JP2012194526A - Colored composition for color filter, and color filter - Google Patents

Abstract

An object of the present invention is to provide a stable blue coloring composition for a color filter having excellent color characteristics, and a color filter having excellent color characteristics using the same.
A coloring composition for a color filter comprising copper phthalocyanine (A), a dispersant (B), a transparent resin (C), an organic solvent (D), and an organic dye (E). Is a α-type coloring composition for a color filter.
A coloring composition for a color filter, wherein the content of α-type in copper phthalocyanine (A) is 90% by weight or more.
[Selection figure] None

Description

  The present invention relates to a blue coloring composition for a color filter used for manufacturing a color filter used in a color liquid crystal display device, a color image pickup tube element, and the like, and a color filter including a filter segment formed using the same. It is. The blue coloring composition can be applied to blue and cyan color filters.

  The color liquid crystal display device controls the amount of light passing through the second polarizing plate by controlling the degree of polarization of the light that has passed through the first polarizing plate by the liquid crystal layer sandwiched between the two polarizing plates. This is a display device that performs display, and a type using a twisted nematic (TN) type liquid crystal is mainly used. The liquid crystal display device can perform color display by providing a color filter between two polarizing plates. Therefore, liquid crystal display devices are being developed for use in televisions and personal computer monitors.

  Other typical liquid crystal display devices include an in-plane switching (IPS) method in which a pair of electrodes is provided on one substrate and electrolysis is applied in a direction parallel to the substrate, negative dielectric anisotropy Vertical alignment (VA) method for vertically aligning nematic liquid crystal with optical properties, and Optical Convencence Bend (OCB) method in which the optical axes of uniaxial retardation films are orthogonal to each other to perform optical compensation Etc., and each has been put to practical use.

  In general, the color filter is a red filter layer (R), green filter layer (G) and blue filter layer (B) formed on the surface of a transparent substrate such as glass, or a complementary color of red, green and blue. Corresponding fine band (striped) filter segments (pixels) composed of a cyan filter layer (C), a magenta filter layer (M), and a yellow color filter layer (Y) are arranged in parallel or crossing each other. Or fine filter segments arranged in a constant vertical and horizontal arrangement. The filter segments are as fine as several microns to several hundreds of microns, and are regularly arranged in a predetermined arrangement for each hue.

  On the color filter used in the color liquid crystal display device, a transparent electrode for driving the liquid crystal is generally formed by vapor deposition or sputtering, and an alignment film for aligning the liquid crystal in a certain direction is formed thereon. Has been. In order to sufficiently obtain the performance of these transparent electrodes and alignment films, it is necessary to perform the formation process at a high temperature of generally 200 ° C. or higher, preferably 230 ° C. or higher.

  Quality items required for the color filter include brightness and contrast ratio. When a color filter with a low contrast ratio is used, the degree of polarization controlled by the liquid crystal is disturbed, and when light must be blocked (OFF state), light must leak or be transmitted (ON) In other words, the transmitted light is attenuated in the state), resulting in a blurred screen. Therefore, in order to realize a high-quality liquid crystal display device, high contrast is indispensable.

  If a color filter with low brightness is used, the light transmittance is low, resulting in a dark screen. In order to obtain a bright screen, it is necessary to increase the number of backlights as light sources. For this reason, from the viewpoint of suppressing an increase in power consumption, increasing the brightness of color filters has become a trend. Furthermore, as described above, since the color liquid crystal device has been used for televisions, personal computer monitors, and the like, the demand for high reliability and high lightness and contrast for color filters has also increased.

  The color filter production method includes a dyeing method using a dye or a salt-forming dye as a colorant, a dye dispersion method, a pigment dispersion method using a pigment as a colorant, a printing method, and an electrodeposition method. Among these, the dyeing method or the dye dispersion method has a drawback that the heat resistance and light resistance are slightly inferior because the colorant is a dye. Therefore, a pigment having excellent heat resistance and light resistance is used as a colorant for the color filter, and a pigment dispersion method is often used as a manufacturing method because of the accuracy and stability of the forming method.

  In the pigment dispersion method, a color resist is formed by mixing and preparing a photosensitizer and additives in a pigment in which pigment particles as a colorant are dispersed in a transparent resin, and this color resist is applied on a substrate such as a spin coater. It is a method for forming a color filter by forming a coating film with an apparatus, selectively exposing through a mask with an aligner, a stepper, etc., patterning by alkali development and thermosetting, and repeating this operation. .

  In general, the pigment particles are subjected to a micronization treatment and a pigment dispersion in which the micronized pigment is brought close to the primary particles as much as possible is used to suppress light scattering by the pigment and achieve high contrast. In addition, since the transparency of the dispersion is improved, the spectral spectrum of the dispersion has high transmittance, and high brightness is realized. By using this dispersion as a color resist, a color filter having high contrast and high brightness can be obtained.

  Conventionally, as a colorant used for forming a blue filter segment (pixel) or a cyan filter segment (pixel), a phthalocyanine pigment generally excellent in durability and color tone is often used. As this phthalocyanine pigment, those having various central metals such as copper, zinc, nickel, cobalt, and aluminum are known. Among these, copper phthalocyanine pigments are widely used because they have the clearest color tone. In addition, metal phthalocyanine pigments such as metal-free phthalocyanine pigments, zinc phthalocyanine pigments, aluminum phthalocyanine pigments, and cobalt phthalocyanine pigments have been put into practical use.

  Phthalocyanine pigments have different crystal types such as α-type, β-type, δ-type, and ε-type. Among these crystal types, ε-type crystal-type copper phthalocyanine is a crystal-type copper such as α-type. Compared with phthalocyanine, it is excellent in sharpness and coloring power and is suitable as a colorant for color filters.

  In conventional display devices, high brightness and a wide color display area can be achieved by combining ε-type copper phthalocyanine pigments, dioxazine pigments, and xanthene dyes with blue filter segments and cyan filter segments. (See, for example, Patent Documents 1 and 2). However, as described above, the color filter is required to have higher brightness and a wider color reproduction region.

JP 2009-265641 A JP 2010-32999 A JP 2000-109720 A

  An object of the present invention is to provide a stable blue coloring composition for a color filter excellent in color characteristics, and a color filter excellent in color characteristics using the same.

  As a result of intensive studies to solve the above problems, the inventors of the present invention contain copper phthalocyanine, a dispersant, a transparent resin, an organic solvent, and an organic dye as a colorant for the color filter coloring composition. The present inventors have found that high brightness and a wide color reproduction region are possible by using a coloring composition in which copper phthalocyanine is α-type, and the present invention has been made based on this finding.

  That is, the present invention relates to a color composition for a color filter containing copper phthalocyanine (A), a dispersant (B), a transparent resin (C), an organic solvent (D), and an organic dye (E). ) Contains α-type, and relates to a coloring composition for a color filter.

Further, in the present invention, the copper phthalocyanine (A) is obtained by subjecting a crude α-type copper phthalocyanine to salt milling or acid pasting in the presence of a compound represented by the following general formula (X). The present invention relates to a coloring composition.
Formula (X)
P-Ln
(However, P represents an organic pigment residue, an anthraquinone residue, an acridone residue or a triazine residue,
L represents a basic substituent, an acidic substituent, or a phthalimidomethyl group which may have a substituent, and represents an integer of n: 1 to 4. )

  The present invention also relates to the above color filter coloring composition, wherein P is a residue of a metal-free or metal phthalocyanine pigment.

  The present invention also relates to the above color filter coloring composition, wherein the content of α-type in copper phthalocyanine (A) is 90% by weight or more based on the total pigment.

  In the present invention, the organic dye (E) is one or more selected from the group consisting of triarylmethane, xanthene, and anthraquinone. About.

  The present invention also relates to a color filter comprising a pixel formed using the above color filter coloring composition.

  In the present invention, a color filter coloring composition containing copper phthalocyanine, a dispersant, a transparent resin, an organic solvent, and an organic dye, and a color filter coloring composition in which copper phthalocyanine (A) is α-type is used. Thus, a color filter having high brightness and a wide color reproduction region can be obtained.

  The coloring composition for a color filter of the present invention contains an α-type phthalocyanine blue pigment (A) and an organic dye (E) as a colorant, and maintains a high transmittance even at a short wavelength of 450 nm or less, while maintaining a high transmittance. The nearby transmittance is improved compared to the conventional one using ε-type copper phthalocyanine and organic dye (E) and the one using α-type phthalocyanine blue pigment and dioxazine pigment system. Can be obtained.

  Hereinafter, the present invention will be described in detail. In addition, “CI” described below means a color index (CI).

  The coloring composition for a color filter of the present invention is a blue coloring composition for a color filter comprising copper phthalocyanine and an organic dye as a coloring agent, and comprising a dispersant, a transparent resin, and an organic solvent.

<Colorant>
As a coloring agent of the coloring composition for a color filter of the present invention, copper phthalocyanine and an organic dye are included. By mixing these, 425 having a characteristic peak of many backlights as described above. In the vicinity of ˜500 nm, the spectral spectrum can have high transmittance, and high brightness and wide color reproducibility can be obtained.
Combining ε-type copper phthalocyanine blue pigment with violet pigment and / or organic dye is a widely used technology, but the chromaticity difference between α-type copper phthalocyanine blue pigment (A) and ε-type copper phthalocyanine blue pigment Therefore, when α-type copper phthalocyanine blue pigment (A) is used, the mixing ratio of violet pigment and organic dye can be increased compared to the case where ε-type copper phthalocyanine blue pigment is used. In that case, it has been found that the mixed colored composition exhibits excellent brightness and viscosity stability.

<Copper phthalocyanine (A)>
The copper phthalocyanine used in the present invention is α-type copper phthalocyanine. Although some ε-type and β-type may be mixed, since the higher α-type ratio is advantageous for brightness, the α-type ratio is preferably 50 to 100% by weight with respect to total copper phthalocyanine More preferably, it is 90 to 100% by weight.

Examples of conditions under which the α-type copper phthalocyanine blue pigment is particularly advantageous are shown below.
When viewed with a C light source, the value of x of the ε-type copper phthalocyanine blue pigment is about 0.135 when y = 0.088. On the other hand, the value of x of the α-type copper phthalocyanine blue pigment is about 0.128 when y = 0.088.
(1) When the desired hue is close to the ε-type copper phthalocyanine blue pigment (example: y = 0.088, x = 0.135)
When an organic dye is mixed with the ε-type copper phthalocyanine blue pigment, the chromaticity is shifted, so that the mixing is basically impossible. Even if it can be mixed, it becomes a small amount. On the other hand, in the case of the α-type copper phthalocyanine blue pigment, when adjusting to the hue of the ε-type copper phthalocyanine blue pigment, x is small and the redness is insufficient. Therefore, it is necessary to prepare a violet pigment or an organic dye, and it becomes possible to obtain a hue of an ε-type copper phthalocyanine blue pigment by mixing an appropriate amount. Here, when the brightness data is confirmed, the organic dye that works more favorably when the dye is mixed with the α-type copper phthalocyanine blue pigment than with the ε-type copper phthalocyanine blue pigment alone (or with a slight amount of the dye). It was confirmed that the lightness became advantageous as much as it was mixed (the amount contained a lot). However, when the violet pigment is mixed, the transmittance of the spectral spectrum around 450 nm, which contributes to the improvement of the brightness of blue, is inferior to the organic dye, and the α-type phthalocyanine pigment is less than the ε-type phthalocyanine pigment. Therefore, since the transmittance is low, improvement in brightness cannot be confirmed as compared with the ε-type copper phthalocyanine blue pigment alone.

(2) When the hue is more reddish than the ε-type copper phthalocyanine blue pigment (example: y = 0.088, x = 0.137)
The desired hue can be obtained by mixing an organic dye with the ε-type copper phthalocyanine blue pigment, but the mixing ratio in that case varies depending on the type of dye to be mixed, but approximately 10 to 20% is mixed. On the other hand, in the case of α-type copper phthalocyanine blue pigment, it is understood that the target hue can be obtained by mixing about 30 to 40% of reddish dye, and that the hue of α works favorably as the dye mixture increases. . In the case of (2), for the same reason as in the case of (1), no improvement in brightness can be confirmed by mixing violet pigments.

(3) When the hue is a hue closer to the α-type copper phthalocyanine blue pigment than the ε-type copper phthalocyanine blue pigment (example: y = 0.088, x = 0.131)
Since the hue of ε-type copper phthalocyanine blue pigment does not match, it is necessary to blend it with other colorants, but none can be blended in the desired hue and has high brightness. In addition, it is most advantageous to increase the brightness by mixing an organic dye with the α-type copper phthalocyanine blue pigment rather than drawing out the desired hue with the α-type copper phthalocyanine blue pigment itself.
If the hue is too red (eg, y = 0.088, x = 0.145 or more), the mixing ratio of the dye exceeds 60% when mixed with the ε-type copper phthalocyanine blue pigment, and the α-type copper phthalocyanine blue In the case of pigments, it exceeds 70%. In this case, since the mixing ratio is reduced, the effect of improving the brightness is reduced. The α-type copper phthalocyanine blue pigment (A) has a lower transmittance than the ε-type copper phthalocyanine blue pigment, and it is excellent by itself. It does not exhibit spectral properties and is essential for mixing with organic dyes. In addition, when a violet pigment is mixed, the transmittance of a spectral spectrum around 450 nm is often inferior to that of an organic dye, and when the mixing ratio of the violet pigment is increased, the brightness is not superior. It is important to select and mix organic dyes with good spectral characteristics.

  The pigment used in the coloring composition for a color filter of the present invention can be refined by salt milling or acid pasting. The primary particle diameter of the pigment is preferably 10 nm or more, more preferably 20 nm or more, because dispersion in the colorant carrier is good. Moreover, since it can form a filter segment with high contrast ratio, it is preferable that it is 100 nm or less. A preferred range is 15 to 85 nm, and a particularly preferred range is 25 to 85 nm. The primary particle diameter of the pigment was measured by directly measuring the size of the primary particle from an electron micrograph of the pigment using a TEM (transmission electron microscope). Specifically, the minor axis diameter and major axis diameter of the primary particles of each pigment were measured, and the average was taken as the particle diameter of the pigment particles. Next, with respect to 100 or more pigment particles, the volume of each particle is obtained by approximating it with a cube of the obtained particle size, and the volume average particle size is defined as the average primary particle size.

  Salt milling means a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent, or a mixture of a pigment, a compound represented by the general formula (X), a water-soluble inorganic salt, and a water-soluble organic solvent. This is a process of removing water-soluble inorganic salts and water-soluble organic solvents by washing with water after mechanically kneading while heating using a kneader such as a two-roll mill, three-roll mill, ball mill, attritor or sand mill. . The water-soluble inorganic salt serves as a crushing aid, and the pigment is crushed using the high hardness of the inorganic salt during salt milling. By optimizing the conditions for the salt milling of the pigment, it is possible to obtain a pigment having a sharp particle size distribution with a very fine primary particle diameter and a wide distribution.

  As the water-soluble inorganic salt, sodium chloride, barium chloride, potassium chloride, sodium sulfate and the like can be used, but sodium chloride (salt) is preferably used from the viewpoint of cost. The water-soluble inorganic salt is preferably used in an amount of 50 to 2000% by weight, and most preferably 300 to 1000% by weight based on the total weight of the pigment (100% by weight) from the viewpoint of both processing efficiency and production efficiency.

  The water-soluble organic solvent functions to wet the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (mixes) in water and does not substantially dissolve the inorganic salt to be used. However, a high boiling point solvent having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety because the temperature rises during salt milling and the solvent is easily evaporated. For example, 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, Liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polyprolene glycol and the like are used. The water-soluble organic solvent is preferably used in an amount of 5 to 1000% by weight, and most preferably 50 to 500% by weight, based on the total weight of the pigment (100% by weight).

  When the salt is milled, a resin may be added as necessary. The type of resin used is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like can be used. The resin used is solid at room temperature, preferably insoluble in water, and more preferably partially soluble in the organic solvent. The amount of resin used is preferably in the range of 5 to 200% by weight based on the total weight of the pigment (100% by weight).

The acid pasting method is a method for producing a treated pigment by co-dissolving an organic pigment in a strongly acidic solvent and taking out the solution in water. As the strongly acidic solvent, sulfuric acid, polyphosphoric acid, chlorosulfonic acid and the like can be used. Industrially, it is desirable to use sulfuric acid from the viewpoint of cost.
When preparing a strongly acidic solvent solution containing the compound represented by copper phthalocyanine (A) and the general formula (X), each powder may be added and dissolved in the strongly acidic solvent. Each strong acidic solvent solution may be mixed after dissolving in the acidic solvent. The order of addition when each powder is added to the strongly acidic solvent is not limited.

  The amount of the strongly acidic solvent needs to be increased or decreased depending on the concentration of the strongly acidic solvent, but is not particularly limited as long as they can be completely dissolved. For example, when 98% by weight of sulfuric acid is used, it is preferably used 3 to 100 times by weight, more preferably 5 to 30% by weight based on the total weight of the compound represented by copper phthalocyanine (A) and general formula (X). Is double. When the amount of sulfuric acid is less than this range, it may be difficult to completely dissolve the copper phthalocyanine (A) and the compound represented by the general formula (X) at a low temperature. Moreover, even if it uses more than this range, there is no merit to quality, and since productivity falls, it is uneconomical.

  Although the temperature at the time of melt | dissolving the compound shown by copper phthalocyanine (A) and general formula (X) in a strong acidic solvent is not specifically limited, For example, when using 98 weight% sulfuric acid, it is 3 to 60 degreeC. It is preferable that it is 3 ° C. or higher and 40 ° C. or lower. When the temperature is less than 3 ° C., it is not preferable because sulfuric acid is solidified and it becomes difficult to stir uniformly. Moreover, when melt | dissolving at temperature higher than said temperature, the compound shown by copper phthalocyanine (A) or general formula (X) may decompose | disassemble.

  In the present invention, the temperature at which the strongly acidic solvent solution of the compound represented by copper phthalocyanine (A) and the general formula (X) is mixed with water and precipitated is not particularly limited. However, although it varies depending on the type of the compound represented by the general formula (X) to be used, in many cases, the particles tend to be finer at a low temperature than when deposited at a high temperature. The following is preferable. Any water that can be used industrially, such as tap water, well water, and warm water, can be used as the water used at that time, but in order to reduce the temperature rise during precipitation, pre-cooled water is used. Is preferably used.

  The method for mixing the strongly acidic solvent solution and water is not particularly limited, and any method may be used as long as the compound represented by copper phthalocyanine (A) and general formula (X) can be completely precipitated. For example, it can be precipitated by a method of injecting a strongly acidic solvent solution into ice water prepared in advance or a method of continuously injecting it into running water using an apparatus such as an aspirator.

  The slurry obtained by the above method is filtered and washed to remove the acidic component, and then dried and pulverized to obtain the pigment composition of the present invention.

<Other colorants>
In addition, other organic pigments can be added to the colored composition for a color filter of the present invention as long as the effect is not hindered. In the case of an organic pigment, it is preferable to use a dioxazine pigment, an anthraquinone pigment, an azo pigment, or a quinacridone pigment in combination. Among them, it is preferable to use a dioxazine pigment in combination. Examples of the dioxazine pigment include C.I. I. Pigment Violet 23 is preferably used. By using a dioxazine pigment in combination with the color filter coloring composition of the present invention, a stable high quality, that is, excellent viscosity stability and high brightness color filter coloring composition can be obtained. Further, as described above, the organic pigment that can be used in combination with these is also preferably refined and used by a method such as salt milling.

<Compound represented by formula (X)>
The compound represented by the general formula (X) can be used for both the acid pasting method and the salt milling treatment. Presumed to function as a crystal transition inhibitor or a crystal growth inhibitor, and by containing the compound represented by the general formula (X), as a result, the refinement of particles is promoted and the particle size distribution is sharpened. The effect works, and the brightness can be improved and the viscosity stability can be improved.

P-Ln Formula (X)
(However, P: organic pigment residue, anthraquinone residue, acridone residue or triazine residue,
L: a basic substituent, an acidic substituent, or an optionally substituted phthalimidomethyl group,
n: an integer of 1 to 4)
Examples of the organic pigment constituting the organic pigment residue of P include, for example, diketopyrrolopyrrole pigments;
Azo pigments such as azo, disazo and polyazo; phthalocyanine pigments such as copper phthalocyanine, halogenated copper phthalocyanine and metal-free phthalocyanine;
Anthraquinone pigments such as aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavantron, anthanthrone, indanthrone, pyranthrone, violanthrone;
Examples include quinacridone pigments; dioxazine pigments; perinone pigments; perylene pigments; thioindigo pigments; isoindoline pigments; isoindolinone pigments; quinophthalone pigments;
Of these, metal-free or metal phthalocyanine pigments are preferred.

Specific examples of the substituent of L include phthalimidomethyl group, 4-nitrophthalimidomethyl group, 4-chlorophthalimidomethyl group, tetrachlorophthalimidomethyl group and the like, which may have a substituent,
Carbamoyl, sulfamoyl, aminomethyl, dimethylaminomethyl, diethylaminomethyl, dibutylaminomethyl, piperidinomethyl, dimethylaminopropylaminosulfonyl, diethylaminopropylaminosulfonyl, dibutylaminopropylaminosulfonyl, morpholinoethylamino Sulfonyl group, dimethylaminopropylaminocarbonyl group, 4- (diethylaminopropylaminocarbonyl) phenylaminocarbonyl group, dimethylaminomethylcarbonylaminomethyl group, diethylaminopropylaminomethylcarbonylaminomethyl group, dibutylaminopropylaminomethylcarbonylaminomethyl group, etc. Basic substituents of sulfonic acid group, sodium sulfonate group, calcium sulfonate group, Mini um sulfonato group, dodecyl ammonio sulfonato group, octadecyl ammonio sulfonato group, trimethyl octadecyl ammonio sulfonato group, dimethyl didecyl ammonio sulfonato group, acid substituents such as carboxylic acid groups,
2-aluminum carboxylato-5-nitrobenzamidomethyl group, and the like.

  When used in the acid pasting method, the compound represented by the general formula (X) is preferably neutral L, particularly one having a phthalimide group. The neutral compound represented by the general formula (X) is preferable in terms of refining with copper phthalocyanine (X) and sharpening the distribution to improve the viscosity stability. Moreover, as a compound shown by general formula (X) in the case of using for a salt milling process, the compound shown by neutral or basic general formula (X) is preferable. Of neutral L, a phthalimide group is preferable, and among basic L, a dimethylaminopropylaminosulfonyl group and a diethylaminopropylaminosulfonyl group are preferable.

In this invention, it is preferable that content of the compound shown by general formula (X) is the range of 0.5 weight%-100 weight part with respect to 100 weight part of copper phthalocyanine (A). The compound represented by the general formula (X) used in the present invention increases the content of the compound represented by the general formula (X) when a colored composition is produced by the acid pasting method together with copper phthalocyanine (A). As a result, the primary particle size of the resulting colored composition becomes fine, and the contrast of a color filter using it can be improved. However, when the addition amount of the compound represented by the general formula (X) exceeds 100 parts by weight in the coloring composition, a remarkable refining effect with an increase in the addition amount cannot be obtained, and further copper phthalocyanine (A) This is not preferable because the coloring power is reduced due to a decrease in the content of.

<Dispersant (B)>
Examples of the dispersant (B) that can be used in the present invention include a dye derivative, a compound represented by the general formula (1), a dispersant having an aromatic carboxyl group (B3), a resin pigment dispersant, and a surfactant. And commercially available resin-type pigment dispersants.

(Dye derivative)
Examples of the pigment derivative that is the dispersant (B) of the present invention include the following compounds.

  Examples of the basic derivative include compounds in which a basic substituent is introduced into an organic pigment, anthraquinone, acridone, or triazine. In the present invention, a pigment derivative is particularly preferable, and the structure thereof is a compound represented by the aforementioned general formula (X).

Examples of the dye derivative include, for example, JP-A-63-305173 and JP-B-57-156.
No. 20, JP-B 59-40172, JP-B 63-17102, JP-B 5
-9469 etc. can be used, These can be used individually or in mixture of 2 or more types. The blending amount of the pigment derivative is preferably 0.5% by weight or more, more preferably 1% by weight or more, most preferably 3% by weight or more based on the total amount of the colorant (100% by weight) from the viewpoint of improving dispersibility. It is. From the viewpoint of heat resistance and light resistance, the total amount of the colorant is preferably 40% by weight or less, most preferably 35%, based on the total amount (100% by weight).
% By weight or less.

  These pigment derivatives can be used alone or in admixture of two or more. As the dye derivative, the same compound as the compound represented by the general formula (X) can be used. However, the pigment derivative as a dispersing agent here is an auxiliary agent for uniformly dispersing a pigment that has already been processed such as miniaturization. Therefore, it is possible to make the dispersant and the crystal growth inhibitor the same, but it is important to select and use optimum materials for the crystal growth inhibitor and the dispersant. In some cases, the dye derivative having a neutral substituent, which has been effective as a crystal growth inhibitor, is less effective when used as a dispersant.

  Examples of the dispersant used in the pigment dispersion of the present invention include the following compounds. For example, a polyester-based, acrylic-based, urethane-based linear or comb-shaped resin or a surfactant can be used.

(Resin type pigment dispersant)
As the resin-type pigment dispersant, those having a basic group, an acidic group, an aromatic group or the like in the main chain or terminal of the linear resin or in the main chain or side chain of the comb-shaped resin in a block or randomly are preferable. Specifically, polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid (partial) amine salt, polycarboxylic acid ammonium salt, polycarboxylic acid alkylamine salt, polysiloxane, long A chain polyaminoamide phosphate, a hydroxyl group-containing polycarboxylic acid ester, a modified product thereof, an amide formed by reaction of poly (lower alkyleneimine) with a polyester having a free carboxyl group, a salt thereof, or the like is used. In addition, water-soluble resins such as (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, and polyvinylpyrrolidone, and water-soluble Polymer compounds, polyesters, modified polyacrylates, ethylene oxide / propylene oxide adducts, phosphate esters, and the like are used. These can be used alone or in admixture of two or more.

  Examples of commercially available resin-type pigment dispersants include various Solsperse dispersants such as Solsperse 13240, 20000, 24000, 26000, 28000, 31000, and 76500 (manufactured by Nippon Lubrizol Co., Ltd.), Dispersic 110, 111, 160, 161, 162, 163, 164, 167, 170, 182, 2000, 2001, 2020, 2025, 2050, 2070, 2096, 2150, etc. (disclosed by Big Chemie), Addisper PB711, PB411, PB111, PB814 , PB821, PB822, etc. Ajisper dispersant (manufactured by Ajinomoto Finetechno Co., Ltd.), Fuka dispersants such as Fuka 46, 47, 4300, 4330, 4340 (manufactured by Fuka Additives Co., Ltd.) Etc., and the like.

(Compound represented by the general formula (1))
As the dispersant used in the pigment dispersion in the present invention, a dispersant represented by the following general formula (1) and / or a dispersant (B3) having an aromatic carboxyl group is preferable in that stability is further improved.

General formula (1)

In the formula, R ₁ is a polyester residue having a number average molecular weight of 500 to 10,000. A more preferred number average molecular weight is 500 to 3,000.
y represents 1-2.

  The phosphate ester represented by the general formula (1) can be obtained by converting a polyester residue having a hydroxyl group at one end to a phosphate ester. A polyester residue having a hydroxyl group at one end can be obtained by ring-opening addition of ε-caprolactone or the like using monoalcohol as an initiator.

(Dispersant (B3) having an aromatic carboxyl group)
The dispersant (B3) having an aromatic carboxyl group of the present invention preferably has a number average molecular weight of 500 to 30,000. If it is less than 500 or more than 30,000, the viscosity and viscosity stability of the pigment dispersion may deteriorate, which is not preferable.

  The dispersant (B3) having an aromatic carboxyl group of the present invention preferably has an acid value of 10 to 200 mgKOH / g.

  The dispersant (B3) having an aromatic carboxyl group of the present invention has an aromatic carboxyl group in the molecule. The production method includes, for example, a method of reacting the aromatic tricarboxylic acid anhydride (b1) and / or the aromatic tetracarboxylic dianhydride (b2) with the polymer (c) having a hydroxyl group, A method for producing a polymer using a monomer having a monomer, a method for reacting an aromatic tricarboxylic acid anhydride (b1) and / or an aromatic tetracarboxylic acid dianhydride (b2) while polymerizing a monomer having a hydroxyl group Any of these may be mentioned. Among these, from the viewpoint of pigment dispersibility, the aromatic tricarboxylic acid anhydride (b1) and / or the polymer (c) having a hydroxyl group that makes it easier to control the number of aromatic carboxyl groups in the dispersant (A). What was made by the method with which aromatic tetracarboxylic dianhydride (b2) is made to react is preferable.

<Polymer (c)>
As the polymer (c) having a hydroxyl group used as a precursor of the dispersant having an aromatic carboxyl group of the present invention, a polymer (c1) having a hydroxyl group at one end and a polymer having a hydroxyl group at a side chain ( C2). Furthermore, the polymer (c3) having two hydroxyl groups at one end is preferable as the polymer (c1) having a hydroxyl group at one end.

[Polymer (c1)]
First, the polymer (c1) having a hydroxyl group at one end will be described. The polymer (c1) having a hydroxyl group at one end used in the present invention includes a polyester and / or polyether polymer (c1-1) having a hydroxyl group at one end and a vinyl polymer having a hydroxyl group at one end. (C1-2).

[Polyester and / or polyether polymer (c1-1)]
As the polyester and / or polyether polymer (c1-1) having a hydroxyl group at one end, those represented by the following general formula (2) are preferable.

General formula (2):

[In general formula (2),
Z ₁ is a monovalent terminal group having 1 to 20 carbon atoms, 0 to 12 oxygen atoms, and 0 to 3 nitrogen atoms,
Z ₂ is —O—, —S—, or —N (Rb) — (wherein Rb is a hydrogen atom or a linear or branched alkyl group having 1 to 18 carbon atoms),
Z ₃ is —OH;
G ₁ is a repeating unit represented by —R ₆ O—,
G ₂ is a repeating unit represented by —C (═O) R ₇ O—,
G ₃ is a repeating unit represented by —C (═O) R ₈ C (═O) —OR ₉ O—,
R ₆ is a linear or branched alkylene group having 2 to 8 carbon atoms, or a cycloalkylene group having 3 to 8 carbon atoms,
R ₇ is a linear or branched alkylene group having 1 to 8 carbon atoms, or a cycloalkylene group having 4 to 8 carbon atoms,
R ₈ is a linear or branched alkylene group having 2 to 6 carbon atoms, a linear or branched alkenylene group having 2 to 6 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, or An arylene group having 6 to 20 carbon atoms,
R ₉ is —CH (R ₁₀ ) —CH (R ₁₁ ) —,
One of R ₁₀ and R ₁₁ is a hydrogen atom, and the other is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkyl group The alkyloxymethylene group having 1 to 20 carbon atoms in the moiety, the alkenyloxymethylene group having 2 to 20 carbon atoms in the alkenyl moiety, the aryl moiety having 6 to 20 carbon atoms in the aryl moiety, and optionally substituted with a halogen atom An aryloxymethylene group which may be present, an N-methylene-phthalimide group,
R ₅ is R ₆ , —C (═O) R ₇ —, or —C (═O) R ₈ C (═O) —OR ₉ —,
m ₁ is an integer from 0 to 100;
m ₂ is an integer of 0-60,
m ₃ is an integer of 0 to 30,
However, m ₁ + m ₂ + m ₃ is 1 or more and 100 or less,
The arrangement of the repeating units G _{1 to} G _{3 in} the general formula (2) does not limit the order thereof, and in the polymer represented by the general formula (2), between the group Z ₂ and the group R _5. Indicates that the repeating units G _{1 to} G ₃ are included in an arbitrary order, and these repeating units G _{1 to} G ₃ may be either random type or block type, respectively. ]

In the general formula (2), Z ₁ is preferably a linear or branched alkyl group having 1 to 18 carbon atoms from the viewpoint of lowering the viscosity of the pigment dispersion and storage stability.

As another embodiment, the Z ₁ in the general formula (2) preferably has an ethylenically unsaturated double bond. In this case, active energy ray curability can be imparted to the dispersant having an aromatic carboxyl group.

Further, in the general formula (2), m ₂ is preferably an integer of ₃ to 15 from the viewpoints of lowering the viscosity and storage stability of the pigment dispersion.

In the general formula (2), when m ₂ = 0 and m ₃ = 0, Z ₁ is a linear or branched alkyl group having 1 to 7 carbon atoms, or an ethylenic group. It preferably has a saturated double bond.

  The polyester and / or polyether polymer (c1-1) having a hydroxyl group at one end represented by the general formula (2) can be produced by a known method, and includes monoalcohol, primary monoamine, secondary It can be easily obtained by ring-opening polymerization of a cyclic compound selected from the group of alkylene oxide, lactone, lactide, dicarboxylic anhydride, and epoxide using a compound selected from the group of monoamine and monothiol as an initiator.

(Surfactant)
Surfactants include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate. , Lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Anionic surfactants such as: polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene Nonionic surfactants such as nylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate; chaotic properties such as alkyl quaternary ammonium salts and their ethylene oxide adducts Surfactants: Examples include amphoteric surfactants such as alkylbetaines such as alkyldimethylaminoacetic acid betaine and alkylimidazolines, and these can be used alone or in admixture of two or more.

<Organic dye (E)>
Examples of the organic dye (E) that can be used include triarylmethanes, xanthenes, and anthraquinones, among which xanthenes are preferably used.

[Xanthene]
Examples of xanthene dyes include C.I. I. Acid Red 51, C.I. I. Acid Red 52, C.I. I. Acid Red 87, C.I. I. Acid Red 92, C.I. I. Acid Red 289, C.I. I. Acid Red 388, Rose Bengal B, Acid Rhodamine G, C.I. I. Acid Violet 9, C.I. I. Acid Violet 9, C.I. I. It is preferable to use Acid Violet 30. Among them, C.I. I. Acid Red 52, C.I. I. Acid Red 87, C.I. I. Acid Red 92, C.I. I. Acid Red 289, C.I. I. It is preferable to use Acid Red 388.

[Triphenylmethane series]
Examples of triphenylmethane dyes include C.I. I. Acid Violet 15, C.I. I. Acid Violet 17, C.I. I. Acid Violet 19, C.I. I. Acid Violet 21, C.I. I. Acid Violet 24, C.I. I. Acid Violet 25, C.I. I. Acid Violet 38, C.I. I. Acid Violet 49, C.I. I. Acid Blue 1, C.I. I. Acid Blue 3, C.I. I. Acid Blue 5, C.I. I. Acid Blue 7, C.I. I. Acid Blue 9, C.I. I. Acid Blue 11, C.I. I. Acid Blue 13, C.I. I. Acid Blue 15, C.I. I. Acid Blue 17, C.I. I. Acid Blue 22, C.I. I. Acid Blue 24, C.I. I. Acid Blue 26, C.I. I. Acid Blue 75, C.I. I. Acid Blue 83, C.I. I. Acid Blue 90, C.I. I. Acid Blue 93, C.I. I. Acid Blue 100, C.I. I. Basic Blue 81, C.I. I. It is preferable to use Basic Blue 83.

[Triarylmethane series (excluding triphenylmethane series)]
Examples of the triarylmethane dye include C.I. I. Basic Violet 1, C.I. I. Basic Violet 2, C.I. I. Basic Violet 3, C.I. I. Basic Violet 4, C.I. I. Basic Violet 14, C.I. I. Basic Blue 1, C.I. I. Basic Blue 5, C.I. I. Basic Blue 7, C.I. I. Basic Blue 11, C.I. I. It is preferable to use Basic Blue 26.

[Anthraquinone]
Examples of anthraquinone dyes include C.I. I. Acid Violet 29, C.I. I. Acid Violet 31, C.I. I. Acid Violet 33, C.I. I. Acid Violet 34, C.I. I. Acid Violet 36, C.I. I. Acid Violet 39, C.I. I. Acid Violet 43, C.I. I. Acid Violet 48, C.I. I. Acid Violet 63, C.I. I. Acid Violet 109, C.I. I. Acid Blue 25, C.I. I. Acid Blue 27, C.I. I. Acid Blue 41, C.I. I. Acid Blue 45, C.I. I. Acid Blue 62, C.I. I. Acid Blue 80, C.I. I. Acid Blue 127, C.I. I. Acid Blue 129, C.I. I. Acid Blue 145, C.I. I. Acid Blue 225, C.I. I. Acid Blue 230, C.I. I. Acid Blue 260, C.I. I. Acid Blue 264, C.I. I. Acid Blue 277, C.I. I. Acid Blue 281, C.I. I. Acid Blue 324, C.I. I. It is preferable to use Acid Blue 350.

  Among the organic dyes (E) listed above, acidic dyes can have high heat resistance, light resistance and solvent resistance by chlorination and sulfonamidation as quaternary ammonium salts.

(Salt-forming compounds consisting of acid dyes and quaternary ammonium salt compounds)
When the organic dye (E) used in the present invention is an acid dye, it is preferably used as a salt-forming compound (a) comprising an acid dye and a quaternary ammonium salt compound.

[Quaternary ammonium salt compound]
The quaternary ammonium salt compound as the counter component of the acid dye will be described. A quaternary ammonium salt compound becomes an acid dye counter by having an amino group.

  A preferred form of the quaternary ammonium salt compound which is a counter component of the salt-forming compound (a) is colorless or white. Here, colorless or white means a so-called transparent state, and is defined as a state where the transmittance is 95% or more, preferably 98% or more in the entire wavelength region of 400 to 700 nm in the visible light region. Is. That is, it is necessary not to inhibit color development of the dye component and to cause no color change.

It is preferable that the molecular weight of the counter part which is a cation component of a quaternary ammonium salt compound is in the range of 190-900. Here, the cation moiety corresponds to the (NR ₁ R ₂ R ₃ R ₄ ) ⁺ moiety in the following general formula (3). When the molecular weight is smaller than 190, light resistance and heat resistance are lowered, and further, solubility in a solvent is lowered. On the other hand, when the molecular weight is larger than 900, the ratio of the color developing component in the molecule is lowered, the color developability is lowered, and the lightness is also lowered. More preferably, the molecular weight of the counter portion is in the range of 240-850. Particularly preferred is a counter portion with a molecular weight in the range of 350-800. Here, the molecular weight was calculated based on the structural formula. The atomic weight of C was 12, the atomic weight of H was 1, and the atomic weight of N was 14.

Moreover, what is represented by following General formula (3) is used as a quaternary ammonium salt compound.
General formula (3)

(In General Formula (3), R _{1 to} R ₄ each independently represents an alkyl group having 1 to 20 carbon atoms or a benzyl group, and at least two of R ₁ , R ₂ , R ₃ , and R ₄ are present. The number of C is 5 to 20. Y ⁻ represents an inorganic or organic anion.)

R ₁ to R ₄ in by the a 5 to 20 the number of at least two and C, solubility in solvents is improved. When the number of alkyl groups having a C number of less than 5 is 3 or more, solubility in a solvent is deteriorated, and coating film foreign matter is likely to be generated. Moreover, when the alkyl group which the number of C exceeds 20 exists, the color development property of a salt-forming compound (A) will be impaired.

  Specifically, tetramethylammonium chloride (molecular weight of the cation moiety is 74), tetraethylammonium chloride (molecular weight of the cation moiety is 122), monostearyltrimethylammonium chloride (molecular weight of the cation moiety is 312), distearyldimethylammonium chloride ( Cation portion molecular weight 550), tristearyl monomethylammonium chloride (cation portion molecular weight 788), cetyltrimethylammonium chloride (cation portion molecular weight 284), trioctylmethylammonium chloride (cation portion molecular weight 368), dioctyl Dimethylammonium chloride (cation part molecular weight 270), monolauryltrimethylammonium chloride (cation part molecule) 228), dilauryldimethylammonium chloride (cation part molecular weight 382), trilaurylmethylammonium chloride (cation part molecular weight 536), triamylbenzylammonium chloride (cation part molecular weight 318), trihexylbenzylammonium Chloride (cation part molecular weight 360), trioctylbenzylammonium chloride (cation part molecular weight 444), trilaurylbenzylammonium chloride (cation part molecular weight 612), benzyldimethylstearyl ammonium chloride (cation part molecular weight 388) ), And benzyldimethyloctylammonium chloride (the molecular weight of the cation moiety is 248), dialkyl (alkyl is C14 to C18) Dimethyl ammonium chloride (hydrogenated tallow) (molecular weight of the cationic moiety is from 438 to 550) is preferably used and the like.

The component of Y ⁻ constituting the anion may be an inorganic or organic anion, but is preferably a halogen, usually chlorine.

  Specific examples of the quaternary ammonium salt compound products include Cotamin 24P, Cotamin 86P Conch, Cotamin 60W, Cotamin 86W, Cotamin D86P, Sanizole C, Sanizole B-50, etc. manufactured by Lion Corp. 2C-75, 2HT-75, 2HT flakes, 2O-75I, 2HP-75, 2HP flakes and the like. ) Dimethylammonium chloride) is preferred.

(Salt-forming compound comprising an acid dye and a resin having a cationic group in the side chain)
When the organic dye (E) used in the present invention is an acid dye, it is also preferably used as a salt-forming compound (a ′) comprising an acid dye and a resin having a cationic group in the side chain.
The resin having a cationic group in the side chain for obtaining the salt-forming compound (a ′) used in the present invention will be described.
The resin having a cationic group in the side chain for obtaining the salt-forming compound (a ′) is not particularly limited as long as it has at least one onium base in the side chain, but has a suitable onium salt structure. Is preferably an ammonium salt, an iodonium salt, a sulfonium salt, a diazonium salt, and a phosphonium salt from the viewpoint of availability and the like. In consideration of storage stability (thermal stability), an ammonium salt, an iodonium salt, and More preferred is a sulfonium salt. More preferred is an ammonium salt.

  When preparing a blue coloring composition for a color filter containing a salt-forming compound (a ′) and exhibiting the characteristics as a color filter, the same kind of resin as the binder resin constituting the blue coloring composition for the color filter is used. It is desirable to do. In the present invention, an acrylic resin is preferably used as a binder resin in the color filter coloring composition. Therefore, the resin having a cationic group in the side chain for obtaining the salt-forming compound (A) is an acrylic resin. It is desirable to be.

  Moreover, as resin which has a cationic group in the side chain of this invention, the vinyl-type resin containing the structural unit represented by following General formula (4) is used.

General formula (4)

[In General Formula (4), R ₁ represents a hydrogen atom or a substituted or unsubstituted alkyl group. R _{2 to} R ₄ each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group, and R _{2 to} R ₄ Two of them may be bonded to each other to form a ring. Q represents an alkylene group, an arylene group, —CONH—R ₅ —, —COO—R ₅ —, and R ₅ represents an alkylene group. Y ^- is representative of an inorganic or organic anion. ]

In General Formula (4), R ₁ represents a hydrogen atom or a substituted or unsubstituted alkyl group. Examples of the alkyl group for R ₁ include a methyl group, an ethyl group, a propyl group, an n-butyl group, an i-butyl group, a t-butyl group, an n-hexyl group, and a cyclohexyl group. As this alkyl group, a C1-C12 alkyl group is preferable, a C1-C8 alkyl group is more preferable, and a C1-C4 alkyl group is especially preferable.

When the alkyl group represented by R ₁ has a substituent, examples of the substituent include a hydroxyl group and an alkoxyl group.

Among the above, R ₁ is most preferably a hydrogen atom or a methyl group.

In general formula (4), R _{2 to} R ₄ are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group. Can be mentioned.

Here, as the alkyl group in R _{2 to} R ₄ , for example, a linear alkyl group (methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-octyl, n-decyl, n-dodecyl, n -Tetradecyl, n-hexadecyl, n-octadecyl, etc.), branched alkyl groups (isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl, 2-ethylhexyl and 1,1,3,3) -Tetramethylbutyl etc.), cycloalkyl groups (cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl etc.) and bridged cyclic alkyl groups (norbornyl, adamantyl and pinanyl etc.). As this alkyl group, a C1-C18 alkyl group is preferable, More preferably, it is a C1-C8 alkyl group.

Examples of the alkenyl group in R _{2 to} R ₄ include linear or branched alkenyl groups (vinyl, allyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1 -Propenyl, 1-methyl-2-propenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl and the like) and cycloalkenyl groups (such as 2-cyclohexenyl and 3-cyclohexenyl). As this alkenyl group, a C2-C18 alkenyl group is preferable, More preferably, it is a C2-C8 alkenyl group.

Examples of the aryl group in R _{2 to} R ₄ include monocyclic aryl groups (such as phenyl), condensed polycyclic aryl groups (such as naphthyl, anthracenyl, phenanthrenyl, anthraquinolyl, fluorenyl, and naphthoquinolyl) and aromatic heterocyclic hydrocarbons. Groups (thienyl (group derived from thiophene)), furyl (group derived from furan), pyranyl (group derived from pyran), pyridyl (group derived from pyridine), 9-oxoxanthenyl (from xanthone) Derived groups) and 9-oxothioxanthenyl (groups derived from thioxanthone) and the like.

When the alkyl group, alkenyl group, or aryl group represented by R _{2 to} R ₄ has a substituent, examples of the substituent include a halogen atom, a hydroxyl group, an alkoxyl group, an aryloxy group, an alkenyl group, an acyl group, Examples include a substituent selected from an alkoxycarbonyl group, a carboxyl group, a phenyl group, and the like. Among these substituents, a halogen atom, a hydroxyl group, an alkoxyl group, and a phenyl group are particularly preferable.

R _{2 to} R ₄ are preferably an alkyl group which may be substituted from the viewpoint of stability, and more preferably an unsubstituted alkyl group.

_Two of R _{2 to} R ₄ may be bonded to each other to form a ring.

In general formula (4), the component of Q connecting the vinyl moiety and the ammonium base represents an alkylene group, an arylene group, —CONH—R ₅ —, —COO—R ₅ —, and R ₅ represents an alkylene group. Among these, —CONH—R ₅ — and —COO—R ₅ — are preferable because of polymerizability and availability. R ₅ is more preferably a methylene group, an ethylene group, a propylene group, or a butylene group, and particularly preferably an ethylene group.

The component Y ⁻ in the general formula (4) constituting the counter anion of the resin may be an inorganic or organic anion. As the counter anion, known ones can be used without limitation. Specifically, hydroxide ions; halogen ions such as chloride ions, bromide ions, and iodide ions; carboxylate ions such as formate ions and acetate ions; Carbonate ions, bicarbonate ions, nitrate ions, sulfate ions, sulfite ions, chromate ions, dichromate ions, phosphate ions, cyanide ions, permanganate ions, and even hexacyanoferrate (III) ions And complex ions. From the viewpoint of synthesis suitability and stability, halogen ions and carboxylate ions are preferable, and halogen ions are most preferable. When the counter anion is an organic acid ion such as a carboxylate ion, the organic acid ion may be covalently bonded in the resin to form an inner salt.

  In order to obtain a vinyl resin containing a structural unit represented by the general formula (4) which is a preferred embodiment of the present invention, only a method of copolymerizing an ethylenically unsaturated monomer having an ammonium base as a monomer component is used. Alternatively, after obtaining a vinyl resin having an amino group obtained by copolymerizing an ethylenically unsaturated monomer having an amino group as a monomer component, it may be obtained by a method in which an onium chlorinating agent is reacted and ammonium salified. good.

  Below, the specific example of the ethylenically unsaturated monomer which can be used in order to obtain the vinyl-type resin containing the structural unit represented by General formula (4) which is a preferable aspect of this invention is shown. In addition, in this specification, when showing either or both of "acryl, methacryl", it may describe as "(meth) acryl". Similarly, when one or both of “acryloyl and methacryloyl” are indicated, it may be described as “(meth) acryloyl”.

  Examples of the ethylenically unsaturated monomer having a quaternary ammonium base include (meth) acryloyloxyethyltrimethylammonium chloride, (meth) acryloyloxyethyltriethylammonium chloride, (meth) acryloyloxyethyldimethylbenzylammonium chloride, (meta ) Alkyl (meth) acrylate quaternary ammonium salts such as acryloyloxyethylmethylmorpholino ammonium chloride, (meth) acryloylaminopropyltrimethylammonium chloride, (meth) acryloylaminoethyltriethylammonium chloride, (meth) acryloylaminoethyldimethylbenzyl Alkyl (meth) acryloylamide quaternary ammonium salts such as ammonium chloride, dimethyl Luzia Lil ammonium methyl sulfate, trimethyl vinyl phenyl ammonium chloride.

  Examples of the ethylenically unsaturated monomer having an amino group include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dipropylaminoethyl (meth) acrylate, diisopropylaminoethyl (meth) acrylate, and dibutylamino. Ethyl (meth) acrylate, diisobutylaminoethyl (meth) acrylate, di-t-butylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylamide, diethylaminopropyl (meth) acrylamide, dipropylaminopropyl (meth) acrylamide, diisopropyl Aminopropyl (meth) acrylamide, dibutylaminopropyl (meth) acrylamide, diisobutylaminopropyl (meth) acrylamide, di-t-butyl Examples include (meth) acrylic acid esters having a dialkylamino group such as minopropyl (meth) acrylamide or (meth) acrylamide, and styrenes having a dialkylamino group such as dimethylaminostyrene and dimethylaminomethylstyrene, diallylmethylamine, diallylamine And amino group-containing aromatic vinyl monomers such as N-vinylpyrrolidine, N-vinylpyrrolidone and N-vinylcarbazole.

  Examples of the onium chloride agent include alkyl sulfates such as dimethyl sulfate, diethyl sulfate, or dipropyl sulfate, sulfonate esters such as methyl p-toluenesulfonate, or methyl benzenesulfonate, methyl chloride, ethyl chloride, propyl chloride, or Examples thereof include alkyl chlorides such as octyl chloride, alkyl bromides such as methyl bromide, ethyl bromide, propyl bromide, and octyl chlorobromide, benzyl chloride, and benzyl bromide.

  The reaction between the ethylenically unsaturated monomer having an amino group and the onium chlorinating agent is usually performed by dropping an equimolar amount or less of the onium chlorinating agent into the amino group-containing ethylenically unsaturated monomer solution. Can be done. The temperature during the ammonium chlorination reaction is about 90 ° C. or less, and particularly when the vinyl monomer is ammonium chlorinated, it is preferably about 30 ° C. or less, and the reaction time is about 1 to 4 hours.

  Alternatively, an alkoxycarbonylalkyl halide can also be used as the onium chlorinating agent. The alkoxycarbonylalkyl halide is represented by the following general formula (5).

General formula (5)
Z-R ₁ -COOR ₂

(In the general formula (5), Z is chlorine or halogen such as bromine, preferably bromine,
R ₁ is an alkylene group having 1 to 6 carbon atoms, preferably 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms,
R ₂ is a lower alkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms. )

Reaction of the ethylenically unsaturated monomer and alkoxycarbonylalkyl halide with an amino group, after equimolar following alkoxycarbonylalkyl halide was reacted in the same manner as in the above onium chloride agent to an amino group, a -COOR ₂ It is obtained by hydrolysis and conversion to carboxylate ions (—COO ⁻ ). Thereby, an ethylenically unsaturated monomer having a carboxybetaine structure represented by the general formula (5) and having an ammonium base can be obtained.

  In addition, examples of the ethylenically unsaturated monomer that can be used other than the structural unit represented by the general formula (4) include (meth) acrylic acid esters, crotonic acid esters, vinyl esters, and maleic acid. Diesters, fumaric acid diesters, itaconic acid diesters, (meth) acrylamides, vinyl ethers, vinyl alcohol esters, styrenes, (meth) acrylonitrile and the like are preferable.

Specific examples of such vinyl monomers include the following compounds.
Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate. , Isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, (meth) acrylic acid 2- Ethylhexyl, t-octyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-Methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate 2- (2-methoxyethoxy) ethyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, (meth) acrylic acid Diethylene glycol monoethyl ether, (meth) acrylic acid triethylene glycol monomethyl ether, (meth) acrylic acid triethylene glycol monoethyl ether, (meth) acrylic acid polyethylene glycol monomethyl ether, (meth) acrylic acid polyethylene glycol monoethyl ether, ( Β-phenoxyethoxyethyl (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclo (meth) acrylate Pentenyloxyethyl, trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tribromophenyl (meth) acrylate And (meth) acrylic acid tribromophenyloxyethyl.

  Examples of crotonic acid esters include butyl crotonate and hexyl crotonate.

Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate, and the like.
Examples of maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.

  Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.

  Examples of itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

  Examples of (meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, Nn -Butyl acryl (meth) amide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N , N-diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholine, diacetone acrylamide and the like.

Examples of vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and methoxyethyl vinyl ether.
Examples of styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chlorostyrene, dichlorostyrene, bromostyrene, chloromethyl Examples thereof include styrene, hydroxystyrene protected with a group that can be deprotected by an acidic substance (for example, t-Boc and the like), methyl vinylbenzoate, and α-methylstyrene.

  In addition, the ethylenically unsaturated monomer that can be used other than the structural unit represented by the general formula (4) may further include a copolymer unit derived from a monomer having an acid group.

  As monomers having an acid group, unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid; maleic acid, maleic anhydride, fumaric acid, itaconic acid, anhydrous Unsaturated dicarboxylic acids such as itaconic acid, citraconic acid, citraconic anhydride and mesaconic acid or their anhydrides; trivalent or higher unsaturated polycarboxylic acids or their anhydrides; succinic acid mono (2-acryloyloxyethyl) ), Succinic acid mono (2-methacryloyloxyethyl), phthalic acid mono (2-acryloyloxyethyl), phthalic acid mono (2-methacryloyloxyethyl) monovalent polyvalent carboxylic acid mono [ (Meth) acryloyloxyalkyl] esters; ω-carboxy-polycaprolactone monoacrylate, ω-carboxy-polycaprolacto Include mono (meth) acrylates such as both terminal carboxy polymers such monomethacrylate.

  Examples of a method for obtaining a vinyl resin containing the structural unit represented by the general formula (4) suitable for the present invention include anionic polymerization, living anionic polymerization, cationic polymerization, living cationic polymerization, free radical polymerization, and living radical polymerization. Any known method can be used. Of these, free radical polymerization or living radical polymerization is preferred.

  In the case of the free radical polymerization method, it is preferable to use a polymerization initiator. As the polymerization initiator, for example, an azo compound and an organic peroxide can be used. Examples of the azo compounds include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane 1-carbonitrile), 2 , 2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2′-azobis (2-methylpropionate) 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis (2-hydroxymethylpropionitrile), or 2,2′-azobis [2- (2-imidazolin-2-yl ) Propane] and the like. Examples of organic peroxides include benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di (2-ethoxyethyl) peroxy Examples thereof include dicarbonate, t-butyl peroxyneodecanoate, t-butyl peroxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, and diacetyl peroxide. These polymerization initiators can be used alone or in combination of two or more. The reaction temperature is preferably 40 to 150 ° C., more preferably 50 to 110 ° C., and the reaction time is preferably 3 to 30 hours, more preferably 5 to 20 hours.

  In the living radical polymerization method, side reactions that occur in general radical polymerization are suppressed, and further, since the growth of polymerization occurs uniformly, it is possible to easily synthesize block polymers and resins with uniform molecular weight.

  Among them, the atom transfer radical polymerization method using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst is applicable to a wide range of monomers, and has a polymerization temperature applicable to existing equipment. It is preferable in that it can be adopted. The atom transfer 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. Am. Chem. Soc. 1995, 117, 5614
(Reference 4) Macromolecules 1995, 28, 7901, Science, 1996, 272, 866
(Reference 5) Pamphlet of International Publication No. 96/030421 (Reference 6) Pamphlet of International Publication No. 97/018247 (Reference 7) JP-A-9-208616 (Reference 8) JP-A-8-411117

  It is preferable to use an organic solvent for the polymerization. The organic solvent is not particularly limited, but for example, ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether Acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, or the like is used. Two or more kinds of these polymerization solvents may be mixed and used.

The amount of the cationic group present in the resin having a cationic group in the side chain used in the present invention is not particularly limited, but the cation salt value of the resin is preferably 10 to 200 mgKOH / g, More preferably, it is 20-130 mgKOH / g. The cation salt value is expressed as an onium salt value, a quaternary ammonium salt value, or an amine salt value.
In addition, among them, the amount of ammonium base and amine base present in the vinyl resin containing the structural unit represented by the general formula (1) suitable for the present invention is such that the ammonium salt value of the resin and the amine salt value are 10 to 200 mgKOH. / G is preferable, and 20 to 130 mgKOH / g is more preferable.
If it is less than 10 mgKOH / g, the concentration of the pigment derived from the xanthene-based acidic dye is low, the resin component increases, and it does not function as a colorant component. Moreover, when it becomes larger than 200 mgKOH / g, a dye component will increase and solvent solubility will fall.

  The molecular weight of the vinyl resin containing the structural unit represented by the general formula (4) used in the present invention is not particularly limited, but the converted weight average molecular weight measured by gel permeation chromatography (GPC). Is preferably 1,000 to 500,000, and more preferably 3,000 to 15,000.

  Moreover, it is preferable that the vinyl-type resin containing the structural unit represented by General formula (4) suitable for this invention has a characteristic melt | dissolved in the solvent widely used for the coloring composition for color filters. Thereby, the coating film without a foreign material generation | occurrence | production can be obtained. In particular, it is more preferable to dissolve in propylene glycol monomethyl ether acetate.

  In the resin having a cationic group in the side chain, the total content of the structural unit represented by the general formula (4) is not particularly limited, but the entire structure contained in the resin having a cationic group in the side chain. When the unit is 100% by weight, the total content of the structural unit represented by the general formula (4) is 5% by weight or more from the viewpoint of solvent solubility and coloring power of the salt-forming compound. Preferably, it is 10 to 50% by weight.

(Salt-forming compounds consisting of basic dyes and anionic compounds)
Among the organic dyes (E) listed above, the basic dye is an anionic compound, and specifically includes, for example, organic sulfonic acids such as heteropolyacids and aromatic sulfonic acids; aromatic carboxylic acids and fatty acids. An organic acid such as an organic carboxylic acid such as: salted with perchloric acid or hexafluorophosphoric acid to form a salt-forming compound can have high heat resistance, light resistance, and solvent resistance.
(Heteropoly acid)
Examples of the heteropolyacid include phosphotungstic acid H3 (PW12O40) .nH2O (n≈30; ≒ represents nearly equal) (molecular weight 3421), silicotungstic acid H4 (SiW12O40) .nH2O (n≈30) (molecular weight 3418) ), Phosphomolybdic acid H3 (PMo12O40) .nH2O (n.apprxeq.30) (molecular weight 2205), silicomolybdic acid H3 (SiMo12O40) .nH2O (n.apprxeq.30) (molecular weight 2202), phosphotungstomolybdic acid H3 (PW12-XMoXO40) NH2O (n≈30) (6 <X <12) and phosphovanadomolybdic acid H15-X (PV12-XMoXO40) nH2O (n≈30).
Lintangst molybdic acid, phosphovanadomolybdic acid, and silicotungsto molybdic acid have a molecular weight in the range of 2202 to 3421 by changing the content of components such as phosphotungstic acid, phosphomolybdic acid, silicotungstic acid, and silicomolybdic acid. Can be adjusted.
When heteropolyacid is used as the counter compound, the average molecular weight is preferably in the range of 2820-3421. This is because when the counter compound contains molybdenum and tungsten, the proportion of tungsten is preferably more than 50%. In the case of phosphotungstomolybdic acid, a colorant having excellent transparency can be obtained by reducing the Mo content and containing a large amount of W.

(Organic acid)
As the organic sulfonic acid, for example, aromatic sulfonic acid can be used. Preferred compounds as the aromatic sulfonic acid include, for example, 1-naphthylamine-4,8-disulfonic acid (molecular weight 303), 1-naphthylamine-3,8-disulfonic acid (molecular weight 303), 1-naphthylamine-5,7-disulfone. Acid (molecular weight 303), 1-naphthylamine-3,6-disulfonic acid (molecular weight 303), 1-naphthylamine-3,6,8-trisulfonic acid (kofoic acid) (molecular weight 383), 2-naphthylamine-6,8 -Disulfonic acid (molecular weight 303), 2-naphthylamine-1,6-disulfonic acid (molecular weight 303), 2-naphthylamine-4,8-disulfonic acid (molecular weight 303), 2-naphthylamine-3,6-disulfonic acid (amino) -R acid) (molecular weight 303), 2-naphthylamine-5,7-disulfonic acid (amino J acid) (molecular weight) 03), 1-naphthol-4,8-disulfonic acid (molecular weight 304), 1-naphthol-3,8-disulfonic acid (ε acid) (molecular weight 304), 1-naphthol-3,6-disulfonic acid (molecular weight 304) ), 1-naphthol-3,6,8-trisulfonic acid (molecular weight 384), 2-naphthol-6,8-disulfonic acid (molecular weight 304), 2-naphthol-3,6-disulfonic acid (R acid) ( Molecular weight 304), 2-naphthol-3,6,8-trisulfonic acid (molecular weight 384), N-phenyl-1-naphthylamine-8-sulfonic acid (molecular weight 299), Np-tolyl-1-naphthylamine-8 -Sulfonic acid (molecular weight 313), N-phenyl-1-naphthylamine-5-sulfonic acid (molecular weight 299), N-phenyl-2-naphthylamine-6-sulfonic acid (min 299), N-acetyl-7-amino-1-naphthol-3-sulfonic acid (molecular weight 281), N-phenyl-7-amino-1-naphthol-3-sulfonic acid (molecular weight 315), N-acetyl -6-amino-1-naphthol-3-sulfonic acid (molecular weight 281), N-phenyl-6-amino-1-naphthol-3-sulfonic acid (molecular weight 315), 1,8-dihydro-3,6-disulfone Acid (chromotropic acid) (molecular weight 320), 8-amino-1-naphthol-3,6-disulfonic acid (molecular weight 319), 8-amino-1-naphthol-5,7-disulfonic acid (molecular weight 319), 1 , 6-Diamino-2-naphthol-4-sulfonic acid (molecular weight 254), 1-amino-2-naphthol-6,8-disulfonic acid (molecular weight 319), 1-amino-2 Naphthol-3,6-disulfonic acid (molecular weight 319), 2,8-diamino-1-naphthol-5,7-disulfonic acid (molecular weight 334), 2,7-diamino-1-naphthol-3-sulfonic acid (molecular weight) 254), 2,6-diamino-1-naphthol-3-sulfonic acid (molecular weight 254), 2,8-diamino-1-naphthol-3,6-disulfonic acid (molecular weight 334), and 2-amino-7- And phenylamino-1-naphthol-3-sulfonic acid (molecular weight 330).

  It is also preferable to use anthracene sulfonic acid (molecular weight 258), anthraquinone-2-sulfonic acid, or anthraquinone-1-sulfonic acid (molecular weight 288).

  When naphthylamine sulfonic acid having one amino group and one sulfonic acid group is used, excellent heat resistance and light resistance can be achieved. Examples of naphthylamine sulfonic acid include 2-amino-1-naphthalene sulfonic acid (tobias acid, molecular weight 223), 4-amino-1-naphthalene sulfonic acid (naphthoic acid, molecular weight 223), and 8-amino-1-naphthalene sulfone. Acid (peric acid, molecular weight 223), 2-amino-6-naphthalenesulfonic acid (brennic acid, molecular weight 223), 1-amino-5-naphthalenesulfonic acid (Lorentzic acid, molecular weight 223), 5-amino-2-naphthalene Sulfonic acid (molecular weight 223), 1-amino-6-naphthalenesulfonic acid (molecular weight 223), 6-amino-1-naphthalenesulfonic acid (molecular weight 223), and 3-amino-1-naphthalenesulfonic acid (molecular weight 223) Can be mentioned. Among these, 2-amino-1-naphthalenesulfonic acid (tobias acid, molecular weight 223) is particularly preferable in terms of color characteristics and resistance.

  It is also preferable to use hydroxynaphthalenesulfonic acid having one hydroxyl group and one sulfonic acid group. Examples of the hydroxy naphthalene sulfonic acid include 2-hydroxy-6-naphthalene sulfonic acid (shephatic acid, molecular weight 224), 1-hydroxy-4-naphthalene sulfonic acid (nevir-winter acid: NW acid, molecular weight 224), 1- Examples include hydroxy-5-naphthalenesulfonic acid (L acid, molecular weight 224), and 2-hydroxy-8-naphthalenesulfonic acid (croseinic acid, molecular weight 224).

  Among them, an organic sulfonic acid having 2 to 3 sulfonic acid groups is preferable in terms of good color developability and high brightness. When there are 4 or more sulfonic acids, environmental stability deteriorates and changes with time are likely to occur. With one sulfonic acid, the basic dye and the counter compound react in a 1: 1 ratio, and color is generated when the main color is used. May be worse.

  However, in the case of an organic sulfonic acid having a molecular weight in the range of 200 to 250, the molecular weight of the counter compound is small, so even if there is one sulfonic acid group per molecule, the color developability is not impaired. .

  As the organic carboxylic acid, for example, an aromatic carboxylic acid or a fatty acid can be used. Specific examples of the organic carboxylic acid include tetrachlorophthalic acid (molecular weight 304), palmitic acid (molecular weight 257), stearic acid (molecular weight 285), arachidic acid (molecular weight 313), behenic acid (molecular weight 341), and lignoceric acid. (Molecular weight 369), oleic acid (molecular weight 282), elaidic acid (molecular weight 282), erucic acid (molecular weight 339), nervonic acid (molecular weight 367), linoleic acid (molecular weight 280), gamolenic acid (molecular weight 278), arachidonic acid Molecular weight 305), α-linolenic acid (molecular weight 278), stearidonic acid (molecular weight 276), eicosapentaenoic acid (molecular weight 302), and docosahexaenoic acid (molecular weight 328).

  The use ratio of copper phthalocyanine (A) and these salt-forming compounds is preferably 1 to 1000 parts by weight of the salt-forming compound with respect to 100 parts by weight of copper phthalocyanine (A). More preferably, it is 3 to 300 parts by weight. If the addition amount of the salt-forming compound is less than 1 part by weight, the reproducible chromaticity region becomes narrow, and if it exceeds 1000 parts by weight, the hue changes, which is not preferable.

<Transparent resin (C)>
Transparent resin (C) is a colorant (copper phthalocyanine pigment (A), organic dye (E), other pigments / dyes added as necessary), especially those that disperse salt-forming compounds, or salt-forming compounds. It is dyed and permeated and includes thermoplastic resins and thermosetting resins.

  The transparent resin (C) is preferably a resin having a spectral transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. Moreover, when using with the form of an alkali image development type colored resist material, it is preferable to use the alkali-soluble vinyl resin which copolymerized the acidic group containing ethylenically unsaturated monomer. In order to further improve the photosensitivity, an active energy ray-curable resin having an ethylenically unsaturated double bond can also be used.

  In order to disperse the colorant preferably, the weight average molecular weight (Mw) of the transparent resin is preferably in the range of 10,000 to 100,000, more preferably in the range of 10,000 to 80,000. The number average molecular weight (Mn) is preferably in the range of 5,000 to 50,000, and the value of Mw / Mn is preferably 10 or less.

  When the transparent resin (C) is used as a photosensitive coloring composition for a color filter, from the viewpoint of dispersibility, permeability, developability, and heat resistance of the pigment and salt-forming compound, the colorant adsorbing group and during development The balance of the carboxyl group, which functions as an alkali-soluble group, and the aliphatic group and aromatic group, which functions as an affinity group for the colorant carrier and solvent, makes the dispersibility, penetrability, developability, and durability of pigments and salt-forming compounds. It is important to use a resin having an acid value of 20 to 300 mgKOH / g. When the acid value is less than 20 mgKOH / g, the solubility in the developing solution is poor and it is difficult to form a fine pattern. When it exceeds 300 mgKOH / g, no fine pattern remains.

  Since the transparent resin has good film formability and various resistances, it is preferably used in an amount of 30% by weight or more based on the total weight of the colorant (100% by weight), and the colorant concentration is high and good. Since color characteristics can be expressed, it is preferably used in an amount of 500% by weight or less.

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

  Examples of the vinyl-based alkali-soluble resin copolymerized with an acidic group-containing ethylenically unsaturated monomer include resins having an acidic group such as a carboxyl group or a sulfone group. Specific examples of the alkali-soluble resin include an acrylic resin having an acidic group, an α-olefin / (anhydrous) maleic acid copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, or Examples include isobutylene / (anhydrous) maleic acid copolymer. Among these, at least one resin selected from an acrylic resin having an acidic group and a styrene / styrene sulfonic acid copolymer, particularly an acrylic resin having an acidic group, is preferably used because of its high heat resistance and transparency.

<Organic solvent (D)>
In the coloring composition for a color filter of the present invention, a coloring agent is sufficiently dispersed and permeated in a coloring agent carrier, and is applied on a substrate such as a glass substrate so that a dry film thickness is 0.2 to 5 μm. An organic solvent (D) can be included to facilitate the formation of the filter segment.

  Examples of the organic solvent (D) include ethyl lactate, benzyl alcohol, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4 -Dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m- Xylene, m-diethylbenzene, m-dichlorobenzene, N, N-dimethylacetamide, N, N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl Acetate, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol Diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether , Ethylene glycol monohexyl ether, ethylene glycol mono Cyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone , Dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether , Dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol Monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methylcyclohexanol, n-amyl acetate, n-butyl acetate, isoacetate Le, isobutyl acetate, propyl acetate, and a dibasic acid ester and the like.

  Among them, alkyls such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate, which have good dispersion and dissolution of the pigment and salt-forming compound (a) of the present invention. Use alcohol ether esters, propylene glycol monomethyl ether, propylene glycol monoethyl ether, alkyl alcohol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, aromatic alcohols such as benzyl alcohol, and ketones such as cyclohexanone. Is preferred. A solvent can be used individually by 1 type or in mixture of 2 or more types. Moreover, since the solvent can adjust the coloring composition to an appropriate viscosity and can form a filter segment having a desired uniform film thickness, 500 to 6000% by weight based on the total weight of the colorant (100% by weight). It is preferable to use it in the quantity.

<Dispersion>
The coloring composition of the present invention comprises a dispersing agent containing a coloring agent containing copper phthalocyanine (A) and an organic dye (E) in a coloring agent carrier comprising the transparent resin (C) and an organic solvent (D). It can be produced by finely dispersing together with (B) using various dispersing means such as a three roll mill, a two roll mill, a sand mill, a kneader, or an attritor. The blue coloring composition of the present invention can also be produced by mixing several types of colorants separately dispersed in a colorant carrier.
At this time, as described above, it is preferable that the copper phthalocyanine (A) is previously subjected to salt milling and / or acid pasting in the presence of the compound represented by the general formula (X).

<Photopolymerizable monomer>
The coloring composition for a color filter of the present invention can contain a photopolymerizable monomer.
Photopolymerizable monomers that can be used in the present invention include monomers or oligomers that are cured by ultraviolet rays or heat to produce transparent resins, and these may be used alone or in combination of two or more. Can do. The blending amount of the monomer is preferably 5 to 400% by weight based on the total weight of the colorant (total of copper phthalocyanine (A) and organic dye (E)) (100% by weight). From the viewpoint of developability, it is more preferably 10 to 300% by weight.

  Examples of monomers and oligomers that are cured by ultraviolet rays or heat to produce a resin include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, Cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) ) Acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglycidyl -Terdi (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodeca Nyl (meth) acrylate, ester acrylate, methylolated melamine (meth) acrylate ester, epoxy (meth) acrylate, urethane acrylate and other acrylic esters and methacrylate esters, (meth) acrylic acid, styrene, vinyl acetate, Hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (Meth) acrylamide, N-vinylformamide, acrylonitrile and the like can be mentioned, but are not necessarily limited thereto.

<Photopolymerization initiator>
In the coloring composition for a color filter of the present invention, when the composition is cured by ultraviolet irradiation and a filter segment is formed by a photolithographic method, a photopolymerization initiator or the like is added to add a solvent developing type or an alkali developing type coloring. It can be adjusted in the form of a resist material. The blending amount when using the photopolymerization initiator is preferably 5 to 200% by weight based on the total amount of the colorant (total of copper phthalocyanine (A) and organic dye (E)). From the viewpoint of developability, it is more preferably 10 to 150% by weight.

  Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- Hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1 Acetophenone compounds such as-[4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; benzoin, benzoin Methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or ben Benzoin compounds such as rudimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, or 3,3 ′, 4 Benzophenone compounds such as 4,4′-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-diethylthioxanthone, etc. 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphene) ) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloro) Methyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2 -(4-Methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4-trichloromethyl- Triazine compounds such as (4′-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], O- (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine and other oxime ester compounds; bis (2,4,6-trimethylbenzoyl) Phosphine compounds such as phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, borate compounds, carbazole compounds, An imidazole compound or a titanocene compound is used.

  These photopolymerization initiators can be used alone or in combination of two or more at any ratio as required. These photopolymerization initiators are 5 to 200% by weight based on the total amount (100% by weight) of the colorants (total of copper phthalocyanine (A) and organic dye (E)) in the color filter coloring composition. It is preferable that it is 10 to 150% by weight from the viewpoint of photocurability and developability.

<Sensitizer>
Furthermore, the coloring composition for a color filter of the present invention can contain a sensitizer.

  Sensitizers include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives , Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives, and other polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, Azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, Trapirazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine Derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes, or Michler's ketone derivatives, α-acyloxy esters, acylphosphine oxides, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl Anthraquinone, 4,4'-diethylisophthalophenone, 3,3 ', or 4,4'-tetra (t-butylperoxycarbonyl) benzophen Enone, 4,4'-diethylaminobenzophenone, and the like.

  More specifically, edited by Shin Okawara et al., “Dye Handbook” (1986, Kodansha), edited by Shin Okawara et al., “Chemistry of Functional Dye” (1981, CMC), edited by Tadasaburo Ikemori et al. Examples include, but are not limited to, sensitizers described in "Special Functional Materials" (1986, CMC). In addition, a sensitizer that absorbs light from the ultraviolet region to the near infrared region can also be contained.

Two or more kinds of sensitizers may be used in any ratio as required. The blending amount when using the sensitizer is preferably 3 to 60% by weight based on the total weight of the photopolymerization initiator contained in the colored composition (100% by weight). From the viewpoint of developability, it is more preferably 5 to 50% by weight.

<Oxygen-reducing amine compound>
Moreover, the coloring composition for a color filter of the present invention can contain an oxygen-reducing amine compound having a function of reducing dissolved oxygen.

  Such oxygen-reducing amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-benzoic acid 2- Examples include dimethylaminoethyl, 2-ethylhexyl 4-dimethylaminobenzoate, and N, N-dimethylparatoluidine.

<Leveling agent>
In order to improve the leveling property of the composition on the transparent substrate, it is preferable to add a leveling agent to the coloring composition for a color filter of the present invention. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in the main chain is preferable. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning, BYK-333 manufactured by Big Chemie. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK Chemie. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can be used in combination. In general, the leveling agent is preferably used in an amount of 0.003 to 0.5% by weight based on the total weight of the blue coloring composition (100% by weight).

  As a particularly preferred leveling agent, it is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, has a hydrophilic group but has low solubility in water, and when added to a blue coloring composition, It has the feature that its surface tension lowering ability is low, and it is useful to have good wettability to the glass plate despite its low surface tension lowering ability, and the added amount that does not cause coating film defects due to foaming In this case, those that can sufficiently suppress the chargeability can be preferably used. As a leveling agent having such preferable characteristics, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. Examples of the polyalkylene oxide unit include a polyethylene oxide unit and a polypropylene oxide unit, and dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

  In addition, the bonding form of the polyalkylene oxide unit with dimethylpolysiloxane includes a pendant type in which the polyalkylene oxide unit is bonded in the repeating unit of dimethylpolysiloxane, a terminal-modified type in which the end of dimethylpolysiloxane is bonded, and dimethylpolysiloxane. Any of linear block copolymer types in which they are alternately and repeatedly bonded may be used. Dimethylpolysiloxane having a polyalkylene oxide unit is commercially available from Toray Dow Corning Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ. -2207, but is not limited thereto.

  An anionic, cationic, nonionic or amphoteric surfactant can be supplementarily added to the leveling agent. Two or more kinds of surfactants may be mixed and used.

  Anionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, alkyl diphenyl ether disulfonic acid Sodium, lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Examples include esters.

  Examples of the chaotic surfactant that is supplementarily added to the leveling agent include alkyl quaternary ammonium salts and their ethylene oxide adducts. Nonionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate And amphoteric surfactants such as alkyl dimethylamino acetic acid betaine and alkylimidazolines, and fluorine-based and silicone-based surfactants.

<Curing agent, curing accelerator>
Moreover, in order to assist hardening of a thermosetting resin, the coloring composition for color filters of this invention may contain the hardening | curing agent, the hardening accelerator, etc. as needed. As the curing agent, phenol resins, amine curing agents, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like are effective, but are not particularly limited to these, and are thermosetting. Any curing agent may be used as long as it can react with the resin. Among these, a compound having two or more phenolic hydroxyl groups in one molecule and an amine curing agent are preferable. Examples of the curing accelerator include amine compounds (for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl). -N, N-dimethylbenzylamine etc.), quaternary ammonium salt compounds (eg triethylbenzylammonium chloride etc.), blocked isocyanate compounds (eg dimethylamine etc.), imidazole derivative bicyclic amidine compounds and salts thereof (eg Imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2- D Ru-4-methylimidazole, etc.), phosphorus compounds (eg, triphenylphosphine, etc.), guanamine compounds (eg, melamine, guanamine, acetoguanamine, benzoguanamine, etc.), S-triazine derivatives (eg, 2,4-diamino-6) -Methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6 Methacryloyloxyethyl-S-triazine / isocyanuric acid adduct, etc.) can be used. These may be used alone or in combination of two or more. As content of the said hardening accelerator, 0.01 to 15 weight% is preferable with respect to the thermosetting resin whole quantity.

<Other additive components>
The coloring composition for a color filter of the present invention can contain a storage stabilizer in order to stabilize the viscosity with time of the composition. Moreover, in order to improve adhesiveness with a transparent substrate, adhesion improving agents, such as a silane coupling agent, can also be contained.

  Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and methyl ethers thereof, t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Organic phosphines, phosphites and the like can be mentioned. The storage stabilizer can be used in an amount of 0.1 to 10% by weight based on the colorant (A) in the coloring composition (100% by weight).

  Examples of the adhesion improver include vinyl silanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane and vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (amino Ethyl) γ-aminopropyltrie Xisilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl Examples include silane coupling agents such as aminosilanes such as -γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. The adhesion improver can be used in an amount of 0.01 to 10% by weight, preferably 0.05 to 5% by weight, based on the total amount of the colorant in the coloring composition (100% by weight).

<Removal of coarse particles>
The colored composition for a color filter of the present invention is a coarse particle having a size of 5 μm or more, preferably a coarse particle having a size of 1 μm or more, more preferably a coarse particle having a size of 0.5 μm or more. It is preferable to remove the mixed dust. Thus, it is preferable that the coloring composition for color filters substantially does not contain particles of 0.5 μm or more. More preferably, all the particles are substantially 0.3 μm or less. Here, the measurement was performed using a particle size distribution measuring apparatus “Nano-S (Sysmex Corporation)” using a dynamic light scattering method.

<Color filter>
The red filter segment can be formed using a normal red coloring composition containing a red pigment and a pigment carrier. Examples of the red coloring composition include C.I. I. Pigment Red 7, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 57: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 122, 146, 166, 168, 169, 176, 177, 178, 179, 184, 185, 187, 200, 202, 207, 208, 210, 221, 242, 246, 254, 255, 264, 270, 272, 273, 274 Red pigments such as 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, or 287 are used. Further, a basic dye or a salt-forming compound of an acid dye exhibiting a red color can also be used.

  The red coloring composition includes C.I. I. Pigment Orange 38, 43, 71, or 73, and / or C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181 182,185,187,188,193,194,198,199,213,214,218,219,220, or may be used in combination of a yellow pigment 221, and the like. In addition, a salt forming compound of a basic dye or an acid dye that exhibits orange and / or yellow can be used.

  The green filter segment can be formed using a normal green coloring composition including a green pigment and a pigment carrier. Examples of the green pigment include C.I. I. Pigment Green 7, 10, 36, 37, 58, etc. are used. A yellow pigment can be used in combination with the green coloring composition. Examples of yellow pigments that can be used in combination include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, Mention may be made of yellow pigments such as 182, 185, 187, 188, 193, 194, 198, 199, 213, 214, 218, 219, 220 or 221. Further, a basic dye exhibiting yellow and a salt-forming compound of an acid dye can be used in combination.

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

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

  When forming a filter segment by photolithography, the photosensitive coloring composition containing the blue coloring composition of the present invention prepared as the solvent development type or alkali development type coloring resist is spray-coated or spin-coated on a transparent substrate. By a coating method such as coating, slit coating, roll coating or the like, the coating is applied so that the dry film thickness is 0.2 to 5 μm. If necessary, the dried film is exposed to ultraviolet rays through a mask having a predetermined pattern provided in contact with or not in contact with the film. Then, after immersing in a solvent or alkali developer or spraying the developer by spraying or the like to remove the uncured portion to form a desired pattern, the same operation is repeated for other colors to produce a color filter. be able to. Furthermore, in order to accelerate the polymerization of the colored resist material, heating can be performed as necessary. According to the photolithography method, a color filter with higher accuracy than the above printing method can be manufactured.

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

  The color filter of the present invention can be produced by an electrodeposition method, a transfer method, or the like in addition to the above method, but the blue coloring composition for a color filter of the present invention can be used in any method. The electrodeposition method is a method for producing a color filter by using a transparent conductive film formed on a substrate and forming each color filter segment on the transparent conductive film by electrophoresis of colloidal particles. . The transfer method is a method in which a filter segment is formed in advance on the surface of a peelable transfer base sheet, and this filter segment is transferred to a desired substrate.

  A black matrix can be formed in advance before forming each color filter segment on a transparent substrate or a reflective substrate. As the black matrix, a chromium, chromium / chromium oxide multilayer film, an inorganic film such as titanium nitride, or a resin film in which a light-shielding agent is dispersed is used, but is not limited thereto. In addition, a thin film transistor (TFT) may be formed in advance on the transparent substrate or the reflective substrate, and then each color filter segment may be formed. In addition, an overcoat film, a transparent conductive film, or the like is formed on the color filter of the present invention as necessary.

  Hereinafter, the present invention will be described in detail with reference to examples and comparative examples according to conventional methods. However, the present invention is not limited to the scope of these examples. In the examples, “part” represents “part by weight” and “%” represents “% by weight”.

  The weight average molecular weight (Mw) of the acrylic resin is a polystyrene conversion measured by using TSKgel column (manufactured by Tosoh Corporation) and GPC equipped with RI detector (manufactured by Tosoh Corporation, HLC-8120GPC) using THF as a developing solvent. The weight average molecular weight (Mw).

  First, the acrylic resin solution, the dispersing agent, the finer pigment, the salt-forming compound (a), the pigment dispersion, and the salt-forming compound-containing resin solution used in Examples and Comparative Examples will be described.

<Example of acrylic resin solution production>
A separable four-necked flask was equipped with a thermometer, a condenser tube, a nitrogen gas inlet tube, and a stirrer, and 250 g of propylene glycol monomethyl ether acetate was charged, stirred while purging with nitrogen, and heated to 120 ° C. From a dropping tube, a mixed solution of 0.78 mol (137.4 g) of benzyl methacrylate, 0.22 mol (18.9 g) of methacrylic acid and 271 g of propylene glycol monomethyl ether acetate was dropped over 2 hours. Two hours after the completion of the dropwise addition, a solution prepared by dissolving 0.6 part of 2,2′-azobisisobutyronitrile in methoxypropyl acetate was added, and the reaction was further continued for 1 hour. A resin A having a nonvolatile content of 30% was obtained. The weight average molecular weight measured by GPC was 18000.

<Production example of resin having cationic group in side chain>
Into a four-necked separable flask equipped with a thermometer, a stirrer, a distillation tube and a condenser, 67.3 parts of methyl ethyl ketone was charged and heated to 75 ° C. under a nitrogen stream. Separately, 34.0 parts of methyl methacrylate, 28.0 parts of n-butyl methacrylate, 28.0 parts of 2-ethylhexyl methacrylate, 10.0 parts of dimethylaminoethyl methacrylate, 2,2′-azobis (2,4-dimethylvaleronitrile) ) And 25.1 parts of methyl ethyl ketone were made uniform, charged in a dropping funnel, attached to a four-necked separable flask, and dropped over 2 hours. Two hours after the completion of the dropwise addition, it was confirmed that the polymerization yield was 98% or more from the solid content, and the weight average molecular weight (Mw) was 6830, and then cooled to 50 ° C. To this, 3.2 parts of methyl chloride and 22.0 parts of ethanol were added, reacted at 50 ° C. for 2 hours, heated to 80 ° C. over 1 hour, and further reacted for 2 hours. Thus, Resin B having a cationic group in the side chain of 47% by weight of the resin component was obtained. The ammonium salt value of the obtained resin was 34 mgKOH / g.

<Example of production of dispersant>
In a reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, 100 parts of methyl methacrylate, 100 parts of n-butyl acrylate, and 40 parts of methoxypropyl acetate were charged and replaced with nitrogen gas. After heating the inside of the reaction vessel to 80 ° C. and adding 12 parts of 3-mercapto-1,2-propanediol, 0.2 part of 2,2′-azobisisobutyronitrile is divided into 20 portions. It was added every minute and reacted for 12 hours at 80 ° C., and it was confirmed by solid content measurement that 95% had reacted. Next, 30 parts of pyromellitic anhydride, 190 parts of methoxypropyl acetate and 0.40 part of 1,8-diazabicyclo- [5.4.0] -7-undecene as a catalyst were added and reacted at 120 ° C. for 7 hours. I let you. It was confirmed by titration that 98% or more of the acid anhydride was half-esterified, and the reaction was terminated. An aromatic carboxyl group having an acid value per solid content of 42 mgKOH / g and a number average molecular weight (Mn) of 4,100 was obtained. Dispersant A having a solid content of 50% was obtained.

<Production method of fine pigment>
The content of α-type phthalocyanine has a diffraction intensity A of 6.8 ° and a maximum diffraction intensity of 9.1 ° ± 0.2 ° when the Bragg angle 2θ is 5 ° and 12 °. B, where C is the minimum diffraction intensity of 8.6 ° ± 0.2 °, and is obtained from the index value calculated as (AC) / (AC−B). This index value is an index indicating the content of α-type copper phthalocyanine blue. When the index value is large, the content is high, and when it is small, the content is small.

[Pigment production example 1]
100 parts of β-type crude copper phthalocyanine is added to 600 parts of 98% sulfuric acid, and the mixture is completely dissolved by stirring at 40 ° C. for 2 hours, and then poured into 1000 parts of water with stirring. After stirring for 30 minutes, filtration, washing with water, drying and pulverization yielded 95 parts of crude α-type phthalocyanine. About the obtained alpha type copper phthalocyanine pigment, the X-ray-diffraction intensity in the range of 2 (theta) = 3.5-15 was measured with the X-ray-diffraction apparatus (RINTKU by RIGAKU), and the index value was computed. The index value was 0.978. The average major axis determined from the transmission electron micrograph was 126 nm, and it was a somewhat non-uniform α-type copper phthalocyanine pigment in which coarse particles of 200 nm or more were also present.

[Comparative Pigment Production Example 2]
65 parts of α-type copper phthalocyanine, 35 parts of ε-type copper phthalocyanine obtained in Pigment Production Example 1, 800 parts of sodium chloride, and 150 parts of diethylene glycol were preliminarily maintained for 5 minutes in a convert mixer (manufactured by Asada Tekko). Mixed. This mixture was supplied to a continuous kneader (“Miracle K.K.K.-42 type” manufactured by Asada Tekko Co., Ltd.) with a screw type quantitative feeder, and the mixture was kneaded to produce an ε-type copper phthalocyanine pigment. The conditions of the continuous kneader are: feed part screw diameter 120 mmφ, 8 kneading part sets composed of a fixed disk and a rotating disk, extrusion rate of kneaded composition 25 kg / hour, residence time 10 minutes, spindle rotation speed 50 rpm, kneading temperature Operated at 140 ° C. The kneaded composition obtained here was taken out into 3500 parts of 1% aqueous sulfuric acid solution at 70 ° C., stirred for 1 hour with heat, filtered, washed with water, and dried. For the obtained ε-type copper phthalocyanine pigment, the X-ray diffraction intensity was measured in the same manner as in Pigment Production Example 1, and the index value was calculated. The index value was 0.07. The average major axis determined from a transmission electron micrograph was 30 nm, and it was a homogeneous particle ε-type copper phthalocyanine pigment.

[Pigment Production Example 3]
92 parts of crude α-type copper phthalocyanine obtained in Pigment Production Example 1 and 8 parts of a crystal transition inhibitor of the following general formula (6), 700 parts of sodium chloride and 150 parts of diethylene glycol were charged into a 1500-volume part double-arm kneader, It knead | mixed at 70 degreeC for 10 hours. After kneading, the mixture was taken out in 3500 parts of a 1% aqueous sulfuric acid solution at 70 ° C., stirred for 1 hour, filtered, washed with water and dried to obtain a pigment. For the obtained α-type copper phthalocyanine, the X-ray diffraction intensity was measured in the same manner as in Production Example 1, and the index value was calculated. The index value was 1.19. The average major axis determined from a transmission electron micrograph was 30 nm, and it was an α-type copper phthalocyanine pigment with uniform particles. The results are shown in Table 1.

General formula (6)

[Pigment Production Example 4]
Kneading was carried out in the same manner as in Pigment Production Example 3 except that the kneading temperature was changed to 50 ° C. The obtained kneaded composition was post-treated in the same manner as in Pigment Production Example 3, the X-ray diffraction intensity of the obtained pigment was measured, and the purity index value was calculated. The index value was 1.25. The average major axis determined from the transmission electron micrograph was 21 nm, and it was an α-type copper phthalocyanine pigment with uniform particles.

[Pigment Production Example 5]
Except for changing to the crude α-type copper phthalocyanine 82.8 parts obtained in Pigment Production Example 1 and the crude ε-type copper phthalocyanine 9.2 parts obtained in Pigment Production Example 2, the same procedure as in Pigment Production Example 3 was performed. The resulting kneaded composition was kneaded with an arm-type kneader and post-treated in the same manner as in Pigment Production Example 3, and the X-ray diffraction intensity was measured in the same manner as in Pigment Production Example 3 to calculate an index value. The index value was 0.91. 10% of ε-type copper phthalocyanine was mixed with α-type copper phthalocyanine. Moreover, the average of the long diameter calculated | required from the transmission electron micrograph was 33 nm, and was uniform.

[Pigment Production Example 6]
A double arm kneader was used in the same manner as in Pigment Production Example 3 except that 46 parts of crude α-type copper phthalocyanine obtained in Pigment Production Example 1 and 46 parts of crude ε-type copper phthalocyanine obtained in Pigment Production Example 2 were used. After kneading, the obtained kneaded composition was post-treated in the same manner as in Pigment Production Example 3, the X-ray diffraction intensity was measured in the same manner as in Pigment Production Example 3, and the index value was calculated. The index value was 0.48. α-type copper phthalocyanine was mixed with 50% ε-type copper phthalocyanine. Moreover, the average of the long diameter calculated | required from the transmission electron micrograph was 35 nm, and was uniform.

[Pigment Production Example 7]
Kneading was performed in the same manner as in Pigment Production Example 3 except that the kneading method was changed to a continuous kneader. The obtained kneaded composition was post-treated in the same manner as in Pigment Production Example 3, the X-ray diffraction intensity of the obtained ε-type copper phthalocyanine was measured, and the purity index value was calculated. The index value was 1.02. The average major axis determined from the transmission electron micrograph was 27 nm, and it was an α-type copper phthalocyanine pigment with uniform particles.

[Pigment Production Example 8]
It knead | mixed similarly to the pigment manufacture example 3 except having changed the crystal transition inhibitor of the said General formula (6) into the crystal transition inhibitor of the following General formula (7). The obtained kneaded composition was post-treated in the same manner as in Pigment Production Example 3, the X-ray diffraction intensity of the obtained ε-type copper phthalocyanine was measured, and the purity index value was calculated. The index value was 1.20. The average major axis determined from a transmission electron micrograph was 36 nm, and it was an α-type copper phthalocyanine pigment with uniform particles.

General formula (7)

[Pigment Production Example 9]
To 600 parts of 98% sulfuric acid, 92 parts of β-type crude copper phthalocyanine and a crystal transition inhibitor of the following general formula (7) are added, stirred at 40 ° C. for 2 hours to completely dissolve, and then added to 1000 parts of water. Pour with stirring. After stirring for 30 minutes, filtration, washing with water, drying and pulverization yielded 95 parts of crude α-type phthalocyanine. The α-type copper phthalocyanine thus obtained was measured for X-ray diffraction intensity, and an index value for purity was calculated. The index value was 1.05. The average of the major axis obtained from the transmission electron micrograph was 25 nm, which was fine, but some particles of 30 nm to 50 nm were present, and it was α-type copper phthalocyanine pigment with slightly non-uniform particles.

[Pigment Production Example 10]
To 600 parts of 98% sulfuric acid, 80 parts of β-type crude copper phthalocyanine and 20 parts of a crystal growth inhibitor of the general formula (7) were added and stirred at 40 ° C. for 2 hours to completely dissolve, then 1000 parts of water Inject with stirring. After stirring for 30 minutes, filtration, washing with water, drying and pulverization yielded 95 parts of crude α-type phthalocyanine. The α-type copper phthalocyanine thus obtained was measured for X-ray diffraction intensity, and an index value for purity was calculated. The index value was 1.15. The average major axis determined from a transmission electron micrograph was 19 nm, and it was an α-type copper phthalocyanine pigment with uniform particles.

[Pigment Production Example 11]
To 600 parts of 98% sulfuric acid, 92 parts of β-type crude copper phthalocyanine and 8 parts of a crystal growth inhibitor of the general formula (6) were added and stirred at 40 ° C. for 2 hours to completely dissolve, then 1000 parts of water Inject with stirring. After stirring for 30 minutes, filtration, washing with water, drying and pulverization yielded 95 parts of crude α-type phthalocyanine. The α-type copper phthalocyanine thus obtained was measured for X-ray diffraction intensity, and an index value for purity was calculated. The index value was 1.19. The average major axis determined from a transmission electron micrograph was 28 nm, and it was a uniform particle α-type copper phthalocyanine pigment.

[Pigment Production Example 12]
To 600 parts of 98% sulfuric acid, 92 parts of β-type crude copper phthalocyanine and 8 parts of a crystal growth inhibitor of the following general formula (8) were added and stirred at 40 ° C. for 2 hours to completely dissolve, then 1000 parts of Pour into water with stirring. After stirring for 30 minutes, filtration, washing with water, drying and pulverization yielded 95 parts of crude α-type phthalocyanine. The α-type copper phthalocyanine thus obtained was measured for X-ray diffraction intensity, and an index value for purity was calculated. The index value was 1.10. The average major axis determined from a transmission electron micrograph was 28 nm, and it was a uniform particle α-type copper phthalocyanine pigment.

General formula (8)

[Pigment Production Example 13]
92 parts of α-type copper phthalocyanine pigment obtained in Pigment Production Example 9 and 8 parts of a crystal growth inhibitor of the following general formula (6), 700 parts of sodium chloride and 150 parts of diethylene glycol were charged into a 1500-volume part double-arm kneader, 70 The mixture was kneaded for 10 hours at a temperature. After kneading, the mixture was taken out in 3500 parts of a 1% aqueous sulfuric acid solution at 70 ° C., stirred for 1 hour, filtered, washed with water and dried to obtain a pigment. For the obtained α-type copper phthalocyanine, the X-ray diffraction intensity was measured in the same manner as in Pigment Production Example 1, and the index value was calculated. The index value was 1.14. The average major axis determined from the transmission electron micrograph was 15 nm, and it was an α-type copper phthalocyanine pigment with uniform particles.

[Pigment Production Example 14]
100 parts of α-type copper phthalocyanine pigment obtained in Pigment Production Example 9, 700 parts of sodium chloride and 150 parts of diethylene glycol were charged into a 1500-volume part double-arm kneader and kneaded at 70 ° C. for 10 hours. After kneading, the mixture was taken out in 3500 parts of a 1% aqueous sulfuric acid solution at 70 ° C., stirred for 1 hour, filtered, washed with water and dried to obtain a pigment. For the obtained α-type copper phthalocyanine, the X-ray diffraction intensity was measured in the same manner as in Pigment Production Example 1, and the index value was calculated. The index value was 1.11. The average major axis determined from a transmission electron micrograph was 14 nm, and it was an α-type copper phthalocyanine pigment with uniform particles.

[Comparative Pigment Example 15]
The crude α-type phthalocyanine of Pigment Production Example 1 was used as it was as Comparative Pigment Example 1, and the X-ray diffraction intensity was measured in the same manner as in Pigment Production Example 3 to calculate the index value. Moreover, the average of the long diameter calculated | required from the transmission electron micrograph was 126 nm, and it was a non-uniform (alpha) -type copper phthalocyanine pigment in which the coarse particle | grains of 200 nm or more existed considerably.

[Comparative Pigment Example 16]
The crude α-type phthalocyanine obtained in Pigment Production Example 1 was kneaded with a double-arm kneader in the same manner as Pigment Production Example 3 except that the crude ε-type phthalocyanine obtained in Pigment Production Example 2 was changed. The obtained kneaded composition was post-treated in the same manner as in Pigment Production Example 3, and for the obtained ε-type copper phthalocyanine, the X-ray diffraction intensity was measured in the same manner as in Pigment Production Example 3, and the index value was calculated. Moreover, the average of the long diameter calculated | required from the transmission electron micrograph was 31 nm, and was the epsilon-type copper phthalocyanine pigment of the homogeneous particle | grains.

<Method for producing salt-forming compound a>
(Salt-forming compound (a-1))
In the following procedure, C.I. I. A salt-forming compound (a-1) composed of Acid Red 52 and tristearyl monomethylammonium chloride which is a quaternary ammonium salt compound was produced. C. so as to obtain a 10% aqueous solution. I. Acid Red 52 is dissolved in water and heated to 30 to 50 ° C., then tristearyl monomethyl ammonium chloride is dissolved in a methanol / water = 20/80 solution so as to form a 5% solution, and the solution is added dropwise little by little. Tristearyl monomethylammonium chloride may be used as a solid. After dropwise addition of tristearyl monomethylammonium chloride, the mixture is stirred for 3 hours at 30 to 50 ° C. and sufficiently reacted. After cooling to room temperature with stirring, suction filtration is performed, and after washing with water, the salt-forming compound remaining on the filter paper is dried by removing moisture with a dryer. I. A salt-forming compound of acid red 52 and tristearyl monomethylammonium chloride, a salt-forming compound (a-1) was obtained.

(Salt-forming compound (a-2))
Synthesize | combined similarly to a-1 except having changed the quaternary ammonium salt compound with distearyl dimethyl ammonium chloride, C.I. I. A salt-forming compound (a-2) of acid red 52 and distearyldimethylammonium chloride was obtained.

(Salt-forming compound (a-3))
In the following procedure, C.I. I. A salt-forming compound (a-3) consisting of Acid Red 52 and Resin B having a cationic group in the side chain was produced.
The resin 1 having a cationic group in the side chain of 51 parts is added to 2000 parts of water. On the other hand, 10 parts of C.I. in 90 parts of water. I. An aqueous solution in which Acid Red 52 is dissolved is prepared and added dropwise to the resin solution. After dropping, the mixture is stirred at 60 ° C. for 120 minutes to sufficiently react. In order to confirm the end point of the reaction, it was judged that a salt-forming compound was obtained with the reaction solution dropped onto the filter paper and the point where the bleeding disappeared as the end point. After cooling to room temperature with stirring, suction filtration was performed, and after washing with water, the salt-forming compound remaining on the filter paper was dried by removing moisture with a dryer, and 32 parts of C.I. I. A salt-forming compound (a-3) between Acid Red 52 and Resin B having a cationic group in the side chain was obtained.

(Salt-forming compound (a-4))
The organic dye is C.I. I. The compound was synthesized in the same manner as a-2 except that it was changed to Acid Red 289. I. A salt-forming compound (a-4) of Acid Red 289 and distearyldimethylammonium chloride was obtained.

(Salt-forming compound (a-5))
The organic dye is C.I. I. The compound was synthesized in the same manner as a-3 except that it was changed to Acid Red 289. I. A salt-forming compound (a-5) was obtained between Acid Red 289 and Resin B having a cationic group on the di-side chain.

(Salt-forming compound (a-6))
The organic dye is C.I. I. Except that it was changed to Acid Blue 1, it was synthesized in the same way as a-2,
C. I. A salt-forming compound (a-6) of acid blue 1 and distearyldimethylammonium chloride was obtained.

(Salt-forming compound (a-7))
The organic dye is C.I. I. Synthesis was carried out in the same manner as a-2 except that it was changed to Acid Violet 29. I. A salt-forming compound (a-7) of acid violet and distearyldimethylammonium chloride was obtained.

(Salt-forming compound (a-8))
In the following procedure, C.I. I. A salt-forming compound (a-8) composed of basic violet 1 and hexafluorophosphoric acid was produced. C. I. Violet 1 (1.0 part), hexafluorophosphoric acid (5.0 parts), dichloromethane (100 parts) and water (200 parts) were mixed and stirred at 20 to 30 ° C. for 2 hours. Then, the organic layer was extracted and washed with water, and the organic layer was concentrated under reduced pressure. And it dried with a 60 degreeC vacuum dryer, C.I. I. A salt-forming compound (a-8) of basic violet 1 and hexafluorophosphoric acid was obtained.

(Salt-forming compound (a-9))
In the following procedure, C.I. I. A salt-forming compound (a-6) comprising Basic Blue 7 and a perchloric acid compound was produced. C. I. 1.0 part of Basic Blue 7, 2.6 parts of sodium perchlorate, 100 parts of dichloromethane and 200 parts of water were mixed and stirred at 20-30 ° C. for 2 hours. Then, the organic layer was extracted and washed with water, and the organic layer was concentrated under reduced pressure. And it dried with a 60 degreeC vacuum dryer, C.I. I. A salt-forming compound (a-9) of Basic Blue 7 and a perchloric acid compound was obtained.

<Method for producing pigment dispersion>
(Preparation of blue pigment dispersion (DP-1))
The following mixture was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. Pigment 1 which was filtered through a filter of 1 to prepare pigment dispersion (DP-1): 12.0 parts acrylic resin solution 1: 13.3 parts cyclohexanone: 25.0 parts propylene glycol monomethyl ether acetate: 41.7 parts Dispersant A : 8.0 parts

  Hereinafter, a pigment dispersion (DP-2 to 14) was prepared in the same manner as the pigment dispersion (DP-1) except that the pigments were changed to pigments 2 to 14 shown in Table 1.

(Production of purple, red and green pigment dispersions (DP-15 to 19))

The following mixture was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. A pigment dispersion (DP-15) was produced by filtration using a filter.
C. I. Pigment Violet 23 Pigment: 12.0 parts acrylic resin solution 1: 13.3 parts cyclohexanone: 25.0 parts propylene glycol monomethyl ether acetate: 41.7 parts resin type dispersant (“EFKA4300” manufactured by Ciba Japan): 8 .0 part

  Hereinafter, pigment dispersions (DP-16 to 19) were prepared in the same manner as the pigment dispersion (DP-15) except that the pigments were changed to the pigments shown in Table 2.

A pigment dispersion (DP-21) was produced in the same manner as the pigment dispersion (DP-1) except that the pigment 1 was changed to Comparative pigment example 15.
A pigment dispersion (DP-22) was produced in the same manner as the pigment dispersion (DP-1) except that the pigment 1 was changed to Comparative pigment example 16.

<Method for producing salt-forming compound-containing resin solution>
(Preparation of salt-forming compound-containing resin solution (DA-1))
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 5.0 μm filter to prepare a salt-forming compound-containing resin solution (DA-1).
Salt-forming compound (A-1): 5.0 parts Acrylic resin solution 1: 50.0 parts Cyclohexanone: 35.0 parts Propylene glycol monomethyl ether acetate: 10.0 parts

  Hereinafter, the salt-forming compound-containing resin is the same as the salt-forming compound-containing resin solution (DA-1) except that the salt-forming compound (a-1) is changed to the salt-forming compound (a-2 to 9). Solution (DA-2 to 9)

<Method for producing red and green resist materials>
(Preparation of red resist material)
The following mixture was stirred and mixed to be uniform and then filtered through a 1.0 μm filter to obtain a red resist material.
Pigment dispersion (DP-16): 50.0 parts Pigment dispersion (DP-17): 10.0 parts Acrylic resin solution: 11.0 parts Trimethylolpropane triacrylate: 4.2 parts (manufactured by Shin-Nakamura Chemical Co., Ltd.) "NK ester ATMPT")
Photopolymerization initiator (“Irgacure 907” manufactured by Ciba Japan Co., Ltd.): 1.2 parts sensitizer (“EAB-F” manufactured by Hodogaya Chemical Co., Ltd.): 0.4 parts ethylene glycol monomethyl ether acetate: 23.2 parts

(Preparation of green resist material)
The following mixture was stirred and mixed to be uniform and then filtered through a 1.0 μm filter to obtain a green resist material.
Pigment dispersion (DP-18): 45.0 parts Pigment dispersion (DP-19): 15.0 parts Acrylic resin solution: 11.0 parts Trimethylolpropane triacrylate: 4.2 parts (manufactured by Shin-Nakamura Chemical Co., Ltd.) "NK ester ATMPT")
Photopolymerization initiator (“Irgacure 907” manufactured by Ciba Japan Co., Ltd.): 1.2 parts Sensitizer (“EAB-F” manufactured by Hodogaya Chemical Co., Ltd.): 0.4 parts Ethylene glycol monomethyl ether acetate: 23.2 parts

(Example 1; Production of colored composition (DB-1))
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 5.0 μm filter to prepare a mixed colored composition.
Salt-forming compound-containing resin solution (DA-1): 55.0 parts Pigment dispersion (DP-1): 45.0 parts

(Examples 2 to 13, Comparative Example 1; Colored composition (DB-2 to 14)
Hereinafter, the pigment dispersion (DP-1) was colored in the same manner as the coloring composition (DB-1) except that the type and blending amount of the pigment dispersions (DP-2 to 14) shown in Table 3 were changed. Compositions (DB-2 to 14) were produced. However, the salt-forming compound-containing resin solution (DA-1) was used in the same manner as in Example 1 in Examples 2 to 13 and Comparative Example 1.

(Examples 14 to 25, 25-1 to 25-17, Comparative Example 25-18, Comparative Example 25-19; Colored Composition (DB-15 to 26, DB-01 to DB-019))
Hereinafter, the colored composition (DB-9) except that the salt-forming compound-containing resin solution (DA-1) is changed to the type and amount of the salt-forming compound-containing resin solutions (DA-2 to 9) shown in Table 4. In the same manner, colored compositions (DB-15 to 25, 25-1 to 25-17, Comparative Example 25-18, Comparative Example 25-19) were produced. However, the pigment dispersion (DP-9) was used in the same manner as in Example 8 in Examples 14 to 25.

Example 26 Production of Colored Composition (DB-27)
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 5.0 μm filter to prepare a mixed colored composition.
C. I. Acid Red 52 (unformed salt / sulfoamide): 50.0 parts Pigment dispersion (DP-9): 50.0 parts

(Comparative Example 2; Preparation of colored composition (DB-28))
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 5.0 μm filter to prepare a mixed colored composition.

Pigment dispersion (DP-15): 20.0 parts Pigment dispersion (DP-9): 80.0 parts

(Comparative Example 3; Production of colored composition (DB-29))
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 5.0 μm filter to prepare a mixed colored composition.

Pigment dispersion (DP-15): 11.0 parts Pigment dispersion (DP-2): 89.0 parts

(Evaluation of coloring composition)
The test of the chromaticity of the coating film of the obtained colored composition (DB-1 to 29) was conducted by the following method. Table 4 shows the test results.

(Evaluation of color characteristics)
A colored composition was applied on a glass substrate so that x = 0.137 and y = 0.088 with a C light source, and this substrate was heated at 230 ° C. for 20 minutes. Thereafter, the brightness (Y) of the obtained substrate was measured with a microspectrophotometer (“OSP-SP200” manufactured by Olympus Optical Co., Ltd.). The results are shown in Table 5 below.

(Evaluation of viscosity)
The viscosity at 25 ° C. was measured using an E-type viscometer (TVE-20L type manufactured by TOKI SANGYO) at a rotation speed of 20 rpm. The viscosity with time was measured in the same manner for the viscosity accelerated at 40 ° C. for 1 week. As for the thickening rate, the numerical value calculated by viscosity with time / initial viscosity was expressed in%. The results are shown in Table 5 below.

[Examples 27 to 52, Comparative Examples 4 to 6]
(Example 27; resist material (R-1))
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 1.0 μm filter to obtain an alkali developing resist material (R-1).

Colorant dispersion coloring composition DB-1: 38.0 parts Acrylic resin solution 1: 15.0 parts Trimethylolpropane triacrylate: 5.0 parts (“NK ester ATMPT” manufactured by Shin-Nakamura Chemical Co., Ltd.)
Photopolymerization initiator (“Irgacure 907” manufactured by Ciba Japan Co., Ltd.): 1.0 part sensitizer (“EAB-F” manufactured by Hodogaya Chemical Co., Ltd.): 0.5 part Propylene glycol monomethyl ether acetate: 40.5 parts

(Examples 28 to 52, Comparative Examples 4 to 6; Resist material (R-2 to 29))
Hereinafter, alkali-developable resist materials (R-2 to 29) were obtained in the same manner as the resist material (R-1) except that the colorant dispersion was changed in the type of the coloring composition shown in Table 6.

(Evaluation of resist material)
The chromaticity and viscosity of the coating film of the obtained resist material (R-1 to 29) were tested in the same manner as the coloring composition. The results of the test are shown in Table 6.

(Example 53: Color filter (CF-1))
A black matrix was patterned on a glass substrate, and a red resist material was applied on the substrate with a spin coater to a thickness such that x = 0.640 and y = 0.330 to form a colored film. The coating was irradiated with 300 mJ / cm 2 of ultraviolet rays through a photomask using an ultrahigh pressure mercury lamp. Next, spray development was performed with an alkaline developer composed of a 0.2% by weight aqueous sodium carbonate solution to remove unexposed portions, followed by washing with ion-exchanged water. The substrate was heated at 230 ° C. for 20 minutes to obtain a red filter segment. Formed. By the same method, the green resist material is formed to have a film thickness of x = 0.300 and y = 0.600, and blue resist material (R-1) is used and x = 0.137, y = 0.088. The green filter segment and the blue filter segment were formed to obtain a color filter (CF-1).

(Production of liquid crystal display device)
A transparent ITO electrode layer was formed on the obtained RGB color filter, and a polyimide alignment layer was formed thereon. A polarizing plate was formed on the other surface of this glass substrate. On the other hand, a TFT array and a pixel electrode were formed on one surface of another (second) glass substrate, and a polarizing plate was formed on the other surface. The two glass substrates prepared in this way are arranged facing each other so that the electrode layers face each other, and are aligned using spacer beads while keeping the distance between the two substrates constant, and an opening for injecting a liquid crystal composition The periphery was sealed with a sealant so as to leave After injecting the liquid crystal composition from the opening, the opening was sealed. A liquid crystal display device thus produced was combined with a three-wavelength CCFL light source of a backlight unit to produce a color display device.

(Examples 54 to 78, Comparative Examples 7 to 9)
Hereinafter, in the same manner as in Example 53, the color filters (CF-2 to 29) and color display devices of Examples 54 to 78 and Comparative Examples 7 to 9 were combined with the resist materials shown in Table 5 and a three-wavelength CCFL light source. Was made.

Thereafter, in the obtained color display device, a light source was emitted to display a color image, and the brightness of each color filter segment portion was measured with a microspectrophotometer (“OSP-SP200” manufactured by Olympus Optical Co., Ltd.). The results are shown in Table 6.

When Examples 53 to 78 were compared with Comparative Example 9 (color filter (CF-29)), in white display, a color formed from a resist material containing a conventionally used ε-type copper phthalocyanine pigment and a dioxazine pigment. Compared with the filter (color filter (CF-29)), the color filter (color filter (CF-1, 3 to 27)) formed from the resist material of the present invention containing α-type copper phthalocyanine and an organic dye is high. The brightness is obtained. When Examples 53 to 78 and Comparative Example 8 (color filter (CF-28)) were compared, in white display, a color filter (color filter (color filter) formed from a resist material containing an α-type copper phthalocyanine pigment and a dioxazine pigment was used. Compared with CF-28)), a color filter (color filter (CF-1, 3-27)) formed from the resist material of the present invention containing α-type copper phthalocyanine and an organic dye can also obtain high brightness. ing. When Examples 53 to 78 and Comparative Example 7 (color filter (CF-2)) were compared, in white display, a color filter (color filter (CF (CF-2)) formed from a resist material containing an ε-type copper phthalocyanine pigment and an organic dye was used. -2)), the color filter (color filter (CF-1, 3 to 27)) formed from the resist material of the present invention containing α-type copper phthalocyanine and an organic dye has high brightness. Yes.

Claims (6)

In the color filter coloring composition containing copper phthalocyanine (A), dispersant (B), transparent resin (C), organic solvent (D), and organic dye (E), copper phthalocyanine (A) contains α-type A colored composition for a color filter.
2. The color for color filter according to claim 1, wherein the copper phthalocyanine (A) is obtained by subjecting crude α-type copper phthalocyanine to salt milling or acid pasting in the presence of a compound represented by the following general formula (X). Composition.
Formula (X)
P-Ln
(However, P represents an organic pigment residue, an anthraquinone residue, an acridone residue or a triazine residue,
L represents a basic substituent, an acidic substituent, or a phthalimidomethyl group which may have a substituent, and represents an integer of n: 1 to 4. )
The coloring composition for a color filter according to claim 2, wherein P is a residue of a metal-free or metal phthalocyanine pigment.
The colored composition for a color filter according to any one of claims 1 to 3, wherein the content of α-type in copper phthalocyanine (A) is 90% by weight or more based on the total pigment. 5. The color filter according to claim 1, wherein the organic dye (E) is one or more selected from the group of triarylmethane, xanthene, and anthraquinone. Coloring composition.
  A color filter comprising pixels formed using the coloring composition for a color filter according to claim 1.