 30.0 parts of MEK were added, and further polymerization was carried out. From the solid content of the polymerization solution after 2 hours, the polymerization yield was confirmed to be 97% or more, 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, and 60 parts of a cation exchange resin "Diaion PK228LH (manufactured by Mitsubishi Chemical Corporation)" was added thereto, and the mixture was stirred at room temperature for 1 hour to further add hydrotalcite. (Kyoward 500SN: manufactured by Kyowa Chemical Industry Co., Ltd.) 10 parts were used as a neutralizing agent and stirred for 30 minutes. The cation exchange resin and the adsorbent are removed by filtration, thereby removing the residue of the polymerization catalyst. Further, the resin solution was concentrated and replaced with ethylene glycol monomethyl ether acetate to obtain a resin type dispersant I-1 having a nonvolatile content of 40% by weight (Mn=10200, Mw=12200, amine price: 86 mgK0H/g). Solution.

Synthesis Example I-2: Synthesis of Resin Dispersant I-2 and Modulation 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 oleolin, and ethyl bromoisobutyrate 1.6 were added in the same manner as in the above Synthesis Example I-1. The mixture was added with 0.9 parts of cuprous chloride to start polymerization. After 3 hours of polymerization, 15.0 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 residue of the polymerization catalyst was removed in the same manner as in the above-mentioned Synthesis Example I-1, and a resin-type dispersant I-2 (Mn=11900, Mw=13200, amine price 54 mgKOH) having a nonvolatile content of 40% by weight was obtained. /g) solution.

Synthesis Example I-3: Synthesis of Resin Dispersant I-3 and Modulation of Its Solution

70 parts of methyl ethyl ketone, 45.0 parts of ethyl acrylate, 43.0 parts of methyl methacrylate, 3.3 parts of oleolin, and 2.8 parts of ethyl bromoisobutyrate were added in the same manner as in the above Synthesis Example I-1. And adding 1.4 parts of cuprous chloride to start polymerization. After 3 hours of polymerization, 12.0 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 residue of the polymerization catalyst was removed in the same manner as in the above-mentioned Synthesis Example I-1, and a resin-type dispersant I-3 having a nonvolatile content of 40% by weight (Mn = 7000, Mw = 8,500, and an amine price of 43 mgKOH) was obtained. /g) solution.

Synthesis Example I-4: Synthesis of Resin Dispersant I-4 and Modulation of Its Solution

70 parts of methyl ethyl ketone, 71.0 parts of n-butyl acrylate, 2.8 parts of oleolin, and 1.9 parts of ethyl bromoisobutyrate were added in the same manner as in the above Synthesis Example I-1, and cuprous chloride was added thereto. 1.4 parts of the polymerization started. After 3 hours of polymerization, 29.0 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 residue of the polymerization catalyst was removed in the same manner as in the above-mentioned Synthesis Example I-1, and a resin type dispersant I-4 having a nonvolatile content of 40% by weight (Mn = 10000, Mw = 12,000, and an amine price of 105 mgKOH) was obtained. /g) solution.

Synthesis Example I-5: Synthesis of Resin Dispersant I-5 and Modulation of Its Solution

70 parts of methyl ethyl ketone, 66.0 parts of n-butyl acrylate, 2.8 parts of oleolin, and 1.9 parts of ethyl bromoisobutyrate were added in the same manner as in the above Synthesis Example I-1, and cuprous chloride was added thereto. 1.4 parts of the polymerization started. 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 residue of the polymerization catalyst was removed in the same manner as in the above-mentioned Synthesis Example I-1, and a resin-type dispersant I-5 having a nonvolatile content of 40% by weight (Mn = 9800, Mw = 12,000, and an amine price of 121 mgKOH) was obtained. /g) solution.

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

BYK-161, 163, 164, 167, 174, 184, 2000, 2050 manufactured by BYK Co., Ltd. as a commercially available resin type dispersant; S0LSPERSE-34750 and 56000 manufactured by Lubrizol Co., Ltd.; EFKA4330, 4046 manufactured by Ciba Japan K.K. 4060, 4080 are not more than 40% of non-volatile components, and the non-volatile content is 60% or more by drying under reduced pressure, and then adjusted to a non-volatile content of 40% by using ethylene glycol monomethyl ether acetate. The % solution was used as a solution of a commercially available resin type dispersant.

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

800 parts of cyclohexanone was added to the reaction vessel, and while heating to 100 ° C while injecting nitrogen into the vessel, 80.0 parts of styrene, 40.0 parts of methacrylic acid, and N, N methacrylate were added dropwise at the same temperature for 1 hour. A polymerization reaction was carried out by mixing a mixture of 85.0 parts of a methyl ester, 95.0 parts of n-butyl methacrylate and 10.0 parts of azobisisobutyronitrile.

After the dropwise addition, the reaction was further carried out at 100 ° C for 3 hours, and then a solution obtained by dissolving 2.0 parts of azobisisobutyronitrile with 50 parts of cyclohexanone was added, and the reaction was continued at 100 ° C for 1 hour to obtain a weight average molecular weight. It is a cyclohexanone solution of 30,000 acrylic acid 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 dried by heating at 180 ° C for 20 minutes to measure non-volatile components, and ethylene glycol monomethyl ether acetate was added to the previously synthesized resin solution so as not to A solution in which an acrylic resin IA was produced in a volatile component of 20% by weight.

Synthesis Example I-B~I-P: Synthesis of Acrylic Resin I-B~I-P and Modulation of Its Solution

The polymerization of the acrylic resin I-B to I-P was carried out in the same manner as in the above-described synthesis method of the acrylic resin I-A using the monomer composition and the starting amount (amount of azobisisobutyronitrile) shown in Table 2 below, and the solution was prepared. Further, the acid value and weight average molecular weight of the synthesized resin are shown in Table 2.

Abbreviation 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): Y>-750X+51000

(G): Y>940X-79000

(H): Y>8000

X: acid value of resin (mgKOH/g)

Y: weight average molecular weight of the resin

[Example I-1]

11.0 parts of a zinc halide phthalocyanine green pigment (CI Pigment Green 58), 2.5 parts of a SOLSPERSE-56000 solution adjusted according to a method for adjusting a solution of the above-mentioned resin dispersion type dispersant, 40.0 parts of a solution of the above acrylic resin IA, and ethylene glycol A mixture of 46.5 parts of monomethyl ether acetate was uniformly stirred and mixed, and then dispersed in EIGER MILL ("Mini Model M-250 MKII" manufactured by EIGER JAPAN Co., Ltd.) for 5 hours using zirconia beads having a diameter of 0.5 mm. It was filtered with a 5.0 μm filter to prepare a green pigment dispersion.

Then, the mixture was stirred and mixed to obtain 60.0 parts of the green pigment dispersion, 11.0 parts of the solution of the acrylic resin IA, and 4.2 parts of trimethylolpropane triacrylate ("NK ESTER ATMPT" manufactured by Shin-Nakamura Chemical Co., Ltd.), and photopolymerization. 1.2 parts of a starter ("Irgacure-907" manufactured by Ciba Japan KK Co., Ltd.), a mixture of 0.4 parts of a sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) and 23.2 parts of ethylene glycol monomethyl ether acetate After it became uniform, it was filtered with a 1.0 μm filter to obtain an alkali-developable green resist material I-1.

[Examples I-2 to I-24]

The alkali-developing resist material I- was obtained in the same manner as in the method shown in Example I-1 using the solution of the above-mentioned resin type dispersant shown in Table 3, the above-mentioned dye derivative, and the above-mentioned acrylic resin solution. 2~I-24. Further, Table 4 shows the type of the resin type dispersant (either a block type or a non-block type).

[Example I-25]

10.0 parts of a zinc halide phthalocyanine green pigment (C.I. Pigment Green 58), a resin solution of SOLSPERSE-56000 (40% by weight of a nonvolatile component), 2.5 parts, and the following formula I-9:

A mixture of 1.0 part of the pigment derivative having a basic functional group, 40.0 parts of the solution of the above acrylic resin IA, and 46.5 parts of ethylene glycol monomethyl ether acetate was uniformly stirred and mixed, and then a diameter of 0.5 mm was used. The zirconia beads were dispersed in an EIGER MILL ("Mini Model M-250 MKII" manufactured by EIGER JAPAN Co., Ltd.) for 5 hours, and then filtered with a 5.0 μm filter to prepare a green pigment dispersion.

Then, the mixture was stirred and mixed to obtain 60.0 parts of the green pigment dispersion, 11.0 parts of the solution of the acrylic resin IA, and 4.2 parts of trimethylolpropane triacrylate ("NK ESTER ATMPT" manufactured by Shin-Nakamura Chemical Co., Ltd.), and photopolymerization. 1.2 parts of a starter ("Irgacure-907" manufactured by Ciba Japan KK Co., Ltd.), a mixture of 0.4 parts of a sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) and 23.2 parts of ethylene glycol monomethyl ether acetate After it became uniform, it was filtered with a 1.0 μm filter to obtain an alkali-developable green resist material I-25.

[Example I-26~I-48]

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

[Examples I-49]

10.0 parts of a zinc halide phthalocyanine green pigment (C.I. Pigment Green 58), 2.5 parts of a SOLSPERSE-56000 solution (40% by weight of a nonvolatile component), and the following Formula I-10:

The three basic functional groups having a fixed portion (anchor portion) of benzimidazolone are shown. 1.0 part of the pigment derivative of the ring skeleton, 40.0 parts of the solution of the above acrylic resin IA, and 46.5 parts of ethylene glycol monomethyl ether acetate were uniformly stirred and mixed, and then zirconia beads having a diameter of 0.5 mm were used. After dispersing for 5 hours in EIGER MILL ("Mini Model M-250 MKII" manufactured by EIGER JAPAN Co., Ltd.), it was filtered with a 5.0 μm filter to prepare a green pigment dispersion.

Then, the mixture was stirred and mixed to obtain 60.0 parts of the green pigment dispersion, 11.0 parts of the solution of the acrylic resin IA, and 4.2 parts of trimethylolpropane triacrylate ("NK ESTER ATMPT" manufactured by Shin-Nakamura Chemical Co., Ltd.), and photopolymerization. 1.2 parts of a starter ("Irgacure-907" manufactured by Ciba Japan KK Co., Ltd.), a mixture of 0.4 parts of a sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) and 23.2 parts of ethylene glycol monomethyl ether acetate It became uniform and then filtered with a 1.0 μm filter to obtain an alkali-developable green resist material I-49.

[Example I-50~I-72]

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

[Comparative Example I-1~I-15]

The alkali-developing type was obtained in the same manner as in Example I-1 except that the solution of the dispersing agent shown in Table 7 (40% by weight of the nonvolatile component) was used instead of the SOLSPERSE-56000 solution used in Example I-1. Etch material I-73~I-87.

[Comparative Example I-16]

An alkali-developing resist material I-88 was obtained in the same manner as in Example I-3 except that a copper halide phthalocyanine green pigment (C.I. Pigment Green 36) was used instead of the zinc halide phthalocyanine green pigment (C.I. Pigment Green 58).

(evaluation method)

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

(1) Method for measuring viscosity characteristics

The viscosity of the obtained alkali-developing resist material was measured using an E-type viscometer ("ELD-type viscometer" manufactured by Toki Sangyo Co., Ltd.), and the viscosity at a rotation number of 20 rpm was measured. Further, the ratio of the viscosity at the rotation number of 6 rpm to 60 rpm (referred to as the thixotropic index, the larger the value, the higher the thixotropy) was obtained, and the thixotropy was evaluated.

(2) Method for determining the increase rate of viscosity over time

The initial viscosity of the obtained alkali-developing resist material after the preparation of the alkali-developing resist material was measured at 25 ° C and a rotation number of 20 rpm using an E-type viscometer ("ELD-type viscometer" manufactured by Toki Sangyo Co., Ltd.). The time-dependent viscosity with time promotion was carried out by leaving at 40 ° C for 1 week. The initial viscosity and the time-dependent viscosity thus determined were substituted into the following formula, and the rate of increase in viscosity over time was measured.

[Change in viscosity over time] = (temporal viscosity / initial viscosity) × 100

(3) Method for measuring brightness

The obtained alkali-developing resist material was changed by the spin coater to change the number of rotations, and three coated substrates were produced in such a manner that the dryness of the film thickness in the CIE chromaticity system was 0.62, 0.6, and 0.58. After coating, the film was dried at 80 ° C for 30 minutes in a hot air oven, and then the film thickness was measured, and the brightness of the chromaticity y was 0.6 by a linear correlation method from three data. The chromaticity was measured using a microscopic spectrophotometer ("OSP-SP100" manufactured by Olympus Optics Co., Ltd.).

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

Using the substrate used for the brightness measurement, the contrast ratio when the chromaticity y was 0.6 was obtained from the three data by a linear correlation method. The chromaticity was measured using a microscopic spectrophotometer ("OSP-SP100" manufactured by Olympus Optics Co., Ltd.).

The apparatus for measuring the contrast ratio of the coating film and the method for calculating the numerical value will be described with reference to Fig. 1 below.

The light emitted from the backlight unit (7) for the liquid crystal display is polarized by the polarizing plate (6), and passes through the dried coating film (4) of the colored composition coated on the glass substrate (5) to reach the polarizing plate (3). . If the polarizing plate (6) is parallel to the polarizing surface of the polarizing plate (3), the light penetrates the polarizing plate (3), but when the polarizing surface is perpendicular, the light is shielded by the polarizing plate (3). However, if the polarized light caused by the polarizing plate (6) passes through the dried coating film (4) of the colored composition, scattering or the like caused by the pigment particles occurs, and a deviation occurs in one of the polarizing surfaces, the polarizing plate is parallel. When the amount of light passing through the polarizing plate (3) is reduced, a part of the light penetrates the polarizing plate (3) when the polarizing plate is vertical. The transmitted light was measured as the brightness on the polarizing plate, and the ratio of the brightness of the polarizing plate in parallel and the brightness in the vertical direction (contrast ratio) was calculated.

(contrast ratio) = (brightness in parallel) / (brightness in vertical)

Therefore, if scattering due to the pigment of the dried coating film (4) of the colored composition occurs, the brightness in parallel decreases, and the brightness in the vertical direction increases, so the contrast ratio becomes low.

Further, a luminance meter (1) is a color luminance meter ("BM-5A" manufactured by Topcon Corporation), and a polarizing plate ("NPF-G1220DUN" manufactured by Nitto Denko Corporation) is used as the polarizing plate. Further, in order to shield the unnecessary light during the measurement, a black mask (2) having a square hole having a side length of 1 cm in the measurement portion was placed.

(5) Method for measuring the rate of change over time

The obtained alkali-developing resist material was allowed to stand at 40 ° C for seven days, and the rate of change of CR (contrast ratio) after standing for seven days with respect to the initial CR (contrast ratio) was determined by the following formula.

Time-dependent CR rate of change = (CR after seven days of standing) / (initial CR)

If the rate of change over time is 90% or more, the practical level can be achieved. It is preferably 95% or more. When it exceeds this range, the storage stability is poor and it cannot become a green coloring composition for a color filter.

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

[Table 8]

As shown in the Example I series, when an alkaline resin type dispersant having an amine price of 35 to 100 mgKOH/g is used, fluidity is good, storage stability is excellent over time, and high brightness and high contrast ratio are achieved. Green coloring composition.

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

Further, when a dye derivative having a basic functional group is used in combination with the above-described resin type dispersant, the initial contrast ratio is increased, and the viscosity characteristics and stability over time are also substantially good. Further, when further used in combination with the following resin, the most excellent green coloring composition can be obtained, and when the X is used as the acid value and Y is the average molecular weight, (F) Y > -750X + 51000 and (G) Y >940X-79000 and the resin represented by the range of (H)Y>8000.

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

(Second embodiment)

Next, the green coloring composition containing the above-described dye derivative (b) as an essential component will be described using the examples (Example II series) and the 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 Modulation of Its Solution

800 parts of cyclohexanone was added to the reaction vessel, and while heating to 100 ° C while injecting nitrogen into the vessel, 80.0 parts of styrene, 40.0 parts of methacrylic acid, and methyl methacrylate 85.0 were added dropwise at the same temperature for 1 hour. A mixture of 95.0 parts of n-butyl methacrylate and 2.0 parts of azobisisobutyronitrile was subjected to a polymerization reaction.

After the dropwise addition, the mixture was further reacted at 100 ° C for 3 hours, and then a solution obtained by dissolving 2.0 parts of azobisisobutyronitrile with 50 parts of cyclohexanone was added, and the reaction was further continued at 100 ° C for 1 hour to obtain a weight average molecular weight of about 30000, a cyclohexanone 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 dried by heating at 180 ° C for 20 minutes to measure non-volatile components, and ethylene glycol monomethyl ether acetate was added to the previously synthesized resin solution so as not to The volatile component was 20% by weight, and a solution of the acrylic resin II-A was prepared.

Synthesis Example II-B~II-P: Synthesis of Acrylic Resin II-B~II-P and Modulation of Its Solution

The synthesis of the acrylic resin II-B~II-P was carried out in the same manner as the above-mentioned synthesis method of the acrylic resin II-A, using the monomer composition and the starting dose (amount of azobisisobutyronitrile) shown in Table 12 below, and Prepare its solution. Further, the acid value and weight average molecular weight of the synthesized resin are shown in Table 12.

Description of the abbreviation 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): Y>-750X+51000

(G): Y>940X-79000

(H): Y>8000

X: acid value of resin (mgKOH/g)

Y: weight average molecular weight of the resin

[Example II-1]

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

Shown with the basic substituent having a fixed moiety benzimidazolone A mixture of 1.0 part of a pigment derivative of a ring skeleton, 40.0 parts of a solution of an acrylic resin II-A, and 48.0 parts of ethylene glycol monomethyl ether acetate was uniformly stirred and mixed, and then zirconia beads having a diameter of 0.5 mm were used. The pellet was dispersed in EIGERMILL ("Mini Model M-250 MKII" manufactured by EIGER JAPAN Co., Ltd.) for 5 hours, and then filtered with a 5.0 μm filter to prepare a green pigment dispersion.

Then, the mixture was stirred and mixed to obtain 60.0 parts of the green pigment dispersion, 11.0 parts of the solution of the acrylic resin II-A, and 4.2 parts of trimethylolpropane triacrylate ("NK ESTER ATMPT" manufactured by Shin-Nakamura Chemical Co., Ltd.). 1.2 parts of a polymerization initiator ("Irgacure-907" manufactured by Chiba Specialty Chemical Co., Ltd.), 0.4 parts of a sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.), and 23.2 parts of ethylene glycol monomethyl ether acetate. The mixture was uniformly formed, and then filtered with a 1.0 μm filter to obtain an alkali-developable green resist material II-1.

[Example II-2]

In addition to the solution of the acrylic resin II-A being 37.0 parts, an acrylic polymer dispersing agent adjusted by adding ethylene glycol monomethyl ether acetate to a nonvolatile content of 20% by weight (Ciba Japan KK Co., Ltd.) An alkali-developing resist material II-2 was obtained in the same manner as in Example II-1 except that 3 parts of a solution of "EFKA4300 (amine price: 56 mgKOH/g)" was prepared.

[Example II-3]

In addition to the solution of the acrylic resin II-A being 37.0 parts, and adding the ethylene glycol monomethyl ether acetate to adjust the non-volatile content to 20% by weight, the adjusted urethane-based polymer dispersant ( The alkali-developing resist material II-3 was obtained in the same manner as in Example II-1 except that 3 parts of a solution of "BYK-163 (amine price: 10 mgKOH/g)) was produced by BYK.

[Example II-4]

In addition to having a basic substituent having a fixed moiety benzimidazolone The pigment derivative of the ring skeleton is changed to the following formula II-10:

Illustrated as having three basic substituents having a fixed moiety An alkali-developing resist material II-4 was obtained in the same manner as in Example II-1 except for the pigment derivative of the ring skeleton.

[Example II-5]

In addition to changing 11.0 parts of the zinc halide phthalocyanine green pigment (CI Pigment Green 58) to 9.0 parts of a zinc halide phthalocyanine green pigment (CI Pigment Green 58) and a metal complex yellow pigment (CI Pigment Yellow 150, manufactured by LANXESS) An alkali-developing resist material II-5 was obtained in the same manner as in Example II-1 except for 2.0 parts of Yellow Pigment E4GN.

[Example II-6]

In addition to having a basic substituent having a fixed moiety benzimidazolone 1.0 part of the pigment derivative of the ring skeleton was changed to the following formula II-11:

The alkali-developing resist material II-6 was obtained in the same manner as in Example II-1 except that 1.0 part of the pigment derivative having a basic substituent of benzimidazolone was used.

[Example II-7]

In addition to having a basic substituent having a fixed moiety benzimidazolone 1.0 part of the pigment derivative of the ring skeleton was changed to the following formula II-12:

An alkali-developing resist material II-7 was obtained in the same manner as in Example II-1 except that 1.0 part of the pigment derivative having a basic substituent of fluorene was used.

[Examples II-8 to II-15]

An alkali-developing 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 a solution of the acrylic resin II-B. In the following, an alkali-developing resist material II-9~II- 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-C~II-I. 15.

[Comparative Example II-1]

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

[Comparative Example II-2]

In addition to 11.0 parts of a zinc halide phthalocyanine green pigment (CI Pigment Green 58), which was changed to 11.0 parts of a copper halide phthalocyanine green pigment (CI Pigment Green 36, "Lionol Green 6YK" manufactured by Toyo Ink Co., Ltd.), In the same manner as in Example II-1, an alkali-developing resist material II-17 was obtained.

[Comparative Example II-3]

In addition to 11.0 parts of a zinc halide phthalocyanine green pigment (CI Pigment Green 58), which was changed to 11.0 parts of a copper halide phthalocyanine green pigment (CI Pigment Green 7, "Lionol Green YS-07" manufactured by Toyo Ink Co., Ltd.), An alkali-developing resist material II-18 was obtained in the same manner as in Example II-1.

[Examples II-16 to II-22]

An alkali-developing 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. In the following, an alkali-developing resist material II-20~II- was 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 resin II-K~II-P. 25.

(evaluation method)

The viscosity, the thixotropic index, the brightness of the coating film, and the contrast ratio of the resist obtained above were evaluated in the same manner as in the first embodiment. The results are shown in Table 13.

As shown in the Example II series, if a dye derivative having a basic substituent is used in dispersing a zinc halide phthalocyanine pigment, a coloring composition excellent in fluidity can be obtained, and high brightness and high contrast ratio can be simultaneously achieved. Coating film. Especially in use with three When the pigment derivative of the skeleton is used, the brightness and the contrast ratio show good values. Further, it is particularly preferable when used in combination with a resin solution in which X is used as an acid value and Y is an average molecular weight, and is represented by a range of Y>-750X+51000 and Y>940X-79000 and Y>8000. Resin solution. On the other hand, the resist material using the coloring composition of Comparative Example II-1 has a much higher viscosity than the resist material obtained in the examples, and the brightness and contrast ratio of the coating film are also low. level. Further, for the resist materials using the color compositions of Comparative Examples II-2 and II-3, the viscosity was the same as that of the resist materials obtained in the examples, and the contrast ratio of the coating films was almost the same level. However, the brightness is lower than that of the coating film obtained in the examples.

(Third embodiment)

Further, the green coloring composition containing the mixed organic solvent (c) as an essential component will be described using the examples (Example III series) and the comparative examples (Comparative Example III series).

First, the evaluation method of the coating property of the resist and the acrylic resin solution used in the Example III series and the comparative example III series will be described.

[Evaluation method of coating property]

The evaluation of the coatability will be described.

Coating was performed by a coating apparatus of a die coating method and a spin coating method to form an average film thickness of 2.0 μm on a glass substrate of a size of 360 mm × 465 mm, and the obtained coated substrate was pretreated at 70 ° C for 20 minutes. Bake to obtain a dry coating film. Hereinafter, methods for expressing evaluation items, contents, and results will be described.

<Only spin coating method> (film thickness uniformity)

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

"Thickness of film thickness (other than the end portion)": The film thickness was measured every 2 cm from the center of the substrate of the coated substrate in the diagonal direction up to 26 cm. Similarly to the above, the film thickness uniformity (other than the end portion) was calculated by the following formula (A).

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

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

<only die coating method> (longitudinal strip unevenness)

"Vertical stripe unevenness": For the coated substrate, the white-penetrating light is used to evaluate the unevenness of the strip shape as the agglomerate originating from the opening of the slit in the direction in which the slit advances. "." When there was no longitudinal stripe unevenness by visual inspection, it was recorded as ○, and when the longitudinal stripe unevenness was observed, it was recorded as ×.

(maximum penetration rate)

The obtained alkali-developing resist material was produced by using a spin coater and changing the number of rotations to produce three coated substrates so that the chromaticity y of the dried film thickness in the CIE chromaticity system was 0.62, 0.6, and 0.58. After coating, it was dried in a hot air oven at 80 ° C for 30 minutes, and then the film thickness was measured, and the maximum transmittance at a chromaticity y of 0.6 was determined from the three data by a linear correlation method. The chromaticity was measured using a microscopic spectrophotometer ("OSP-SP100" manufactured by Olympus Optics Co., Ltd.).

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 Acrylic Resin III-A Solution

800 parts of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMAC) was added to the reaction vessel, and while heating to 100 ° C while injecting nitrogen into the vessel, 60.0 parts of styrene was added dropwise at the same temperature for 1 hour. A polymerization reaction was carried out by mixing a mixture of 60.0 parts of acrylic acid, 65.0 parts of methyl methacrylate, 65.0 parts of butyl methacrylate, and 10.0 parts of azobisisobutyronitrile.

After the dropwise addition, the mixture was further reacted at 100 ° C for 3 hours, and then a solution obtained by dissolving 2.0 parts of azobisisobutyronitrile in 50 parts of PGMAC was added, and the reaction was further continued at 100 ° C for 1 hour to obtain a weight average molecular weight (Mw). A solution of 40,000 acrylic resin III-A.

After cooling to room temperature, about 2 g of the resin solution was sampled, and dried by heating at 180 ° C for 20 minutes to measure a nonvolatile matter, and PGMAC was added to the previously synthesized resin solution so that the nonvolatile content was 20% by weight to produce A solution of acrylic resin III-A.

Pigment preparation example

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

(primary particle size measurement method)

The average primary particle diameter of the pigment was measured by directly measuring the size of the primary particles by an electron micrograph of a transmission electron microscope (TEM). Specifically, the minor axis diameter and the major axis diameter of the primary particles of each pigment are measured, and the average value is taken as the particle diameter of the pigment particles. Next, the volume (weight) of each of the 100 pigment particles was determined by approximating the cube of the particle diameter, and the volume average particle diameter was referred to as the average primary particle diameter.

(Modulation of Green Pigment III-1)

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

(Modulation of Green Pigment III-2)

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

(Modulation of Green Pigment III-3)

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

(modulation of yellow pigment)

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

Pigment dispersion preparation example

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

(Modulation of Green Pigment Dispersion III-1)

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 a mixture of 1.0 parts of a resin type dispersant (EFKA 4300) After uniformly stirring and mixing, zirconia beads having a diameter of 0.5 mm were used, and dispersed in an EIGER MILL ("Mini Model M-250 MKII" manufactured by EIGER JAPAN Co., Ltd.) for 5 hours, and then filtered through a 5.0 μm filter. To prepare a green pigment dispersion III-1.

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

[Example of manufacturing resist material]

Next, a method of measuring the dispersion particle size of the green resist material and a preparation method will be described.

(Measurement of dispersed particle size)

Microtrac UPA-EX 150, which uses the dynamic light scattering method (FFT power spectroscopy), uses particle permeability as the absorption mode, the particle shape is non-spherical, and D50 is taken as the average diameter. The dilution solvent used for the measurement was measured for the sample treated by the ultrasonic wave using the solvent used in the dispersion.

(particle size measured by SEM)

The particle size of the pigment measured by SEM was measured by a method of directly measuring the size of the largest particle by an electron micrograph of a scanning electron microscope (SEM). Specifically, 50 pigment particles are photographed in the photograph, and the minor axis diameter and the major axis diameter of the primary particles of each pigment are measured, and the average value is taken as the particle diameter of the pigment particles, and the effective number of one bit is retained after the decimal point. The way it is expressed is its largest particle size.

(Green resist material III-1)

60.0 parts of green pigment dispersion III-1

11.0 parts of acrylic resin solution

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

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

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

15.0 PGMAC

8.2 parts of cyclohexyl acetate

After stirring and mixing to uniformly form the above mixture, the mixture was filtered with a 1.0 μm filter to obtain an alkali-developable green resist material III-1. The compounding ratio of PGMAC in all solvents was 89.8%, and the compounding ratio of cyclohexyl acetate was 10.2%. Further, the particle diameter of the dispersed green pigment particles as measured by SEM was 0.2 μm.

(Green resist material III-2)

60.0 parts of green pigment dispersion III-1

11.0 parts of acrylic resin solution

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

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

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

23.2 parts of cyclohexyl acetate

After stirring and mixing to uniformly form the above mixture, the mixture was filtered with a 1.0 μm filter to obtain an alkali-developable green resist material III-2. The compounding ratio of PGMAC in all solvents was 71.0%, and the compounding ratio of cyclohexyl acetate was 29.0%. Further, the particle diameter of the dispersed green pigment particles as measured by SEM was 0.2 μm.

Hereinafter, green resist materials III-3 to III-11 were obtained in the same manner as in the preparation of the green resist material III-1 using the materials shown in Table 15. Further, in Table 15, the particle diameters of the respective resist materials measured by SEM are shown.

[Comparative example]

The green resist material was prepared in the same manner as the green resist material III-1 by using the material shown in Table 16. Further, for the green resist materials III-12 and III-19, 23.2 parts of one solvent was added. Further, in Table 16, the particle diameter of each resist material measured by SEM is shown.

[Table 16]

Further, the characteristic values of the organic solvents used in the examples III series and the comparative example III series are shown in Table 17.

The viscosity, the thixotropic index, the brightness of the coating film, and the contrast ratio of the resist obtained above were evaluated in the same manner as in the first embodiment, and the results of evaluation of the dispersed particle diameter, the maximum transmittance, and the coating property were shown in Table 18 and Table 19.

(Manufacture of red pigment dispersion)

Next, a color filter was produced using a red resist material and a green resist material, and evaluated. First, a description will be given of a red resist material used in the production of a color filter.

8.0 parts of CI Pigment Red 177, 40 parts of acrylic resin solution, 48.0 parts of propylene glycol monomethyl ether acetate (PGMAC), and 1.0 part of resin type dispersant (EFKA4300) were uniformly stirred and mixed, and then the diameter was 0.5. The zirconia beads of mm were dispersed in an EIGER MILL ("Mini Model M-250 MKII" manufactured by EIGER JAPAN Co., Ltd.) for 5 hours, and then filtered with a 5.0 μm filter to prepare a red pigment dispersion.

(modulation of red resist material)

The mixture was stirred and mixed to obtain 60.0 parts of a red pigment dispersion, 11.0 parts of an acrylic resin solution, and 4.2 parts of trimethylolpropane triacrylate ("NK ESTER ATMPT" manufactured by Shin-Nakamura Chemical Co., Ltd.), and a photopolymerization initiator (Ciba Japan). 1.2 parts of "Irgacure-907" manufactured by KK Corporation, a mixture of 0.4 parts of sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) and 23.2 parts of PGMAC were uniformly formed, and then filtered with a 1.0 μm filter to obtain Alkali-developed red resist material.

(production of color filters)

The red resist material having a thickness of about 2 μm was coated on a 10 cm × 10 cm glass substrate by a spin coater, and allowed to stand in an oven at 70 ° C for 15 minutes, and the remaining solvent was removed and dried. Next, the stripe pattern exposure is performed using an exposure device. The exposure amount was 100 mJ/cm ² . Further, spray development was carried out using a developing solution containing a 2% aqueous sodium carbonate solution, the unexposed portion was removed, and then washed with ion-exchanged water, and the substrate was heated at 230 ° C for 30 minutes to form a red filter having a line width of about 50 μm. Fragment. Then, through the same operation, the filter segments are formed using the green resist material of Example III-1 adjacent to the red filter segments, thereby producing a color filter having filter segments of two colors. .

When a solvent (c1) is used as in the green resist materials III-1 to III-11 shown in the embodiment III series, and a resist using a zinc halide phthalocyanine pigment dispersion is used, at least a solvent is used. When the organic solvent is mixed with the solvent (c2) and the solvent (c2), a coloring composition excellent in fluidity and coatability can be obtained, and a coating film capable of achieving high brightness, high transmittance, and high contrast ratio can be obtained. On the other hand, in the green resist materials III-12 to III-21 shown in the comparative example III series, a coating film which can simultaneously satisfy the brightness, the contrast ratio, the transmittance, and the coatability cannot be obtained.

1. . . Luminance meter

2. . . Mask

3. . . Polarizer

4. . . Coloring composition drying coating film

5. . . glass substrate

6. . . Polarizer

7. . . Backlight unit

Fig. 1 is a schematic explanatory view of a measuring device for measuring a contrast ratio.

1. . . Luminance meter

2. . . Mask

3. . . Polarizer

4. . . Coloring composition drying coating film

5. . . glass substrate

6. . . Polarizer

7. . . Backlight unit

Claims (12)

A green coloring composition for a color filter, comprising: (A) a pigment component containing at least a zinc halide phthalocyanine pigment; and (B) a pigment carrier comprising a resin, a precursor thereof or a mixture thereof; At least one selected from the group consisting of (a) a basic resin type dispersant having an amine price of 35 to 100 mg KOH/g; (b) a pigment derivative having a basic substituent; and (c) a solubility The parameter (SP value) is 8.0 to 10.0 (cal/cm ³ ) ^1/2 , the organic solvent (c1) having a boiling point of 140 to 159 ° C at 760 mmHg, and the solubility parameter (SP value) is 8.0 to 10.0 (cal/cm). ³ ) a mixed organic solvent of organic solvent (c2) having a boiling point of 160 to 200 ° C at ^1/2 and 760 mmHg; wherein, (1) when the acid value is referred to as X (mg KOH/g), the weight average molecular weight is recorded as In the case of Y, the resin constituting the above pigment carrier (B) is a resin which satisfies all the conditions of the following formulas (F), (G) and (H): (F) Y > -750X + 51000 (G) Y > 940X - 79000 (H)Y>8000; (2) The content of the pigment carrier (B) is 30 to 500% by weight based on the total weight of the above pigment component (A); (3) containing the above-mentioned basic resin type dispersant ( a), based on the total weight of the above pigment component (A), The amount is 0.001 to 50% by weight; (4) when the pigment derivative (b) is contained, the content is 0.001 to 40% by weight based on the total weight of the pigment component (A); In the case of the solvent (c), the content is from 800 to 4,000% by weight based on the total weight of the above pigment component (A). The green coloring composition for a color filter according to the first aspect of the invention, wherein the basic resin type dispersing agent (a) comprises a basic copolymer block (a1) and a pigment carrier affinity copolymer block. Block copolymer resin of (a2). The green coloring composition for a color filter according to the second aspect of the invention, wherein the block copolymer resin is a block copolymer resin obtained by living radical polymerization. The green coloring composition for a color filter according to the first aspect of the invention, wherein the organic solvent (c1) is selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and ethylene glycol. One or more solvents of monomethyl ether acetate and ethylene glycol monoethyl ether acetate. The green coloring composition for a color filter according to the first aspect of the invention, wherein the organic solvent (c2) is selected from the group consisting of cyclohexyl acetate, propylene glycol diacetate, diethylene glycol diethyl ether, and One or more solvents of ethyl ethoxypropionate. The green coloring composition for a color filter according to the first aspect of the invention, wherein the organic solvent (c1) is 50% by weight to 95% by weight based on the total of the mixed organic solvent (c). The organic solvent (c2) is 5% by weight to 50% by weight. A green coloring composition for a color filter according to the first aspect of the invention, further comprising a photopolymerization initiator. The green coloring composition for a color filter according to the first aspect of the invention, wherein the basic resin type dispersing agent (a) and the coloring matter derivative (b) are contained. The green coloring composition for a color filter according to the first aspect of the invention, wherein the basic resin type dispersing agent (a) and the mixed organic solvent (c) are contained. The green coloring composition for a color filter according to the first aspect of the invention, wherein the coloring matter derivative (b) and the mixed organic solvent (c) are contained. The green coloring composition for a color filter according to claim 10, further comprising the above basic resin type dispersing agent (a). A color filter comprising a green filter segment formed by a green coloring composition for a color filter according to any one of claims 1 to 11.