JP2017053979A - Colored composition for color filter and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a blue colored composition for a color filter excellent in high lightness, a high contrast ratio and heat resistance, and a color filter excellent in high lightness, a high contrast ratio and heat resistance using the above composition.SOLUTION: A colored composition for a color filter is provided, comprising a colorant (A), a binder resin (B) and an organic solvent (C). The colorant (A) comprises: a resin salt-forming compound (A1) obtained by allowing a vinyl resin (a1) having a structural unit having a cationic group in a side chain and represented by general formula (1) to react with an anionic dye (a2); and a colorant (A2) that is a colorant (A2-1) represented by general formula (2) or a colorant (A2-2) represented by general formula (3), having a peak wavelength λmax2 in a longer wavelength side by 5 to 100 nm than a peak wavelength λmax1 of the resin salt-forming compound (A1).SELECTED DRAWING: None

Description

  The present invention relates to a color liquid crystal display device, a color composition for a color filter used for the production of a color filter used for a color imaging device, and the like, and a color filter including a filter segment formed using the same. is there.

  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.

  As a colorant used for forming a blue filter segment (pixel) and a cyan filter segment (pixel) in a color filter, a phthalocyanine pigment having excellent durability and color tone is often used. Phthalocyanine pigments have different crystal types such as α-type, β-type, δ-type, and ε-type, and each has excellent properties such as clearness and high coloring power. It is suitable. 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, different 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.

  In a display device such as a liquid crystal display device using a conventional cold cathode tube type backlight, a combination of a copper phthalocyanine pigment and a dioxazine pigment is combined with a blue filter segment or a cyan filter segment to achieve high brightness and wide color. The display area could be achieved. However, as described above, the color filter is required to have higher brightness and a wider color reproduction region.

  In order to solve the above problems, a technique has been proposed in which a dye, not a pigment, is dissolved as a colorant in a resin or the like (see, for example, Patent Document 1).

  Further, as a colorant used for a blue filter segment or a cyan filter segment, it has been proposed to use a triarylmethane dye, particularly a triarylmethane dye, as a color filter colorant (see, for example, Patent Document 2). Dyes have a problem that they are inferior in heat resistance, light resistance, and solvent resistance as compared with pigments.

  On the other hand, xanthene dyes are known as dyes exhibiting magenta color. Among them, xanthene dyes have excellent spectral characteristics and are therefore often used for magenta color filters (for example, patents). Reference 3).

In addition, since the spectrum of xanthene dyes has a high transmittance in the vicinity of 400 to 450 nm when compared with copper phthalocyanine pigments and cyanine pigments, a blue color filter was prepared in combination with the above pigments and other blue pigments. In this case, it has been proposed that a blue color filter with higher brightness that does not disturb the color balance can be obtained. (For example, see Patent Documents 4 and 5)
However, because of the high solubility of the dye, it was expected that a color filter with a high contrast ratio could be obtained without the occurrence of scattering, etc. as seen when using only pigments. When a fluorescent dye is used, there is a problem that the contrast ratio is low (see, for example, Patent Document 6), and a color filter capable of achieving both high brightness and high contrast ratio has not been realized. It was.

JP-A-6-75375 JP 2001-81348 A JP 2005-292305 A JP 2009-265641 A JP 2010-32999 A JP 2005-025175 A

  An object of the present invention is to provide a blue coloring composition for a color filter having high brightness, a high contrast ratio and excellent heat resistance, and a color filter using the same and having high brightness, high contrast ratio and excellent heat resistance. .

  As a result of intensive studies to solve the above problems, the present inventors have found that an anionic dye (resin salt-forming compound (A1) salted with a resin as a colorant in a blue coloring composition for a color filter. )), And by adding a specific colorant (colorant (A2)) having a peak wavelength λmax2 longer than the peak wavelength λmax1 of the resin salt-forming compound (A1), a color filter is obtained. In addition, it has been found that high brightness, a wide color reproduction region, and a high contrast ratio can be realized, and that the heat resistance is also excellent, and the present invention has been made based on this finding.

That is, the present invention is a color filter coloring composition comprising a colorant (A), a binder resin (B), and an organic solvent (C),
A resin obtained by reacting a vinyl resin (a1) having a structural unit represented by the following general formula (1) having a cationic group in the side chain with an anionic dye (a2) The salt-forming compound (A1) and a colorant (A2-) having a peak wavelength λmax2 on the longer wavelength side of 5 to 100 nm from the peak wavelength λmax1 of the resin salt-forming compound (A1) and represented by the following general formula (2) 1) or a colorant (A2) that is a colorant (A2-2) represented by the following general formula (3).
General formula (1)


[In General Formula (1), R ¹¹ represents a hydrogen atom or a substituted or unsubstituted alkyl group. R ^{12 to} R ¹⁴ each independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group, and R ^{12 to} R ¹⁴ Two of them may be bonded to each other to form a ring. Q represents an alkylene group, an arylene group, —CONH—R ¹⁵ —, —COO—R ¹⁵ —, and R ¹⁵ represents an alkylene group. Y ^- is representative of an inorganic or organic anion. ]
General formula (2)

[In General Formula (2), R21 to R28 are each independently and independently of each other, a hydrogen atom, a halogen atom, a hydroxy group, a cyano group, a nitro group, an alkyl group, an amino group, an alkoxyl group, an aryl group, an aryl group. It represents an oxy group, an arylthio group, an aralkyloxy group, an acyl group, a carboxyl group, a sulfonic acid group, -SO3Mb, -SO3R29, -SO2NH2, -SO2NHR30, or -SO2NR31R32. However, the hydrogen atom contained in the alkyl group, amino group, alkoxyl group, aryl group, aryloxy group, arylthio group, aralkyloxy group is a halogen atom, hydroxy group, cyano group, nitro group, alkyl group, amino group, It may be substituted with an alkoxyl group, aryl group, aryloxy group, arylthio group, aralkyloxy group, acyl group, carboxyl group, sulfonic acid group, -SO3Mc, -SO3R33, -SO2NH2, -SO2NHR34, or -SO2NR35R36. R29 to R36 each independently represent an alkyl group which may have a substituent. Ma is a metal atom that may have a divalent to tetravalent substituent, and Mb and Mc are metal atoms that neutralize the valence of the molecule. The substituents of R21 and R22, R23 and R24, R25 and R26, and R27 and R28 may be interchanged, or a mixture of isomers having different configurations may be used. ]
General formula (3)

[In General Formula (3), R ^{41 to} R ⁴³ are each independently a hydrogen atom, a halogen atom, a hydroxy group, a cyano group, a nitro group, an alkyl group, an amino group, an alkoxyl group, an aryl group, or an aryloxy group. , an arylthio group, an aralkyloxy group, an acyl group, a carboxyl group, a sulfonic acid _{^{group, -SO 3 M d, -SO 3}} R 44, -SO 2 NH 2, -SO 2 NHR 45, or _-SO 2 ^NR 46 ^{R 47} Represents. However, the hydrogen atom contained in the alkyl group, amino group, alkoxyl group, aryl group, aryloxy group, arylthio group, aralkyloxy group is a halogen atom, hydroxy group, cyano group, nitro group, alkyl group, amino group, an alkoxyl group, an aryl group, an aryloxy group, an arylthio group, an aralkyloxy group, an acyl group, a carboxyl group, a sulfonic acid _{^{group, -SO 3 M e, -SO 3}} R 48, -SO 2 NH 2, -SO 2 NHR 49 , or it may be substituted by _-SO 2 ^NR 50 ^{R 51.} R ⁴⁴ to R ⁵¹ are independently of each other, represent an alkyl group which may have a substituent. M ^d and ^Me are metal atoms that neutralize the valence of the molecule. n1 is an integer of 1 to 8, and m1 is an integer of 0 to 7. When n1 or m1 is plural, each of R ⁴¹ , R ⁴² , and R ⁴³ may have a different structure. ]

  In the present invention, the colorant (A2) content is 0.03 to 0.5 parts by weight with respect to 1 part by weight of the effective pigment component of the resin salt-forming compound (A1). Coloring composition for filters.

In the present invention, the colorant (A) has a peak wavelength λmax3 on the longer wavelength side of 5 to 100 nm from the peak wavelength λmax1 of the resin salt-forming compound (A1), and is represented by the following general formula (4). The coloring composition for color filters characterized by containing an agent (A3).

General formula (4)
P-Lm
[In General Formula (4), P is an m-valent phthalocyanine pigment residue, m is an integer of 1 to 4, and L is General Formulas (5), (6), and (7). Any of the substituents selected from the group shown. The phthalocyanine pigment residue has a metal atom which may have a divalent to tetravalent substituent as a central metal. ]
General formula (5)

General formula (6):

General formula (7)

[In General Formulas (5) to (7), X represents —SO ₂ —, —CO—, —CH ₂ —,
_{-CH 2 NHCOCH 2 -, - CH} 2 NHSO 2 CH 2 -, or a direct bond,
Y ⁰ is —NH—, —O—, or a direct bond,
n is an integer of 1 to 10,
Y ¹ is —NH—, —NR ⁹ —Z—NR ¹⁰ —, or a direct bond;
R ⁹ and R ¹⁰ are each independently a hydrogen atom, an alkyl group having 1 to 36 carbon atoms, an alkenyl group having 2 to 36 carbon atoms, or a phenyl group,
Z represents an alkylene group having 1 to 20 carbon atoms or an arylene group having 1 to 20 carbon atoms.
R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, or a combination of R ¹ and R ² together with further nitrogen, oxygen, Or a heterocycle containing a sulfur atom,
R ³ , R ⁴ , R ⁵ , and R ⁶ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms. ,
R ⁷ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms,
R ⁸ is a substituent represented by the general formula (5) or a substituent represented by the general formula (6),
Q represents a hydroxyl group, an alkoxyl group having 1 to 20 carbon atoms, a substituent represented by the general formula (5), or a substituent represented by the general formula (6). ]

  The present invention also relates to the solubility ratio (A3) / [A3] of the colorant (A3) in the organic solvent (C) and the solubility [A2] of the colorant (A2) in the organic solvent (C). A2]) is 10% or less, and it relates to the coloring composition for a color filter.

In the present invention, the content of the colorant (A3) is 0.2 to 1.2 parts by weight with respect to 1 part by weight of the effective pigment component of the resin salt-forming compound (A1).
It is related with the said coloring composition for color filters characterized by the weight ratio of a coloring agent (A2) and a coloring agent (A3) being 5: 95-90: 10.

  In addition, the present invention relates to the coloring composition for a color filter, which further contains a photopolymerization initiator (H).

In addition, the present invention relates to the coloring composition for a color filter, wherein the binder resin (B) has a dicyclo ring structural unit represented by the following general formula (8).
General formula (8)

[In General Formula (8), Ring A is formed by a bond of any element of hydrogen or carbon which may have a substituent, nitrogen, oxygen or sulfur which may have hydrogen or a substituent. A 10-membered ring structure, and B is formed by a bond of hydrogen or an optionally substituted carbon, hydrogen or an optionally substituted nitrogen, oxygen, or sulfur element 1 It is a linking chain that forms a 6-membered second ring. The general formula (8) may further have a linking chain forming a ring structure. ]

  In addition, the present invention relates to a color filter comprising a filter segment formed on the substrate with the color filter coloring composition.

  In the present invention, the resin salt-forming compound (A1) and the specific colorant (A2) having a peak wavelength λmax2 longer than the peak wavelength λmax1 of the resin salt-forming compound (A1) are contained as the colorant. By using a color filter formed from a coloring composition for color filter, it has excellent heat resistance and light resistance, and has a high brightness, a wide color reproduction region, and a high contrast ratio by suppressing the generation of fluorescence. A color image display device can be obtained.

Especially, it is suitable to use the coloring composition for color filters of this invention especially for a blue filter segment. In that case, the anionic dye (a2) of the resin salt-forming compound (A1) is preferably a xanthene dye.
The transmittance spectrum of a blue coloring composition for a color filter, which is a combination of a copper phthalocyanine blue pigment and a dioxazine pigment, which is a toning component, used in a conventional blue color filter has a transmittance peak position around 450 nm. It exists, and on the short wavelength side of 450 nm or less, it is rapidly lowered due to the influence of the dioxazine pigment.

  On the other hand, the blue coloring composition for a color filter of the present invention contains a resin salt-forming compound (A1) as a toning component, so that the transmission spectrum maintains a high transmittance even on the short wavelength side of 450 nm or less. ing. Therefore, when a cold cathode tube having a peak near 425 to 440 nm or an LED having a peak near 450 nm is a backlight, high brightness can be obtained, and a region of 550 to 700 nm can be obtained more effectively. Since the fluorescence emitted from the light can be suppressed, a high contrast ratio can be obtained.

  Furthermore, by combining with the colorant (A3), fluorescence can be more efficiently suppressed and a high contrast ratio can be obtained.

Hereinafter, the present invention will be described in detail.
In the present application, when “(meth) acryloyl”, “(meth) acryl”, “(meth) acrylic acid”, “(meth) acrylate”, or “(meth) acrylamide” is particularly described, Unless otherwise indicated, “acryloyl and / or methacryloyl”, “acrylic and / or methacrylic”, “acrylic acid and / or methacrylic acid”, “acrylate and / or methacrylate”, or “acrylamide and / or methacrylamide”, respectively. It shall represent.
Further, “CI” in this specification means a color index (CI).

  The colored composition for a color filter of the present invention is obtained by reacting a vinyl resin (a1) having a structural unit represented by the general formula (1) having a cationic group in a side chain with an anionic dye (a2). The resin salt-forming compound (A1) obtained, and a colorant (2) having a peak wavelength λmax2 on the longer wavelength side of 5 to 100 nm from the peak wavelength λmax1 of the resin-forming salt compound (A1) ( A colorant (A) containing a colorant (A2) which is a colorant (A2-2) represented by A2-1) or the following general formula (3), a binder resin (B), and an organic solvent (C ). More preferably, the colorant (A) further has a peak wavelength λmax3 of 5 to 100 nm longer than the peak wavelength λmax1 of the resin salt-forming compound (A1), and is represented by the following general formula (4) ( A3) is contained.

  Hereinafter, the present invention will be described in detail.

<< Colorant (A) >>
As the colorant (A) of the color filter coloring composition of the present invention, a vinyl resin (a1) having a structural unit represented by the general formula (1) having a cationic group in the side chain and an anionic dye (a2) And a resin salt-forming compound (A1) obtained by reacting with a resin compound, and further having a peak wavelength λmax2 of 5-100 nm longer than the peak wavelength λmax1 of the resin salt-forming compound (A1), 2) or a colorant (A2) which is a colorant (A2-2) represented by the following general formula (3).
More preferably, the resin salt-forming compound (A1) has a peak wavelength λmax3 on the longer wavelength side of 5 to 100 nm from the peak wavelength λmax1 and contains the colorant (A3) represented by the general formula (4).

The colored composition for a color filter of the present invention is preferably used in a blue filter segment in combination with a blue pigment (A4).
By using the blue pigment (A4) and the resin salt-forming compound (A1) in combination and mixing, the spectral spectrum is high in the vicinity of 425 to 500 nm having the characteristic peaks of many backlights as described above. It becomes possible to have transmittance, and higher brightness and wider color reproducibility can be obtained than a color filter combining conventional copper phthalocyanine pigments and dioxazine pigments.

<Blue pigment (A4)>
As the blue pigment, a phthalocyanine pigment, a triarylmethane lake pigment, or the like is used. As the phthalocyanine pigment, it is preferable to use a copper phthalocyanine blue pigment.

  Examples of the copper phthalocyanine blue pigment include C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 2, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, and the like. Among them, copper phthalocyanine blue pigments having ε-type and α-type structures are preferable. Such preferred pigments are specifically C.I. I. Pigment blue 15: 6 and C.I. I. Pigment Blue 15: 1.

  Examples of triarylmethane lake pigments include C.I. I. Pigment blue 1, 1: 2, 1: 3, C.I. I. Pigment Blue 2, 2: 1, 2: 2, C.I. I. Pigment blue 3, C.I. I. Pigment Blue 8, C.I. I. Pigment blue 9, C.I. I. Pigment Blue 10, 10: 1, C.I. I. Pigment blue 11, C.I. I. Pigment blue 12, C.I. I. Pigment blue 18, C.I. I. Pigment blue 19, C.I. I. Pigment blue 24, 24: 1, C.I. I. Pigment blue 53, C.I. I. Pigment blue 56, 56: 1, C.I. I. Pigment blue 57, C.I. I. Pigment blue 58, C.I. I. Pigment blue 59, C.I. I. Pigment blue 61, C.I. I. Pigment blue 62 and the like.

  Among these, C.I. I. It is particularly preferable to use CI Pigment Blue 15: 6.

<Other pigments>
In addition, other organic pigments can be added to the blue coloring composition of the present invention as long as the effect is not hindered.

  As other organic pigments, dioxazine pigments, anthraquinone pigments, azo pigments, and quinacridone pigments are preferably used 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 blue coloring composition of the present invention, it is possible to obtain a stable and high-quality blue coloring composition which is further excellent in heat resistance, light resistance and solvent resistance.

(Miniaturization of pigment)
The blue pigment (A4) used in the blue coloring composition of the present invention or other pigments that can be used in combination can be refined by a salt milling treatment. The primary particle diameter of the pigment is preferably 20 nm or more because of good dispersion in the colorant carrier. Moreover, since it can form a filter segment with high contrast ratio, it is preferable that it is 100 nm or less. Therefore, it is preferable to have the range of 20-100 nm. A particularly preferable range is a range of 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, for 100 or more pigment particles, 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. At this time, the pigment particles were sampled on a grid mesh to prepare a sample for TEM observation.

  Salt milling is a process in which a mixture of pigment, water-soluble inorganic salt and water-soluble organic solvent is heated using a kneader such as a kneader, two-roll mill, three-roll mill, ball mill, attritor, or sand mill. After kneading, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt 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 salt milling the pigment, it is possible to obtain a pigment having a very fine primary particle diameter, a narrow distribution width, and a sharp particle size 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 polypropylene 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).

<Resin salt forming compound (A1)>
The resin salt-forming compound (A1) is a resin salt-forming compound obtained by reacting a resin (a1) having a cationic group in the side chain with an anionic dye (a2).

(Resin (a1) having a cationic group in the side chain)
The resin (a1) having a cationic group in the side chain is not particularly limited as long as it has at least one onium base in the side chain, but a preferable onium salt structure is from the viewpoint of availability and the like. Is preferably an ammonium salt, an iodonium salt, a sulfonium salt, a diazonium salt, and a phosphonium salt, and more preferably an ammonium salt, an iodonium salt, or a sulfonium salt in view of storage stability (thermal stability). . More preferred is an ammonium salt.

  When the coloring composition for color filters containing the resin salt-forming compound (A1) of the present invention is prepared and the characteristics as a color filter are expressed, the same kind as the binder resin (B) constituting the coloring composition for color filters It is desirable to use this resin. In the present invention, since an acrylic resin is preferably used for the color filter coloring composition, the resin (a1) having a cationic group in the side chain for obtaining a resin salt-forming compound may be an acrylic resin. desirable.

As the resin (a1) having a cationic group in the side chain of the present invention, a vinyl resin containing a structural unit represented by the following general formula (1) is preferably used.
General formula (1)

[In General Formula (1), R ¹¹ represents a hydrogen atom or a substituted or unsubstituted alkyl group. R ^{12 to} R ¹⁴ each independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group, and R ^{12 to} R ¹⁴ Two of them may be bonded to each other to form a ring. Q represents an alkylene group, an arylene group, —CONH—R ¹⁵ —, —COO—R ¹⁵ —, and R ¹⁵ represents an alkylene group. Y ^- is representative of an inorganic or organic anion. ]

  In general formula (1), R11 represents a hydrogen atom or a substituted or unsubstituted alkyl group. Examples of the alkyl group in R11 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 R11 has a substituent, examples of the substituent include a hydroxyl group and an alkoxyl group.

  Among the above, R11 is most preferably a hydrogen atom or a methyl group.

  In general formula (1), R12 to R14 each independently include a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group. .

  Here, examples of the alkyl group in R12 to R14 include linear alkyl groups (methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl). , N-hexadecyl and n-octadecyl, etc.), branched alkyl groups (isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl, 2-ethylhexyl and 1,1,3,3-tetra Methylbutyl etc.), cycloalkyl groups (cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl etc.) and bridged cyclic alkyl groups (norbornyl, adamantyl, 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 R12 to R14 include linear or branched alkenyl groups (vinyl, aryl, 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, etc.) and cycloalkenyl groups (2-cyclohexenyl, 3-cyclohexenyl, etc.). 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 R12 to R14 include a monocyclic aryl group (such as phenyl), a condensed polycyclic aryl group (such as naphthyl, anthracenyl, phenanthrenyl, anthraquinolyl, fluorenyl, and naphthoquinolyl) and an aromatic heterocyclic hydrocarbon group ( Thienyl (group derived from thiophene), furyl (group derived from furan), pyranyl (group derived from pyran), pyridyl (group derived from pyridine), 9-oxoxanthenyl (derived from xanthone) Group) and 9-oxothioxanthenyl (group derived from thioxanthone) and the like.

  When the alkyl group, alkenyl group, or aryl group represented by R12 to R14 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, and alkoxycarbonyl. And a substituent selected from a 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.

  R12 to R14 are preferably an alkyl group which may be substituted from the viewpoint of stability, and more preferably an unsubstituted alkyl group.

  Two of R12 to R14 may be bonded to each other to form a ring.

  In general formula (1), the component of Q connecting the vinyl moiety and the ammonium base represents an alkylene group, an arylene group, -CONH-R15-, -COO-R15-, and R15 represents an alkylene group. Among these, -CONH-R15- and -COO-R15- are preferable because of polymerizability and availability. R15 is more preferably a methylene group, an ethylene group, a propylene group, or a butylene group, and particularly preferably an ethylene group.

  The Y − component in the general formula (1) 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 (1) 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 an acrylic 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.

  When copolymerizing an ethylenically unsaturated monomer having an ammonium base as a monomer component, examples of the ethylenically unsaturated monomer having a quaternary ammonium base include (meth) acryloyloxyethyltrimethylammonium chloride, ( Alkyl (meth) acrylate quaternary ammonium salts such as (meth) acryloyloxyethyltriethylammonium chloride, (meth) acryloyloxyethyldimethylbenzylammonium chloride, (meth) acryloyloxyethylmethylmorpholinoammonium chloride, (meth) acryloylaminopropyl Trimethylammonium chloride, (meth) acryloylaminoethyltriethylammonium chloride, (meth) acryloylaminoethyldimethylbenzylammoni Alkyl (meth) acryloyl amide quaternary ammonium salts such as Mukuroraido, dimethyl diallyl ammonium methyl sulfate, trimethyl vinyl phenyl ammonium chloride.

  When an acrylic resin having an amino group is obtained and then reacted with an onium chlorinating agent to be 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, dibutylaminoethyl (meth) acrylate, diisobutylaminoethyl (meth) acrylate, di-t-butylaminoethyl (meth) acrylate, dimethylamino Propyl (meth) acrylamide, diethylaminopropyl (meth) acrylamide, dipropylaminopropyl (meth) acrylamide, diisopropylaminopropyl (meth) acrylamide, dibutylaminopro (Meth) acrylic acid ester or (meth) acrylamide having a dialkylamino group such as ru (meth) acrylamide, diisobutylaminopropyl (meth) acrylamide, di-t-butylaminopropyl (meth) acrylamide, and the like, dimethylaminostyrene, Styrenes having a dialkylamino group such as dimethylaminomethylstyrene, diallylamine compounds such as diallylmethylamine and diallylamine, and amino group-containing aromatic vinyl monomers such as N-vinylpyrrolidine, N-vinylpyrrolidone and N-vinylcarbazole Is mentioned.

  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 amino group and the onium chlorinating agent can usually be carried out by dropping an equimolar or less onium chlorinating agent with respect to the amino group into the polymer solution having the amino group. 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 (14).

General formula (14)
ZR ¹⁵ -COOR ¹⁶

[In general formula (14), Z is a halogen such as chlorine or bromine, preferably bromine, and R ¹⁵ is an alkylene group having 1 to 6 carbon atoms, preferably 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms. R ¹⁶ is a lower alkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms. ]

The reaction between an amino group and an alkoxycarbonylalkyl halide is carried out by reacting an equimolar or less alkoxycarbonylalkyl halide with respect to the amino group in the same manner as the above onium chlorinating agent, then hydrolyzing -COOR ¹⁶ to produce carboxylate ions (- It is obtained by converting to COO ⁻ ). Thereby, a polymer having a carboxybetaine structure represented by the general formula (14) and having an ammonium base can be obtained.

  Other ethylenically unsaturated monomers that can be used in combination with an ethylenically unsaturated monomer that forms a structural unit having a cationic group in the side chain of the present invention include crotonic acid esters, vinyl Esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, vinyl alcohol esters, (meth) acrylamides, vinyl ethers, vinyl alcohol esters, styrenes, (meth) acrylonitrile, etc. . Moreover, the copolymer unit derived from the monomer which has an acid group may be included.

  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.

  Examples of the monomer having an acid group include maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid and other unsaturated dicarboxylic acids or anhydrides thereof; trivalent Unsaturated polyvalent carboxylic acids or anhydrides thereof; succinic acid mono (2-acryloyloxyethyl), succinic acid mono (2-methacryloyloxyethyl), phthalic acid mono (2-acryloyloxyethyl), Mono [(meth) acryloyloxyalkyl] esters of divalent or higher polyvalent carboxylic acids such as mono (2-methacryloyloxyethyl) phthalate; ω-carboxy-polycaprolactone monoacrylate, ω-carboxy-polycaprolactone Examples include mono (meth) acrylates of both terminal carboxy polymers such as monomethacrylate.

  In the present invention, as a method for obtaining a copolymer having a structural unit having a cationic group in the side chain, particularly a structural unit represented by the general formula (1), anionic polymerization, living anionic polymerization, cationic polymerization, living cation Known methods such as polymerization, free radical polymerization, and living radical polymerization 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 occurring in general radical polymerization are suppressed, and further, the growth of polymerization occurs uniformly, so that a block polymer or a resin having a uniform molecular weight can be easily synthesized.

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 ammonium base present in the vinyl resin containing the structural unit represented by the general formula (1) suitable for the present invention is not particularly limited, but the resin has an ammonium salt value of 10 to 200 mgKOH / It is preferable that it is g, and it is more preferable that it is 20-130 mgKOH / g.

  The molecular weight of the vinyl resin containing the structural unit represented by the general formula (1) suitable for the present invention is not particularly limited, but the converted weight average molecular weight measured by gel permeation chromatography (GPC) is It 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 (1) suitable for this invention has the 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 (a1) having a cationic group in the side chain, the total content of the structural unit represented by the general formula (1) is not particularly limited, but is contained in the resin (a1) having a cationic group in the side chain. When the total structural unit is 100% by weight, it is preferably 5% by weight or more, and preferably 10 to 50% by weight from the viewpoint of solvent solubility and coloring power of the resin salt-forming compound (A1). Is more preferable.

(Anionic dye (a2))
The anionic dye (a2) may be a colored compound that is ionically bonded to the above-described resin having a cationic group in the side chain. Such a coloring compound is not particularly limited as long as it has a carboxylic acid group, a sulfonic acid group, a phenolic hydroxyl group, a phosphoric acid group, or a metal salt thereof in the molecule, and an organic solvent or developer. Can be appropriately selected in consideration of all the required performance such as solubility in water, salt-forming property, absorbance, interaction with other components in the composition, light resistance, heat resistance and the like.

Examples of the anionic dye (a2) include anthraquinone anionic dyes, monoazo anionic dyes, disazo anionic dyes, oxazine anionic dyes, aminoketone anionic dyes, xanthene anionic dyes, and quinoline anions. Dyes, triphenylmethane anionic dyes and the like. Moreover, as an aspect of an anionic dye (a2), it is preferable to use an acidic dye and a direct dye. Specific examples of the anionic dye (a2) that can be used for the synthesis of the resin salt-forming compound are shown below.
Among them, the colored composition for a color filter of the present invention is preferable because when the anionic dye (a2) is a xanthene-based anionic dye, it can be excellent in lightness, contrast ratio, and heat resistance. .

  Examples of red dyes include C.I. I. Acid Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 22, 23, 24, 25, 25: 1, 26, 26: 1, 26: 2, 27, 29, 30, 31, 32, 33, 34, 35, 36, 37, 39, 40, 41, 42, 43, 44, 45, 47, 50, 52, 53, 54, 55, 56, 57, 59, 60, 62, 64, 65, 66, 67, 68, 70, 71, 73, 74, 76, 76: 1, 80, 81, 82, 83, 85, 86, 87, 88, 89, 91, 92, 93, 97, 99, 102, 104, 106, 107, 108, 110, 111, 113, 114, 115, 116, 120, 123, 125, 127, 128, 131, 132, 133, 134, 135 137, 138, 141, 142, 143, 144, 148, 150, 151, 152, 154, 155, 157, 158, 160, 161, 163, 164, 167, 170, 171, 172, 173, 175, 176, 177, 181, 229, 231, 237, 239, 240, 241, 242, 249, 252, 253, 255, 257, 260, 263, 264, 266, 267, 274, 276, 280, 286, 289, 299, 306, 309, 311, 323, 333, 324, 325, 326, 334, 335, 336, 337, 340, 343, 344, 347, 348, 350, 351, 353, 354, 356, 388 and the like.

  In addition, C.I. I. Direct Red 1, 2, 2: 1, 4, 5, 6, 7, 8, 10, 10: 1, 13, 14, 15, 16, 17, 18, 21, 22, 23, 24, 26, 26: 1, 28, 29, 31, 33, 33: 1, 34, 35, 36, 37, 39, 42, 43, 43: 1, 44, 46, 49, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 67, 67: 1, 68, 72, 72: 1, 73, 74, 75, 77, 78, 79, 81, 81: 1, 85, 86, 88, 89, 90, 97, 100, 101, 101: 1, 107, 108, 110, 114, 116, 117, 120, 121, 122, 122: 1, 124, 125, 127, 127: 1, 127: 2, 128, 129, 130, 132, 134, 135, 136, 137, 1 38, 140, 141, 148, 149, 150, 152, 153, 154, 155, 156, 169, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 186, 189, 204, 211, 213, 214, 217, 222, 224, 225, 226, 227, 228, 232, 236, 237, 238, etc. can also be used.

  Examples of yellow dyes include C.I. I. Acid Yellow 2,3, 4, 5, 6, 7, 8, 9, 9: 1, 10, 11, 11: 1, 12, 13, 14, 15, 16, 17, 17: 1, 18, 20, 21, 22, 23, 25, 26, 27, 29, 30, 31, 33, 34, 36, 38, 39, 40, 40: 1, 41, 42, 42: 1, 43, 44, 46, 48, 51, 53, 55, 56, 60, 63, 65, 66, 67, 68, 69, 72, 76, 82, 83, 84, 86, 87, 90, 94, 105, 115, 117, 122, 127, 131, 132, 136, 141, 142, 143, 144, 145, 146, 149, 153, 159, 166, 168, 169, 172, 174, 175, 178, 180, 183, 187, 188, 189, 190, 191, 192, 199 And the like.

  In addition, C.I. I. Direct Yellow 1, 2, 4, 5, 12, 13, 15, 20, 24, 25, 26, 32, 33, 34, 35, 41, 42, 44, 44: 1, 45, 46, 48, 49, 50, 51, 61, 66, 67, 69, 70, 71, 72, 73, 74, 81, 84, 86, 90, 91, 92, 95, 107, 110, 117, 118, 119, 120, 121, 126, 127, 129, 132, 133, 134, etc. can also be used.

  Examples of orange dyes include C.I. I. Acid Orange 1, 1: 1, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 17, 18, 19, 20, 20: 1, 22, 23, 24, 24: 1 25, 27, 28, 28: 1, 30, 31, 33, 35, 36, 37, 38, 41, 45, 49, 50, 51, 54, 55, 56, 59, 79, 83, 94, 95, 102, 106, 116, 117, 119, 128, 131, 132, 134, 136, 138 and the like.

  In addition, C.I. I. Direct Orange 1, 2, 3, 4, 5, 6, 7, 8, 10, 13, 17, 19, 20, 21, 24, 25, 26, 29, 29: 1, 30, 31, 32, 33, 43, 49, 51, 56, 59, 69, 72, 73, 74, 75, 76, 79, 80, 83, 84, 85, 87, 88, 90, 91, 92, 95, 96, 97, 98, 101, 102, 102: 1, 104, 108, 112, 114, etc. can also be used.

  Examples of blue dyes include C.I. I. Acid Blue 1, 2, 3, 4, 5, 6, 7, 8, 9, 11, 13, 14, 15, 17, 19, 21, 22, 23, 24, 25, 26, 27, 29, 34, 35, 37, 40, 41, 41: 1, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 62, 62: 1, 63, 64, 65, 68, 69, 70, 73, 75, 78, 79, 80, 81, 83, 84, 85, 86, 88, 89, 90, 90: 1, 91, 92, 93, 95, 96, 99, 100, 103, 104, 108, 109, 110, 111, 112, 113, 114, 116, 117, 118, 119, 120, 123, 124, 127, 127: 1, 128, 129, 135, 137, 138, 143, 145, 147 150, 155, 159, 169, 174, 175, 176, 183, 198, 203, 204, 205, 206, 208, 213, 227, 230, 231, 232, 233, 235, 239, 245, 247, 253, 257, 258, 260, 261, 262, 264, 266, 269, 271, 272, 273, 274, 277, 278, 280 and the like.

  In addition, C.I. I. Direct Blue 1, 2, 3, 4, 6, 7, 8, 8: 1, 9, 10, 12, 14, 15, 16, 19, 20, 21, 21: 1, 22, 23, 25, 27, 29, 31, 35, 36, 37, 40, 42, 45, 48, 49, 50, 53, 54, 55, 58, 60, 61, 64, 65, 67, 79, 96, 97, 98: 1, 101, 106, 107, 108, 109, 111, 116, 122, 123, 124, 128, 129, 130, 130: 1, 132, 136, 138, 140, 145, 146, 149, 152, 153, 154, 156, 158, 158: 1, 164, 165, 166, 167, 168, 169, 170, 174, 177, 181, 184, 185, 188, 190, 192, 193, 206, 207, 209, 21 3,215,225,226,229,230,231,242,243,244,253,254,260,263, etc. can also be used.

  Examples of purple dyes include C.I. I. Acid Violet 1, 2, 3, 4, 5, 5: 1, 6, 7, 7: 1, 9, 11, 12, 13, 14, 15, 16, 17, 19, 20, 21, 23, 24, 25, 27, 29, 30, 31, 33, 34, 36, 38, 39, 41, 42, 43, 47, 49, 51, 63, 67, 72, 76, 96, 97, 102, 103, 109, etc. Is mentioned.

  In addition, C.I. I. Direct violet 1, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 16, 17, 18, 21, 22, 25, 26, 27, 28, 29, 30, 31, 32, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 45, 51, 52, 54, 57, 58, 61, 62, 63, 64, 71, 72, 77, 78, 79, 80, 81, 82, 83, 85, 86, 87, 88, 93, 97, etc. can also be used.

  Examples of the green dye include C.I. I. Acid Green 2, 3, 5, 6, 7, 8, 9, 10, 11, 13, 14, 15, 16, 17, 18, 19, 20, 22, 25, 25: 1, 27, 34, 36, 37, 38, 40, 41, 42, 44, 54, 55, 59, 66, 69, 70, 71, 81, 84, 94, 95 and the like.

  In addition, C.I. I. Direct green 11, 13, 14, 24, 30, 34, 38, 42, 49, 55, 56, 57, 60, 78, 79, 80, etc. can also be used.

(Salt formation)
The resin salt-forming compound used in the present invention is prepared by stirring or vibrating an aqueous solution in which a resin (a1) having a cationic group in the side chain and an anionic dye (a2) is dissolved, or a cationic group in the side chain. It can be easily obtained by mixing an aqueous solution of the resin (a1) having an aqueous solution of the anionic dye (a2) with stirring or vibration. In the aqueous solution, the cationic group of the resin and the anionic group of the dye are ionized, these are ionically bonded, and the ion-bonded portion becomes water-insoluble and precipitates. On the contrary, the salt composed of the counter anion of the resin and the counter cation of the acidic dye is water-soluble and can be removed by washing or the like. The resin (a1) and anionic dye (a2) each having a cationic group in the side chain to be used may be a single type or a plurality of types having different structures.

  As an aqueous solution used at the time of salt formation, a mixed solution of water and a water-soluble organic solvent may be used in order to dissolve the resin (a1) having a cationic group in the side chain and the anionic dye (a2). Examples of the water-soluble organic solvent include methanol, ethanol, n-propanol, isopropanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, n-butanol, isobutanol, 2- (methoxymethoxy) ethanol, 2- Butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, ethylene glycol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene Glycol, propylene glycolic monomethyl ether acetate, dipropylene glycol, dipropylene glycol Monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol, triethylene glycol monomethyl ether, polyethylene glycol, glycerin, tetraethylene glycol, dipropylene glycol, acetone, diacetone alcohol, aniline, pyridine, ethyl acetate, isopropyl acetate, methyl ethyl ketone , N, N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran (THF), dioxane, 2-pyrrolidone, 2-methylpyrrolidone, N-methyl-2-pyrrolidone, 1,2-hexanediol, 2,4,6-hexanetriol , Tetrafurfuryl alcohol, 4-methoxy-4-methylpentanone and the like. These water-soluble organic solvents are preferably used in an amount of 5 to 50% by weight, and most preferably 5 to 20% by weight, based on the total weight of the aqueous solution (100% by weight).

  The content of the pigment component derived from the anionic dye (a2) in the resin salt-forming compound (A1) used in the present invention is adjusted to a range of 10 to 60% by weight in 100% by weight of the resin salt-forming compound (A1). Especially, it is preferable to set it as the range of 15 to 55 weight%. By controlling in this range, a resin salt-forming compound having excellent solvent solubility can be obtained.

  In addition, the weight percentage of the effective pigment component (excluding counter ions such as alkali metal ions) in the anionic dye (a2) contained in the resin salt compound (A1) is the same as that of the resin salt compound ( A1) It can be calculated by measuring the spectral spectrum of the solution and the anionic dye (a2) solution and determining the spectral intensity ratio of the maximum absorption wavelength.

For example, a resin salt-forming compound (A1) solution and an anion are prepared using a solvent (N-methyl-2-pyrrolidone or the like) that can well dissolve both the resin salt-forming compound (A1) and the anionic dye (a2). The absorbance at the maximum absorption wavelength of the resin salt-formation compound (A1) solution and the anionic dye (a2) solution obtained by preparing a light-sensitive dye (a2) solution at a certain concentration is Xa and Xb, respectively. . Many anionic dyes (a2) contain a counter ion such as an alkali metal ion. In that case, the number of counter ions present in one molecule is Na and the atomic weight of the counter ion is Ma. When the molecular weight of the dye is Mb, the weight% of the effective pigment component in the anionic dye (a2) is given by the following formula.
(1-Ma × Na / Mb) × 100 [wt%]
And using this formula, the weight% of the effective pigment component in the anionic dye (a2) contained in the resin salt-forming compound (A1) can be calculated from the following formula.
(Xa / Xb) × (1-Ma × Na / Mb) × 100 [wt%]
The ratio of the resin (a1) having a cationic group in the side chain and the anionic dye (a2) is such that the molar ratio of the total cationic unit of the resin to the total anionic group of the anionic dye (a2) is 10/1. The resin salt-forming compound of the present invention can be suitably adjusted if it is in the range of ˜¼, and more preferably in the range of 2/1 to ½.

<Colorant (A2)>
The colorant (A2) has a peak wavelength λmax2 on the longer wavelength side of 5 to 100 nm from the peak wavelength λmax1 of the resin salt-forming compound (A1), and is represented by the following general formula (2) (A2-1) Or it is a coloring agent (A2-2) represented by following General formula (3).
When the colorant (A2) strongly shows two absorptions in the visible part, such as the colorant (A2-2), both wavelengths correspond to the peak wavelength λmax2, and either peak wavelength is a resin salt. The compound (A1) is located on the longer wavelength side of 5 to 100 nm from the peak wavelength λmax1.
More preferably, it is a case on the long wavelength side of 6 to 60 nm.

  The peak wavelength λmax of the colorant is measured by forming a colorant dispersion or colorant solution on a glass substrate by spin coating, and measuring this with a spectroscope (Nippon Bunko spectrophotometer V-570). The maximum wavelength position in the visible light region can be obtained from the obtained Absorbance data.

  The peak wavelength λmax is a maximum absorption wavelength, and is a wavelength at which the absorbance of the coating film is maximum. However, when another absorption peak is present at an intensity within 70% with respect to the maximum absorption peak of the maximum intensity, this absorption also exhibits an effective quenching effect on the fluorescence emission. Therefore, in the present invention, the peak wavelength λmax is did.

  On the other hand, when the resin salt-forming compound (A1) is used as a colorant, a color filter with high brightness can be obtained from the high transparency derived from the high solubility of the dye, compared to the case where only the pigment is used, There is a problem that fluorescence is generated from the dye itself and the contrast ratio is lowered. This is mainly due to the presence of fluorescence in the leakage light at the time of measuring the contrast ratio, and the luminance on the cross side increases.

  As a result of studies conducted by the present inventors to solve the problem of reduction in contrast ratio due to fluorescence emission, the resin salt compound (A1) and a length of 5 to 100 nm longer than the peak wavelength λmax1 of the resin salt compound (A1). By using a colorant having a peak wavelength λmax2 on the wavelength side and the colorant (A2-1) represented by the general formula (2) or (A2-2) represented by the following general formula (3), It was possible to realize high contrast by eliminating the generation of fluorescence from the anionic dye and lowering the brightness on the cross side.

This is because the colorant (A2) has no absorption in the transmission region of the resin salt-forming compound (A1), and is 5 to 100 nm longer than the peak wavelength λmax1 that is the fluorescent light-emitting region of the resin salt-forming compound (A1). Since it has a peak wavelength λmax2, it seems that the generation is suppressed by absorbing fluorescence. The effect of increasing the contrast is reduced when the anionic dye (a2) is used alone without salt formation with the resin (a1) having a cationic group in the side chain. Since the anionic dye (a2) has a salt-forming structure with the resin (a1) having a cationic group in the side chain, the colorant (A2) is a resin salt-forming compound (A1) in the resin matrix of the colorant-dispersed film. It seems to be due to the fact that it can be distributed homogeneously together.
Furthermore, since the colorant (A2) is easily dissolved in the organic solvent (C) used in the color filter coloring composition, as in the case of the resin salt-forming compound (A1), a color filter having high brightness from a high transparency can be obtained. can get.

(Colorant (A2-1))
The colorant (A2-1) is a colorant having a peak wavelength λmax2 of 5 to 100 nm longer than the peak wavelength λmax1 of the resin salt-forming compound (A1) and represented by the following general formula (2).
General formula (2)

[In General Formula (2), R ^{21 to} R ²⁸ are each independently, independently of each other, a hydrogen atom, a halogen atom, a hydroxy group, a cyano group, a nitro group, an alkyl group, an amino group, an alkoxyl group, or an aryl group. , an aryloxy group, an arylthio group, an aralkyloxy group, an acyl group, a carboxyl group, a sulfonic acid _{^{group, -SO 3 M b, -SO 3}} R 29, -SO 2 NH 2, -SO 2 NHR 30, or -SO ₂ NR ³¹ R ³² is represented. However, the hydrogen atom contained in the alkyl group, amino group, alkoxyl group, aryl group, aryloxy group, arylthio group, aralkyloxy group is a halogen atom, hydroxy group, cyano group, nitro group, alkyl group, amino group, an alkoxyl group, an aryl group, an aryloxy group, an arylthio group, an aralkyloxy group, an acyl group, a carboxyl group, a sulfonic acid _{^{group, -SO 3 M c, -SO 3}} R 33, -SO 2 NH 2, -SO 2 NHR 34 , or it may be substituted by _-SO 2 ^NR 35 ^{R 36.} R ^{29 to} R ³⁶ each independently represent an alkyl group which may have a substituent. M ^a is a divalent to tetravalent substituent may metal atoms have, M ^b, M ^c is a metal atom to neutral power value of the molecule. The substituents of R ²¹ and R ²² , R ²³ and R ²⁴ , R ²⁵ and R ²⁶ , R ²⁷ and R ²⁸ may be interchanged, or a mixture of isomers having different configurations may be used. ]

When R ^{21 to} R ²⁸ and R ^{29 to} R ³⁶ have an alkyl group, it may be either a saturated aliphatic hydrocarbon group or a saturated alicyclic hydrocarbon group. Further, the saturated aliphatic hydrocarbon group may be in a linear or branched form.
Among them, any of R ²¹ , R ²² , any of R ²³ , R ²⁴ , any of R ²⁵ , R ²⁶ , and any one of R ²⁷ , R ²⁸ is a branched saturated group having 3 to 10 carbon atoms. It is an aliphatic hydrocarbon, and the other is preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms, and has a halogen atom at a position (ortho position) next to the bonding position of the aromatic hydrocarbon group. More preferably. Specific examples _{^{M a, Cu, Zn, Si}} (OH) 2, Si (R 29) 2, Pd, Co, Ni, but is preferably such as VO, Cu is particularly preferred ^{(R 29} has a substituent And may be an alkoxyl group, an aryloxy group, or a siloxy group).

Moreover, the hydrogen atom in the alkyl group which may have a substituent of R ^{29 to} R ³⁶ may be substituted with a substituent selected from the following substituent group X.

“Substituent Group X”
Substituents include halogen atoms, alkyl groups, cycloalkyl groups, alkenyl groups, cycloalkenyl groups, alkynyl groups, aryl groups, heterocyclic groups, cyano groups, hydroxyl groups, nitro groups, carboxyl groups, alkoxy groups, aryloxy groups, Silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (including alkylamino group and anilino group), acylamino group, aminocarbonylamino group, alkoxycarbonylamino Group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl Is an arylsulfinyl group, alkyl or arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl or heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphini Examples include a ruamino group and a silyl group.

(Colorant (A2-2))
The colorant (A2-1) is a colorant having a peak wavelength λmax2 of 5 to 100 nm longer than the peak wavelength λmax1 of the resin salt-forming compound (A1) and represented by the following general formula (2).
General formula (3)

[In General Formula (3), R ^{41 to} R ⁴³ are each independently a hydrogen atom, a halogen atom, a hydroxy group, a cyano group, a nitro group, an alkyl group, an amino group, an alkoxyl group, an aryl group, or an aryloxy group. , an arylthio group, an aralkyloxy group, an acyl group, a carboxyl group, a sulfonic acid _{^{group, -SO 3 M d, -SO 3}} R 44, -SO 2 NH 2, -SO 2 NHR 45, or _-SO 2 ^NR 46 ^{R 47} Represents. However, the hydrogen atom contained in the alkyl group, amino group, alkoxyl group, aryl group, aryloxy group, arylthio group, aralkyloxy group is a halogen atom, hydroxy group, cyano group, nitro group, alkyl group, amino group, an alkoxyl group, an aryl group, an aryloxy group, an arylthio group, an aralkyloxy group, an acyl group, a carboxyl group, a sulfonic acid _{^{group, -SO 3 M e, -SO 3}} R 48, -SO 2 NH 2, -SO 2 NHR 49 , or it may be substituted by _-SO 2 ^NR 50 ^{R 51.} R ⁴⁴ to R ⁵¹ are independently of each other, represent an alkyl group which may have a substituent. M ^d and ^Me are metal atoms that neutralize the valence of the molecule. n1 is an integer of 1 to 8, and m1 is an integer of 0 to 7. When n1 or m1 is plural, each of R ⁴¹ , R ⁴² , and R ⁴³ may have a different structure. ]

If ^{R 41 ~R 43, R 44 ~R} 51 has an alkyl group, it may be either a saturated aliphatic hydrocarbon group and a saturated alicyclic hydrocarbon group. Further, the saturated aliphatic hydrocarbon group may be in a linear or branched form.

In addition, the hydrogen atom in the alkyl group that may have a substituent of R ^{44 to} R ⁵¹ may be substituted with a substituent selected from the substituent group X. The “substituent group X” has the same meaning as the “substituent X” mentioned in the section of the colorant (A2-1).

Among them, R ⁴¹ is a hydrogen atom, R ⁴² is a saturated hydrocarbon group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms, n is 2, and the general formula (3-b ) ^Are preferably bonded to R ⁵² and R ⁵³ positions. Further, when R ⁴² is an aromatic hydrocarbon group having 6 to 10 carbon atoms, it is further preferable that at least one of R ⁴² is substituted with —SO ₂ NHR ⁴⁹ or —SO ₂ NR ⁵⁰ R ^51. preferable.

Formula (3-b)


R52 or R53 is independently -NR41R42 or R43.

<Colorant (A3)>
As a result of studies conducted by the present inventors to solve the problem of reduction in contrast due to fluorescence, the resin salt-forming compound (A1) is further added to the colorant containing the resin salt-forming compound (A1) and the colorant (A2). By including the colorant (A3) represented by the general formula (4) having a peak wavelength λmax3 on the longer wavelength side of 5 to 100 nm from the peak wavelength λmax1, it is possible to realize higher contrast. I found out that I can do it. Furthermore, higher heat resistance can be obtained.

  The colorant (A3) has a structure having a substituent in the phthalocyanine skeleton, and the solubility in the organic solvent (C) is higher than that of the blue pigment (A4) and inferior to that of the colorant (A2). It is considered that the solubility which becomes a neutrality with the resin salt-forming compound (A1) and the colorant (A2) which are easily soluble in the blue pigment (A4) contributes to the effect of increasing the contrast.

The content of the colorant (A3) is preferably 0.2 to 1.2 parts by weight with respect to 1 part by weight of the effective pigment component of the resin salt-forming compound (A1). When the amount is 0.2 parts by weight or more, the effect of increasing the contrast ratio is improved, and when the amount is 1.2 parts by weight or less, brightness and heat resistance are better. More preferably, it is 0.3-1.2 weight part, More preferably, it is 0.5-1.1 weight part.
Furthermore, the weight blending ratio of the colorant (A2) and the colorant (A3) is desirably 5:95 to 90:10.
More desirably, the weight blending ratio is 10:90 to 80:20. The effect of increasing the contrast ratio is improved when the weight blending ratio is within this range.

  In the case where the resin salt-forming compound (A1) is a salt-forming compound of a xanthene-based anionic dye and a copper phthalocyanine sulfonic acid amide compound is used among the amine compounds of the phthalocyanine which is the colorant (A3), Since it is easy to form a charge transfer complex with a xanthene dye, it is considered that the fluorescence emission itself is remarkably suppressed and the fluorescence is remarkably quenched. In addition to the above-described fluorescence quenching effect, the high compatibility between the dye and the copper phthalocyanine blue pigment when using the copper phthalocyanine sulfonic acid amide compound is due to the light scattering due to the uneven distribution of the copper phthalocyanine particles and the dye in the resist. As a result, it is considered that the cross luminance becomes extremely low and the contrast ratio is particularly excellent.

General formula (4)
P-Lm
[In General Formula (4), P is an m-valent phthalocyanine pigment residue, m is an integer of 1 to 4, and L is General Formulas (5), (6), and (7). Any of the substituents selected from the group shown. The phthalocyanine pigment residue has a metal atom which may have a divalent to tetravalent substituent as a central metal. ]
The colorant (A3) can be used alone, but two or more kinds may be used in combination.
General formula (5):

General formula (6)

General formula (7)

[In General Formulas (5) to (7), X represents —SO ₂ —, —CO—, —CH ₂ —,
_{-CH 2 NHCOCH 2 -, - CH} 2 NHSO 2 CH 2 -, or a direct bond,
Y ⁰ is —NH—, —O—, or a direct bond,
n is an integer of 1 to 10,
Y ¹ is —NH—, —NR ⁹ —Z—NR ¹⁰ —, or a direct bond;
R ⁹ and R ¹⁰ are each independently a hydrogen atom, an alkyl group having 1 to 36 carbon atoms, an alkenyl group having 2 to 36 carbon atoms, or a phenyl group,
Z represents an alkylene group having 1 to 20 carbon atoms or an arylene group having 1 to 20 carbon atoms.
R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, or a combination of R ¹ and R ² together with further nitrogen, oxygen, Or a heterocycle containing a sulfur atom,
R ³ , R ⁴ , R ⁵ , and R ⁶ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms. ,
R ⁷ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms,
R ⁸ is a substituent represented by the general formula (5) or a substituent represented by the general formula (6),
Q represents a hydroxyl group, an alkoxyl group having 1 to 20 carbon atoms, a substituent represented by the general formula (5), or a substituent represented by the general formula (6). ]

  Examples of the amine component used for forming the substituents represented by the general formulas (5) to (7) include dimethylamine, diethylamine, methylethylamine, N, N-ethylisopropylamine, N, N-ethyl. Propylamine, N, N-methylbutylamine, N, N-methylisobutylamine, N, N-butylethylamine, N, N-tert-butylethylamine, diisopropylamine, dipropylamine, N, N-sec-butylpropylamine , Dibutylamine, di-sec-butylamine, diisobutylamine, N, N-isobutyl-sec-butylamine, diamylamine, diisoamylamine, dihexylamine, dicyclohexylamine, di (2-ethylhexyl) amine, dioctylamine, N, N-methyloctadeci Amine, didecylamine, diallylamine, N, N-ethyl-1,2-dimethylpropylamine, N, N-methylhexylamine, dioleylamine, distearylamine, N, N-dimethylaminomethylamine, N, N-dimethylamino Ethylamine, N, N-dimethylaminoamylamine, N, N-dimethylaminobutylamine, N, N-diethylaminoethylamine, N, N-diethylaminopropylamine, N, N-diethylaminohexylamine, N, N-diethylaminobutylamine, N , N-diethylaminopentylamine, N, N-dipropylaminobutylamine, N, N-dibutylaminopropylamine, N, N-dibutylaminoethylamine, N, N-dibutylaminobutylamine, N, N-diisobutylaminopen Ruamine, N, N-methyl-laurylaminopropylamine, N, N-ethylhexylaminoethylamine, N, N-distearylaminoethylamine, N, N-dioleylaminoethylamine, N, N-distearylaminobutylamine, Piperidine, 2-Pipecoline, 3-Pipecoline, 4-Pipecoline, 2,4-Lupetidine, 2,6-Lupetidine, 3,5-Lupetidine, 3-Piperidinmethanol, Pipecolic acid, Isonipecotic acid, Methyl isonipecotate, Isonicopetic acid Ethyl, 2-piperidineethanol, pyrrolidine, 3-hydroxypyrrolidine, N-aminoethylpiperidine, N-aminoethyl-4-pipecholine, N-aminoethylmorpholine, N-aminopropylpiperidine, N-aminopropyl-2-pipecholine, -Aminopropyl-4-pipecholine, N-aminopropylmorpholine, N-methylpiperazine, N-butylpiperazine, N-methylhomopiperazine, 1-cyclopentylpiperazine, 1-amino-4-methylpiperazine, 1-cyclopentylpiperazine, etc. Is mentioned.

  The amine compound of phthalocyanine having a basic substituent of the present invention can be synthesized by various synthetic routes. For example, after introducing the substituents represented by the following general formulas (9) to (12) into copper phthalocyanine or other metal phthalocyanines, they react with the above substituents and are represented by the general formulas (5) to (7). The amine component forming the substituent, for example, N, N-dimethylaminopropylamine, N-methylpiperazine, diethylamine, or 4- [4-hydroxy-6- [3- (dibutylamino) propylamino] -1, It can be obtained by reacting 3,5-triazin-2-ylamino] aniline or the like.

Formula (10): —SO ₂ Cl
Formula (11): -COCl
Formula (12): —CH ₂ NHCOCH ₂ Cl
Formula (13): —CH ₂ Cl
In the reaction of the substituents of the general formulas (10) to (13) with the amine component, a part of the substituents of the general formulas (10) to (13) are hydrolyzed and chlorine is substituted with a hydroxyl group. It may be mixed. In that case, the general formula (10) and the general formula (13) are a sulfonic acid group and a carboxylic acid group, respectively. Or a salt with a monoamine.

  Of the colorant (A3) of the present invention, the substituent represented by the general formula (7) can be synthesized by various synthetic routes. For example, an amine component starting from cyanuric chloride and forming a substituent represented by the general formulas (5) and (6) on at least one chlorine of cyanuric chloride, such as N, N-dimethylaminopropylamine or N- It can be obtained by reacting methylpiperazine or the like and then reacting the remaining chlorine of cyanuric chloride with various amines or alcohols.

  The most preferred form of the phthalocyanine amine compound used in the present invention is a copper phthalocyanine sulfonic acid amide compound which is a copper phthalocyanine basic compound.

The copper phthalocyanine sulfonic acid amide compound is a general formula (5) to (7) among the copper phthalocyanine compounds having the above basic substituents.
X in the general formulas (5) to (7) is —SO ₂ —, —CH ₂ NHSO ₂ CH ₂ —,
Y ⁰ is —NH— or a direct bond;
n is an integer of 1 to 10,
Y ¹ is a compound that is —NH— or —NR ⁹ —Z—NR ¹⁰ —.
[Wherein R ⁹ and R ¹⁰ are each independently a hydrogen atom, an alkyl group having 1 to 36 carbon atoms, an alkenyl group having 2 to 36 carbon atoms, or a phenyl group; 20 alkylene groups, preferably an alkylene group having 1 to 10 carbon atoms, or an arylene group having 1 to 20 carbon atoms, preferably an arylene group having 1 to 10 carbon atoms. Examples include a methylene group, an ethylene group, and propylene. Group and phenylene group. ]

  The colorant (A3) is preferably an amine compound of copper phthalocyanine, a basic compound having a basic substituent on the copper phthalocyanine pigment (copper phthalocyanine sulfonic acid amide compound), or a resin of an acidic substituent and a quaternary ammonium salt. Examples thereof include a salt-forming compound (a copper phthalocyanine sulfonate ammonium salt) or a compound into which a phthalimidomethyl group which may have a substituent is introduced. This will be specifically described below.

  As the phthalocyanine, in addition to the copper phthalocyanine, metal-free phthalocyanine, aluminum phthalocyanine, zinc phthalocyanine, cobalt phthalocyanine, nickel phthalocyanine and the like can also be used.

  Among the above, the colorant (A3) used in the present invention is a basic compound having a basic substituent on the copper phthalocyanine pigment, in particular, a copper phthalocyanine sulfonate ammonium salt, a copper phthalocyanine tertiary amine compound, a copper phthalocyanine sulfonate amide. Compounds are preferred. Similarly, a basic compound having a basic substituent on the zinc phthalocyanine pigment can also be preferably used.

  In the present invention, both the colorant (A2) and the colorant (A3) have a quenching effect on the fluorescence emitted from the resin salt-forming compound (A1). And there is a difference in solubility between the colorant (A2) and the colorant (A3), the colorant (A2) is easily soluble in the organic solvent (C), and contains the organic solvent (C). In the product, the resin salt-forming compound (A1) is uniformly present and exhibits a quenching effect, and the colorant (A3) has low solubility (partially soluble) in the organic solvent (C). In the coloring composition containing (C), it is distributed in the vicinity of the blue pigment (A4), and a synergistic effect of exhibiting a quenching effect against fluorescence scattering is obtained.

  Here, the solubility ratio ([A3] / [A2]) of the solubility [A3] of the colorant (A3) in the organic solvent (C) and the solubility [A2] of the colorant (A2) in the organic solvent (C) is obtained. 10% or less is preferable because the contrast ratio can be excellent. More preferably, it is 6% or more.

The solubility of the colorant can be calculated, for example, as follows.
For example, when the organic solvent (C) in the coloring composition is propylene glycol monomethyl ether acetate, the coloring agent (A2) or coloring agent (A A3) is blended and sonicated. When it is completely dissolved, the blending amount of the colorant is increased until the precipitation is recognized even after the ultrasonic treatment, and the ultrasonic treatment liquid is prepared. The treated solution is filtered through a 0.2 micron membrane filter (PTFE), and the weighed filtrate is evaporated to dryness at 200 ° C. for 30 minutes and weighed again. Solubility can be calculated as

  When the organic solvent (C) in the coloring composition is composed of a single component or an organic solvent component (C-1) having a content ratio of 90% by weight or more, the solubility of the colorant in the organic solvent (C) is Calculated as solubility in the main solvent (C-1). When the organic solvent (C) in the coloring composition does not contain an organic solvent component having a content ratio of 90% by weight or more, the solubility is calculated as the solubility of the content ratio actually used in the coloring composition.

<< Binder resin (B) >>
The binder resin (B) plays a role of dispersing the colorant or dyeing and penetrating, and the transmittance is preferably 80% or more, more preferably in the entire wavelength region of 400 to 700 nm in the visible light region. A resin of 95% or more is preferred. For example, there are a thermoplastic resin and a thermosetting resin, and these can be used alone or in combination of two or more. Moreover, when using the coloring composition of this invention with the form of an alkali image development type | mold coloring resist material, it is preferable to use the alkali-soluble resin which copolymerized the acidic group containing ethylenically unsaturated monomer. In order to further improve the photosensitivity, a photosensitive resin having an ethylenically unsaturated double bond can be used.

  In particular, the alkali-soluble photosensitive resin (B1) having both alkali-soluble performance and photocuring performance in the binder resin (B) is preferable as having both performances.

  Examples of the thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, and polyester resin. , Acrylic resins, alkyd resins, polystyrene, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene, polybutadiene, polyimide resins, and the like. Examples of the thermosetting resin include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenol resins.

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

  Examples of the alkali-soluble resin obtained by copolymerizing an acidic group-containing ethylenically unsaturated monomer include resins having an acidic group such as a carboxyl group and 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.

  The weight average molecular weight (Mw) of the binder resin (B) is preferably in the range of 5,000 to 100,000, more preferably in the range of 5,000 to 80,000, still more preferably 5,000 to 30. , 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 weight average molecular weight (Mw) of the binder resin (B) exceeds 100,000, the interaction between the resins becomes strong, and the viscosity of the color filter coloring composition is increased, which makes it difficult to handle. Further, if the weight average molecular weight (Mw) is less than 5,000, problems may occur in developability and adhesion to a substrate such as glass.

  The acid value of the binder resin (B) is preferably a resin having an acid value of 20 to 300 mgKOH / g from the viewpoints of dispersibility, penetrability, developability and resistance of the pigment. 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, a fine pattern may not remain.

The binder resin (B) can be used in an amount of 20 to 400 parts by weight, preferably 50 to 250 parts by weight, with respect to 100 parts by weight of the colorant (A) in the coloring composition.
(Alkali-soluble photosensitive resin (B1))
It is preferable that binder resin (B) used for the coloring composition of this invention contains alkali-soluble photosensitive resin (B1).

  Examples of the alkali-soluble photosensitive resin (B1) in the present invention include resins in which an ethylenically unsaturated double bond is introduced by the following methods (i) and (ii).

[Method (i)]
As the method (i), for example, a side chain epoxy group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having an epoxy group and one or more other monomers is used. Then, the carboxyl group of an unsaturated monobasic acid having an ethylenically unsaturated double bond is subjected to an addition reaction, and the resulting hydroxyl group is reacted with a polybasic acid anhydride to introduce an ethylenically unsaturated double bond. There is a method of introducing a carboxyl group having the function of a functional resin and having an alkali-soluble function.

  Examples of the ethylenically unsaturated monomer having an epoxy group include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 2-glycidoxyethyl (meth) acrylate, 3,4 epoxybutyl (meth) acrylate, And 3,4 epoxy cyclohexyl (meth) acrylates, and these may be used alone or in combination of two or more. From the viewpoint of reactivity with the unsaturated monobasic acid in the next step, glycidyl (meth) acrylate is preferred.

  Examples of unsaturated monobasic acids include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, cyano substituted products, etc. Monocarboxylic acid etc. are mentioned, These may be used independently or may use 2 or more types together.

  Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc., and these may be used alone or in combination of two or more. It doesn't matter. If necessary, use a tricarboxylic anhydride such as trimellitic anhydride or a tetracarboxylic dianhydride such as pyromellitic dianhydride to increase the number of carboxyl groups. The group can be hydrolyzed. Moreover, when an etrahydrophthalic anhydride or maleic anhydride having an ethylenically unsaturated double bond is used as the polybasic acid anhydride, the ethylenically unsaturated double bonds can be further increased.

  As a method similar to the method (i), for example, a side chain of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a carboxyl group and one or more other monomers. There is a method in which an ethylenically unsaturated monomer having an epoxy group is added to a part of a carboxyl group to introduce an ethylenically unsaturated double bond and a carboxyl group.

[Method (ii)]
As the method (ii), an ethylenically unsaturated monomer having a hydroxyl group is used, and an unsaturated monobasic acid monomer having another carboxyl group or another monomer is copolymerized. There is a method of reacting the isocyanate group of an ethylenically unsaturated monomer having an isocyanate group with the side chain hydroxyl group of the obtained copolymer.

  Examples of the ethylenically unsaturated monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, and glycerol. Examples thereof include hydroxyalkyl (meth) acrylates such as (meth) acrylate or cyclohexanedimethanol mono (meth) acrylate, and these may be used alone or in combination of two or more. Further, polyether mono (meth) acrylate obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to the above hydroxyalkyl (meth) acrylate, (poly) γ-valerolactone, (poly) ε-caprolactone And / or (poly) 12-hydroxystearic acid added (poly) ester mono (meth) acrylate can also be used. From the viewpoint of suppressing foreign matter on the coating film, 2-hydroxyethyl (meth) acrylate or glycerol (meth) acrylate is preferable.

  Examples of the ethylenically unsaturated monomer having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate, 1,1-bis [(meth) acryloyloxy] ethyl isocyanate, and the like. In addition, two or more types can be used in combination.

  Examples of the alkali-soluble photosensitive resin (B1) include unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, or α-chloroacrylic acid, and carboxyls such as unsaturated dicarboxylic acids such as maleic acid or fumaric acid. And a resin containing a group and having an ethylenically unsaturated double bond. Other ethylenically unsaturated monomers that are precursors of the alkali-soluble photosensitive resin (B1) include methyl (meth) methacrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and isopropyl (meth). Acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl acrylate, neopentyl (meth) acrylate, t-pentyl ( (Meth) acrylate, 1-methylbutyl (meth) acrylate, hexyl (meth) acrylate, hepta (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) Examples include alkyl or alkenyl (meth) acrylates such as acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, cyclohexyl (meth) acrylate, allyl (meth) acrylate, or oleyl (meth) acrylate, depending on the purpose. In addition, other ethylenically unsaturated monomers can be selected without being limited to these, and two or more types can be used in combination. Of these, methyl (meth) acryl methacrylate or ethyl (meth) acrylate is preferred from the viewpoint of pigment dispersibility.

Furthermore, the binder resin (B) preferably has a dicyclo ring structural unit represented by the following general formula (8).

[In General Formula (8), Ring A is formed by a bond of any element of hydrogen or carbon which may have a substituent, nitrogen, oxygen or sulfur which may have hydrogen or a substituent. A 10-membered ring structure, and B is formed by a bond of hydrogen or an optionally substituted carbon, hydrogen or an optionally substituted nitrogen, oxygen, or sulfur element 1 It is a linking chain that forms a 6-membered second ring. The general formula (8) may further have a linking chain forming a ring structure. ]

  As a manufacturing method in which the binder resin (B) includes a dicyclo ring structural unit represented by the general formula (8), a compound having an unsaturated bond together with the structural unit in one molecule is used as a raw material, and another unsaturated bond is included. An example is a method of polymerizing with a compound.

Examples of the skeleton having a dicyclo ring structural unit represented by the general formula (8) in one molecule include norbornane, norbornene, and an adamantane skeleton.
As precursors for introducing a dicyclo ring structural unit represented by the general formula (8) having an unsaturated bond with these skeletons, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) Acrylate, dicyclopentanyl (meth) acrylate, dimethylol dicyclopentane di (meth) acrylate, tricyclodecane dimethanol (meth) acrylate, isobornyl (meth) acrylate, 3-hydroxy-1-adamantyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate, 2-propyl-2-adamantyl (meth) acrylate, 3,5-dihydroxy-1-adamantyl (meth) acrylate, 1,3-adamantyldiol Examples include di (meth) acrylate, 1,3,5-adamantyl (meth) acrylate, 3-hydroxy-1,5-adamantyl di (meth) acrylate, 3,5-dihydroxy-1-adamantyl (meth) acrylate, and the like. Particularly preferred are dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dimethylol dicyclopentane di (meth) acrylate, 3-hydroxy-1 -Adamantyl acrylate, 2-methyl-2-adamantyl acrylate, 2-ethyl-2-adamantyl acrylate are preferred.

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

Examples of the organic solvent (C) include 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-propylacetate , 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, acetic acid Iso Mill, isobutyl acetate, propyl acetate, dibasic esters, butyl lactate and the like.
These organic solvents can be used individually by 1 type or in mixture of 2 or more types.

  Among these, since the dispersibility, solubility, and permeability of the colorant (A) of the present invention are good, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate It is preferable to use glycol acetates such as, aromatic alcohols such as benzyl alcohol, and ketones such as cyclohexanone. Of these, cyclohexanone is preferably used.

  In addition, the organic solvent (C) can adjust the coloring composition to an appropriate viscosity to form a filter segment having a desired uniform film thickness, so that the total weight of the coloring agent (A) is based on (100% by weight). Thus, it is preferably used in an amount of 800 to 4000% by weight.

  The blue coloring composition of the present invention can be used as a photosensitive coloring composition (resist material) for color filters by further adding a photopolymerizable monomer and / or a photopolymerization initiator.

<< Photopolymerizable monomer >>
Photopolymerizable monomers that may be added to the colored composition of the present invention include monomers or oligomers that are cured by ultraviolet rays or heat to produce a transparent resin.

Examples of monomers and oligomers that are cured by ultraviolet rays or heat to produce a transparent resin include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 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 diglycy Luether di (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 Examples include, but are not necessarily limited to, til (meth) acrylamide, N-vinylformamide, acrylonitrile and the like.
These photopolymerizable compounds can be used singly or in combination of two or more at any ratio as required.

  The content of the photopolymerizable monomer is preferably 5 to 500 parts by weight with respect to 100 parts by weight of the colorant, and more preferably 10 to 400 parts by weight from the viewpoint of photocurability and developability. .

<< Photopolymerization initiator >>
In the colored composition of the present invention, a photopolymerization initiator is added to form a filter segment by photolithography by curing the composition by ultraviolet irradiation, and a solvent development type or alkali development type photosensitive coloring composition is added. It can be prepared in the form of

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 a benzoin compound such as benzyldimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, or 3,3 ′, Benzophenone compounds such as 4,4′-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4-diethylthioxanthone Thioxanthone compounds such as 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p- Toxiphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis ( Trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (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-benzoylo Shim)], or oxime ester compounds such as O- (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4,6 Phosphine compounds such as trimethylbenzoyl) phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone; borate compounds; A carbazole compound; an imidazole compound; or a titanocene compound is used.
These photoinitiators can be used individually by 1 type or in mixture of 2 or more types by arbitrary ratios as needed.

  The content of the photopolymerization initiator is preferably 1 to 500 parts by weight with respect to 100 parts by weight of the colorant, and more preferably 5 to 400 parts 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 unsaturated ketones typified by chalcone derivatives and dibenzalacetone, 1,2-diketone derivatives typified by 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, tetraphyrin derivatives, annulene derivatives, spiropyran derivatives, spirooxazine Derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes, Michler's ketone derivatives and the like.
These sensitizers can be used singly or in combination of two or more at any ratio as necessary.

Specific examples include Okawara Nobu et al., “Dye Handbook” (1986, Kodansha), Okawara Nobu et al., “Functional Dye Chemistry” (1981, CMC), Ikemori Chusaburo et al., “Special Examples include, but are not limited to, sensitizers described in “Functional Materials” (1986, CMC). In addition, a sensitizer that absorbs light from the ultraviolet region to the near infrared region can also be contained.
Among the sensitizers, particularly preferred sensitizers include thioxanthone derivatives, Michler ketone derivatives, and carbazole derivatives. More specifically, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 4,4′-bis (Dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (ethylmethylamino) benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, 3,6-dibenzoyl- N-ethylcarbazole or the like is used.

  The content of the sensitizer is preferably 3 to 60 parts by weight with respect to 100 parts by weight of the photopolymerization initiator contained in the colored composition, and 5 to 50 parts by weight from the viewpoint of photocurability and developability. It is more preferable that

《Oxygen-reducing amine compound》
In addition, the colored composition 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 colored composition 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 content is preferably 0.003 to 0.5% by weight based on the total weight of the 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 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 colored composition of the present invention can contain a storage stabilizer in order to stabilize the viscosity of the composition over time. 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 parts by weight with respect to 100 parts by weight of the colorant (A) in the coloring composition.

  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 parts by weight, preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the total amount of the colorant in the coloring composition.

<< Method for Producing Colored Composition for Color Filter >>
The coloring composition for a color filter of the present invention contains a coloring agent, if necessary, in a coloring agent carrier such as a binder resin (B) and / or a solvent, if necessary, and a dispersing aid if necessary. Together with a kneader, a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, or an attritor and the like. Agent dispersion). At this time, as for the colorant, two or more kinds of colorants are simultaneously colored for the resin salt-forming compound (A1), the colorant (A2), the blue pigment (A4) used as necessary, and the colorant (A3). You may disperse | distribute to an agent support | carrier and may mix what was disperse | distributed to a coloring material support | carrier separately.
When the solubility of the colorant such as a dye is high, specifically, it is highly soluble in the solvent to be used, and if it is dissolved and no foreign matter is confirmed by stirring, it is finely dispersed as described above. There is no need.

  Moreover, when using as a photosensitive coloring composition (resist material) for color filters, it can prepare as a solvent developing type or an alkali developing type coloring composition. The solvent development type or alkali development type coloring composition includes the colorant dispersion, a photopolymerizable monomer and / or a photopolymerization initiator, and, if necessary, a solvent, other pigment dispersants, and additives. Etc. can be mixed and adjusted. The photopolymerization initiator may be added at the stage of preparing the colored composition, or may be added later to the prepared colored composition.

<Dispersing aid>
When the colorant (A) is dispersed in the colorant carrier, a dispersion aid such as a resin-type dispersant and a surfactant can be appropriately used. Since the dispersion aid is excellent in dispersing the pigment component in the colorant (A) and has a great effect of preventing re-aggregation of the colorant after dispersion, the colorant (A) is used as a colorant carrier using the dispersion aid. When a blue coloring composition dispersed therein is used, a color filter having a high spectral transmittance can be obtained.

(Resin type dispersant)
The resin-type dispersant has a colorant affinity part having a property of adsorbing to a colorant, particularly a pigment, and a part compatible with the colorant carrier, and adsorbs to the colorant to provide a colorant carrier for the colorant. It works to stabilize dispersion in the water. Specific examples of resin-type dispersants include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamine salts. , Polysiloxane, long-chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, modified products thereof, amides formed by reaction of poly (lower alkyleneimine) and polyester having a free carboxyl group, and salts thereof Oil-soluble dispersants such as, (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, etc. Resin, water-soluble polymer, polyester, modified poly Acrylate-based, ethylene oxide / propylene oxide addition compound, phosphate ester-based and the like are used, it can be used alone or in admixture of two or more.

  Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, and 170 manufactured by Big Chemie Japan. 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155 or Anti-Terra-U, 203, 204, or BYK- P104, P104S, 220S, 6919, or SOLPERSE-3000, 9000, 13000, 13240, 13650, 13940, 1600 manufactured by Nihon Lubrizol Corporation, such as Lactimon, Lactimon-WS, or Bykumen. 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc., BASF Manufactured by EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 101,120,150,1501,1502,1503, etc., Ajinomoto Fine-Techno Co., Ltd. of AJISPER PA111, PB711, PB821, PB822, PB824, and the like.

(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 Anionic surfactants such as lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate; Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Nonionic surfactants such as alkyl ether phosphates, polyoxyethylene sorbitan monostearate and polyethylene glycol monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyldimethylamino Examples include amphoteric surfactants such as alkylbetaines such as betaine acetate and alkylimidazolines, and these may be used alone or in admixture of two or more, but are not necessarily limited thereto.

  When a resin-type dispersant and a surfactant are added, the total amount of the colorant (A) is preferably 0.1 to 55% by weight, more preferably 0.1 to 45% by weight based on the total amount (100% by weight). %. When the blending amount of the resin type dispersant and the surfactant is less than 0.1% by weight, it is difficult to obtain the added effect. When the blending amount is more than 55% by weight, the dispersion is affected by an excessive dispersant. May affect.

<Removal of coarse particles>
The colored composition for a color filter of the present invention is 5 μm or more coarse particles, preferably 1 μm or more coarse particles, more preferably 0.5 μm or more coarse particles by means of centrifugation, sintered filter, membrane filter or the like. 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. Moreover, here, it can confirm using the particle size distribution measuring apparatus "Nano-S (Sysmex Corporation)" using the dynamic light scattering method.

《Color filter》
Next, the color filter of the present invention will be described.
The color filter of the present invention preferably includes a red filter segment, a green filter segment, and a blue filter segment on a substrate, and further includes a magenta filter segment, a cyan filter segment, or a yellow filter segment. The at least 1 filter segment may be formed from the coloring composition of the present invention.
Particularly preferably, the blue filter segment is formed by the color filter coloring composition of the present invention.

  As the filter segment other than the filter segment formed from the colored composition of the present invention, a conventionally known colorant can be used and those obtained by a conventionally known method can be used.

  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, 168, 169, 177, 178, 184, 185, 187, 200, 202, 208, 210, 242, 246, 254, 255, 264, 270, 272, 273, 274, 276, 277, 278, 279, 280, Red pigments such as 281, 282, 283, 284, 285, 286, or 287 are used. In addition, a basic dye that exhibits a red color, or a resin salt-forming compound of an acidic dye can also be used.

  The red coloring composition includes C.I. I. Pigment orange 43, 71, 73 or the like 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. Further, a basic salt of orange and / or yellow, or a resin salt-forming compound of an acid dye 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, 82,185,187,188,193,194,198,199,213,214,218,219,220, or it can be mentioned yellow pigment 221, and the like. Further, a basic dye having a yellow color and a resin salt-forming compound of an acidic dye can be used in combination.

  The blue filter segment can be formed using a normal blue coloring composition containing a blue pigment and a colorant carrier. Examples of blue pigments include C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64 or the like is used.

  In addition, C.I. I. Purple pigments such as CI Pigment Violet 23, C.I. I. A metal lake pigment of a rhodamine dye such as CI Pigment Red 81, 81: 1, 81: 2, 81: 3, 81: 4, 81: 5 can be used in combination. Also, basic dyes exhibiting blue or purple, acidic dyes, salt forming compounds of acidic dyes, and the like can be used.

《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 blue coloring composition of the present invention prepared as a printing ink. Excellent in 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 a photolithography method, a 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 formed on a substrate such as a transparent substrate. By a coating method such as spray coating, spin coating, slit coating, or roll coating, 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 based on examples, but the present invention is not limited thereto. Unless otherwise specified, “parts” means “parts by weight”.

  Also, the weight average molecular weight (Mw) of the resin, the specific surface area of the pigment, the average primary particle diameter of the pigment particles, the ammonium salt value of the resin having a cationic group in the side chain, the peak wavelength λmax of the colorant, and the contrast of the coating film The ratio measurement method and the colorant (A2) and colorant (A3) identification method are as follows.

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

(Specific surface area of pigment)
The specific surface area of the pigment was measured by an automatic vapor adsorption amount measuring apparatus (“BELSORP18” manufactured by Nippon Bell Co., Ltd.) using the nitrogen adsorption BET method.

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

(Ammonium salt value of a resin having a cationic group in the side chain)
The ammonium salt value of the resin having a cationic group in the chain is a value converted to an equivalent of potassium hydroxide after being obtained by titration with a 0.1N silver nitrate aqueous solution using a 5% potassium chromate aqueous solution as an indicator, The ammonium salt value of solid content is shown.

(Peak wavelength λmax (maximum absorption wavelength) of the colorant)
The method for measuring the peak wavelength λmax of each colorant is that a colorant dispersion solution or a colorant solution is formed on a glass substrate by spin coating, and this is measured with a spectroscope (absorption spectrophotometer V-570 manufactured by JASCO Corporation). The wavelength position of the maximum value in the visible light region was determined from the measured Absorbance data. In addition, as in the case of the colorant (A2-2), when the visible portion has another absorption peak with an intensity within 70% with respect to the maximum absorption peak of the maximum absorption value, this absorption also affects the fluorescence emission. Therefore, the peak wavelength λmax is set.

(Contrast ratio of coating film)
The light emitted from the backlight unit for liquid crystal display passes through the polarizing plate, is polarized, passes through the dried coating film of the colored composition applied on the glass substrate, and reaches the polarizing plate. If the polarizing planes of the polarizing plate and the polarizing plate are parallel, light is transmitted through the polarizing plate, but if the polarizing plane is perpendicular, the light is blocked by the polarizing plate. However, when the light polarized by the polarizing plate passes through the dried coating film of the colored composition, scattering by the pigment particles occurs, resulting in deviation in a part of the polarization plane. When the amount of light transmitted through the plate is reduced and the polarizing plate is perpendicular, a part of the light is transmitted through the polarizing plate. This transmitted light was measured as the luminance on the polarizing plate, and the ratio (contrast ratio) between the luminance when the polarizing plate was parallel and the luminance when it was orthogonal was calculated.

(Contrast ratio) = (Luminance when parallel) / (Luminance when direct)
Accordingly, when scattering occurs due to the pigment in the coating film, the brightness when parallel is reduced and the brightness when perpendicular is increased, the contrast ratio is lowered.

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

(Identification method of coloring agent (A2) and coloring agent (A3))
The identification of the compound is carried out by the agreement between the molecular ion peak of the mass spectrum obtained using the time-of-flight mass spectrometer autoflex III (TOF-MS) manufactured by Bruker Daltonics, and the mass number obtained by calculation. The ratio of carbon, hydrogen and nitrogen obtained using an Elmer 2400CHN elemental analyzer was matched with the theoretical value.

  Subsequently, binder resin solutions, fine pigments, pigment dispersions, resins having a cationic group in the side chain, a colorant (A2), and a method for producing the colorant (A3) used in Examples and Comparative Examples, It demonstrates from the solubility measurement result of a coloring agent (A2) and a coloring agent (A3), and the manufacturing method of the red and green resist material used at the time of color filter preparation.

<Method for producing binder resin solution>
(Method for producing alkali-soluble photosensitive resin (B1))
[Binder resin solution (B1-1)]
Place 100 parts of propylene glycol monomethyl ether acetate in a reaction vessel equipped with a thermometer, cooling tube, nitrogen gas inlet tube and stirrer in a separable four-necked flask, and heat to 120 ° C while injecting nitrogen gas into the vessel A mixture of 5.2 parts of styrene, 35.5 parts of glycidyl methacrylate, 41.0 parts of dicyclopentanyl methacrylate, and 1.0 part of azobisisobutyronitrile was dropped over 2.5 hours from the dropping tube at a temperature to polymerize. Reaction was performed.
Next, the inside of the flask was purged with air, and 0.3 part of trisdimethylaminomethylphenol and 0.3 part of hydroquinone were added to 17.0 parts of acrylic acid, and the reaction was continued at 120 ° C. for 5 hours. The reaction was terminated when it reached 0.8, and a resin solution having a weight average molecular weight of about 12000 (measured by GPC) was obtained.
Further, 30.4 parts of tetrahydrophthalic anhydride and 0.5 part of triethylamine were added and reacted at 120 ° C. for 4 hours. Propylene glycol monomethyl ether acetate was added so that the nonvolatile content was 20%, and a binder resin solution (B1-1 )

[Binder resin solution (B1-2)]
The binder resin solution (B1-2) is synthesized by the same method as the binder resin solution (B1-1) except that dicyclopentanyl methacrylate in the binder resin solution (B1-1) is changed to dicyclopentenyl methacrylate. Got. The weight average molecular weight was 12500.

[Binder resin solution (B1-3)]
A separable four-necked flask equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe and a stirring device was charged with 370 parts of propylene glycol monomethyl ether acetate, heated to 80 ° C., and the flask was purged with nitrogen, and then dropped. From the tube, 18 parts of paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 10 parts of benzyl methacrylate, 18.2 parts of glycidyl methacrylate, 25 parts of methyl methacrylate, and 2,2′-azobisisobutyro A mixture of 2.0 parts of nitrile was added dropwise over 2 hours. After dropping, the reaction was further carried out at 100 ° C. for 3 hours, and then 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 100 ° C. for 1 hour. Next, the inside of the container was replaced with air, 0.5 parts of trisdimethylaminophenol and 0.1 part of hydroquinone were added to 9.3 parts of acrylic acid (equivalent of glycidyl group), and 6 parts at 120 ° C. The reaction was continued for a period of time, and the reaction was terminated when the acid value of the solid content reached 0.5 to obtain an acrylic resin solution. Further, 19.5 parts of tetrahydrophthalic anhydride (equivalent of the generated hydroxyl group) and 0.5 parts of triethylamine were added and reacted at 120 ° C. for 3.5 hours to obtain an acrylic resin solution.
After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. Propylene glycol monomethyl ether so that the nonvolatile content of the previously synthesized resin solution was 20% by weight Acetate was added to obtain a binder resin solution (B1-3). The weight average molecular weight (Mw) was 19000.

[Binder resin solution (B1-4)]
The binder resin solution (B1-3) is subjected to a synthesis reaction in the same manner as the binder resin solution (B1-1) except that the dicyclopentanyl methacrylate in the binder resin solution (B1-1) is changed to n-decyl methacrylate. Got. The weight average molecular weight was 12800.

(Method for producing alkali-soluble non-photosensitive resin solution)
[Binder resin solution (B2-1)]
70.0 parts of propylene glycol monomethyl ether acetate was charged into a separable four-necked flask equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe and a stirrer, the temperature was raised to 80 ° C., and the inside of the reaction vessel was purged with nitrogen After that, 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.) ) A mixture of 7.4 parts and 0.4 part of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain an acrylic resin solution having a solid content of 30% by weight and a weight average molecular weight of 26000.
After cooling to room temperature, about 2 g of resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. Acetate was added to obtain a binder resin solution (B2-1).

<Production method of fine pigment>
(Blue fine pigment (A4-1))
Phthalocyanine blue pigment C.I. I. Pigment Blue 15: 6 (“LIONOL BLUE ES” manufactured by Toyocolor Co., Ltd.) 200 parts, sodium chloride 1400 parts, and diethylene glycol 360 parts were charged in a stainless steel 1 gallon kneader (Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. . Next, the kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of a blue fine pigment (A4-1) were obtained. The specific surface area of the blue fine pigment (A4-1) was 80 m ² / g, and the average primary particle size by TEM observation was 50 nm.

(Red fine pigment)
Diketopyrrolopyrrole red pigment C.I. I. 200 parts of Pigment Red 254 (“IRGAZIN RED L 3660 HD” manufactured by BASF), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of a red fine pigment were obtained. The specific surface area of the red fine pigment was 65 m ² / g, and the average primary particle size by TEM observation was 54 nm.

(Green fine pigment)
Phthalocyanine green pigment C.I. I. 200 parts of Pigment Green 36 (“Lionol Green 6YK” manufactured by Toyocolor Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, this kneaded product is put into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of a green fine pigment were obtained. The specific surface area of the green fine pigment was 75 m ² / g, and the average primary particle size by TEM observation was 51 nm.

(Yellow fine pigment 1)
Isoindoline yellow pigment C.I. I. 500 parts of Pigment Yellow 139 (BASF “Pariotor Yellow D1819”), 500 parts of sodium chloride and 250 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 120 ° C. for 8 hours. Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 490 parts of yellow fine pigment 1 were obtained. The specific surface area of the yellow fine pigment 1 was 80 m < ² > / g, and the average primary particle diameter by TEM observation was 49 nm.

(Yellow fine pigment 2)
Nickel complex yellow pigment C.I. I. 200 parts of Pigment Yellow 150 (“E-4GN” manufactured by LANXESS), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of yellow fine pigment 2 were obtained. The specific surface area of the yellow fine pigment 2 was 70 m ² / g, and the average primary particle size by TEM observation was 53 nm.
there were.

(Purple fine pigment)
Dioxazine-based purple pigment C.I. I. 200 parts of Pigment Violet 23 (“LIONOGEN VIOLET RL” manufactured by Toyocolor Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, this kneaded product is put into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of a violet fine pigment were obtained. The specific surface area of the purple fine pigment was 95 m ² / g, and the average primary particle size by TEM observation was 45 nm.
there were.

<Method for producing pigment dispersion>
(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. And a pigment dispersion (DP-1) was produced.

Blue fine pigment (A4-1): 11.0 parts (CI Pigment Blue 15: 6)
Binder resin solution (B2-1): 40.0 parts Resin type dispersant: 1.0 part ("EFKA4300" manufactured by BASF)
Solvent: 48.0 parts (propylene glycol monomethyl ether acetate)

(Pigment dispersion (DP-2 to 6))
Hereinafter, pigment dispersions (DP-2 to 6) were prepared in the same manner as the pigment dispersion (DP-1) except that the pigments were changed to the pigments shown in Table 1.

<Method for Producing Resin (a1) Having Cationic Group in Side Chain>
(Resin having a cationic group in the side chain (a1-1))
74.1 parts of isopropyl alcohol was charged into a four-necked separable flask equipped with a thermometer, a stirrer, a distillation tube, and a condenser, and the temperature was raised to 75 ° C. under a nitrogen stream. Separately, 33.2 parts of methyl methacrylate, 27.3 parts of n-butyl methacrylate, 27.3 parts of 2-ethylhexyl methacrylate, 12.2 parts of dimethylaminoethylmethyl chloride methacrylate, and 15.6 parts of methyl ethyl ketone were homogenized. Thereafter, the mixture was placed 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 7420, and the mixture was cooled to 50 ° C. Thereafter, 72 parts of isopropyl alcohol was added to obtain a resin (a1-1) having a cationic group in the side chain of 40% by weight of the resin component. The ammonium salt value of the obtained resin was 33 mgKOH / g.

(Resin having a cationic group in the side chain (a1-2))
74.1 parts of isopropyl alcohol was charged into a four-necked separable flask equipped with a thermometer, a stirrer, a distillation tube, and a condenser, and the temperature was raised to 75 ° C. under a nitrogen stream. Separately, 15.7 parts of methyl methacrylate, 27.3 parts of n-butyl methacrylate, 27.3 parts of 2-ethylhexyl methacrylate, 12.2 parts of dimethylaminoethyl methyl chloride salt, 15.0 parts of hydroxyethyl methacrylate, methacrylic acid After 2.5 parts and 15.6 parts of methyl ethyl ketone were made uniform, they were charged into 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 7420, and the mixture was cooled to 50 ° C. Thereafter, 72 parts of isopropyl alcohol was added to obtain a resin (a1-2) having a cationic group in the side chain of 40% by weight of the resin component. The ammonium salt value of the obtained resin was 33 mgKOH / g.

<Method for producing resin salt-forming compound (A1)>
The peak wavelength λmax1 (maximum absorption wavelength) of the resin salt-forming compound (A1) was determined as follows.
[Peak wavelength λmax1 (maximum absorption wavelength) of resin salt-forming compound (A1)]
Using a colorant-treated solution obtained by ultrasonic dissolution treatment with the following composition, a film was formed on a glass substrate by spin coating, and this was measured with a spectroscope (Nippon Bunko spectrophotometer V-570). It was calculated | required as a wavelength position of the maximum value of a visible region from the obtained Absorbance data.

Resin salt forming compound (A1): 0.8 part Binder resin solution (B2-1): 50.0 parts Resin-type dispersant: 2.0 parts ("EFKA4300" manufactured by BASF)
Solvent: 50.0 parts (propylene glycol monomethyl ether acetate)

(Resin salt forming compound (A1-1))
In the following procedure, C.I. I. A resin salt-forming compound (A1-1) comprising Acid Red 52 and a resin (a1-1) having a cationic group in the side chain was produced.
The resin (a1-1) having 51 parts of a cationic group was added to 2000 parts of water, and after sufficiently stirring and mixing, the mixture was heated to 60 ° C. On the other hand, 10 parts of C.I. in 90 parts of water. I. An aqueous solution in which Acid Red 52 was dissolved was prepared and added dropwise little by little to the previous resin solution. After dropping, the mixture was stirred at 60 ° C. for 120 minutes to sufficiently react. In order to confirm the end point of the reaction, it was judged that the resin 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. The mixture was allowed to cool to room temperature with stirring, filtered with suction, washed with water, and the resin salt compound remaining on the filter paper was dried by removing moisture with a dryer. I. A resin salt-forming compound (A1-1) between Acid Red 52 and a resin (a1-1) having a cationic group in the side chain was obtained. At this time, C.I. in the resin salt-forming compound (A1-1). I. The content of the effective pigment component derived from Acid Red 52 was 25% by weight.
The peak wavelength λmax1 of the resin salt-forming compound (A1-1) was 561 nm.

(Resin salt forming compound (A1-2))
In the following procedure, C.I. I. A resin salt-forming compound (A1-2) comprising Acid Red 52 and a resin (a1-2) having a cationic group in the side chain was produced.
The resin (a1-2) having 51 parts of a cationic group was added to 2000 parts of water, and after sufficiently stirring and mixing, the mixture was heated to 60 ° C. On the other hand, 10 parts of C.I. in 90 parts of water. I. An aqueous solution in which Acid Red 52 was dissolved was prepared and added dropwise little by little to the previous resin solution. After dropping, the mixture was stirred at 60 ° C. for 120 minutes to sufficiently react. In order to confirm the end point of the reaction, it was judged that the resin 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. The mixture was allowed to cool to room temperature with stirring, filtered with suction, washed with water, and the resin salt compound remaining on the filter paper was dried by removing moisture with a dryer. I. Resin salt-forming compound (A1-2) between acid red 52 and resin (a1-2) having a cationic group in the side chain was obtained. At this time, C.I. in the resin salt-forming compound (A1-2). I. The content of the effective pigment component derived from Acid Red 52 was 25% by weight.
The peak wavelength λmax1 of the resin salt-forming compound (A1-2) was 562 nm.

(Resin salt forming compound (A1-3))
In the following procedure, C.I. I. A resin salt-forming compound (A1-3) comprising Acid Red 289 and a resin (a1-1) having a cationic group in the side chain was produced.
The resin (a1-1) having a cationic group in the side chain of 88 parts was added to 2000 parts of a 10% aqueous methanol solution, and after sufficiently stirring and mixing, the mixture was heated to 60 ° C. On the other hand, 10 parts of C.I. in 90 parts of water. I. An aqueous solution in which Acid Red 289 was dissolved was prepared and added dropwise to the previous resin solution little by little. After dropping, the mixture was stirred at 60 ° C. for 120 minutes to sufficiently react. In order to confirm the end point of the reaction, it was judged that the resin 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. The mixture was allowed to cool to room temperature with stirring, filtered with suction, washed with water, and the resin salt-forming compound remaining on the filter paper was dried by removing moisture with a dryer. I. Resin salt-forming compound (A1-3) with Acid Red 289 and resin (a1-1) having a cationic group in the side chain was obtained. At this time, C.I. in the resin salt-forming compound (A1-3). I. The content of the effective pigment component derived from Acid Red 289 was 25% by weight.
The peak wavelength λmax1 of the resin salt-forming compound (A1-3) was 538 nm.

<Method for producing colorant (A2)>
The peak wavelength λmax2 (maximum absorption wavelength) of the colorant (A2) was determined as follows.
[Peak wavelength λmax2 (maximum absorption wavelength) of colorant (A2)]
Using a colorant-treated solution obtained by ultrasonic dissolution treatment with the following composition, a film was formed on a glass substrate by spin coating, and this was measured with a spectroscope (Nippon Bunko spectrophotometer V-570). It was calculated | required as a wavelength position of the maximum value of a visible region from the obtained Absorbance data.
Since the colorant (A2-2) strongly shows two absorptions in the visible part, both wavelength positions are described as the peak wavelength λmax2.

Colorant (A2): 0.2 parts Binder resin solution (B2-1): 50.0 parts Resin-type dispersant: 2.0 parts ("EFKA4300" manufactured by BASF)
Solvent: 50.0 parts (propylene glycol monomethyl ether acetate)

<< Method for Producing Colorant (A2-1) >>
The colorants (A2-1-1) to (A2-1-7) were synthesized based on the following references.

(Reference 9) JP 2002-129052 (Reference 10) JP 2006-321925 (Reference 11) JP 2007-099744 (Reference 12) JP 2007-186708 (Reference) Reference 13) Japanese Patent Application Laid-Open No. 2012-121821

(Colorant (A2-1-1))
The colorant (A2-1-1) was obtained by synthesizing by the synthesis method of Example 8 replaced with the raw material obtained by the synthesis method of Reference 11 and Example 4. A typical example of the isomer structure of the colorant (A2-1-1) is shown below.

Colorant (A2-1-1)

(Colorant (A2-1-2))
The colorant (A2-1-2) was obtained by synthesis using Reference 9 and the synthesis method of Synthesis Example 1.

(Colorant (A2-1-3))
By the synthesis method of Reference Document 10, Example 1 and Example 3, cupric chloride was replaced with palladium chloride and synthesized to obtain a colorant (A2-1-3).

(Colorant (A2-1-4))
The colorant (A2-1-4) was obtained by replacing the cuprous chloride with palladium chloride by the synthesis methods of Reference 13, Example 4, and Example 10.

(Colorant (A2-1-5))
The colorant (A2-1-5) was obtained by synthesis by the synthesis method of Reference Document 13, Example 4 and Example 10.

(Colorant (A2-1-6))
The colorant (A2-1-6) was obtained by synthesizing by the synthesis method of Example 10 replaced with the raw material obtained by the synthesis method of Reference 13 and Example 6.

(Colorant (A2-1-7))
The colorant (A2-1-7) was obtained by synthesizing by the synthesis method of Example 10 replaced with the raw material obtained by the synthesis method of Reference 13 and Example 5.

  Table 2 shows the specific chemical structure and peak wavelength λmax2 (maximum absorption wavelength) corresponding to the general formula (2) of the colorants (A2-1-1) to (A2-1-7).

The substituents of R ²¹ and R ²² may be interchanged. The same applies to R ²³ and R ²⁴ , R ²⁵ and R ²⁶ , R ²⁷ and R ²⁸ , and the colorant (A2-1) may be a mixture of isomers having different configurations.

<< Method for Producing Colorant (A2-2) >>
The colorants (A2-2-1) to (A2-2-7) were synthesized based on the following references.

(Reference 14) JP2012-093696A

(Colorant (A2-2-1))
In the synthesis method of Reference Document 14 and Compound (13), 2-ethylhexylamine was replaced with tetrahydrofurfurylamine and synthesized to obtain a colorant (A2-2-1).

(Colorant (A2-2-2))
In the synthesis method of Reference Document 10, Reference Document 14, and Compound (13), Compound (13A) was converted to C.I. I. The solvent was changed to Solvent Blue 104 (Polysynthrene Blue RBL P; manufactured by Clariant) and synthesized by replacing 2-ethylhexylamine with n-decylamine to obtain a colorant (A2-1-2) represented by the following chemical formula.

Colorant (A2-2-2)

(Colorant (A2-2-3))
In Reference 14, the method for synthesizing compound (13), compound (13A) was converted to C.I. I. The solvent was changed to Solvent Blue 104 (Polysynthesis Blue RBL P; manufactured by Clariant), and 2-ethylhexylamine was replaced with 3-methoxypropylamine to synthesize, thereby obtaining a colorant (A2-1-3).

(Colorant (A2-2-4))
C. I. Solvent Blue 104 (Polysynthesis Blue RBL P; manufactured by Clariant) was used as a colorant (A2-2-4).

(Colorant (A2-2-5))
C. I. Solvent Blue 45 (Savinyl Blue RS; manufactured by Clariant) was used as a colorant (A2-2-5).

(Colorant (A2-2-6))
C. I. Solvent Blue 35 (Sudan Blue II; manufactured by Aldrich) was used as a colorant (A2-2-6).

(Colorant (A2-2-7))
In Reference 14, the method for synthesizing compound (13), compound (13A) was converted to C.I. I. The solvent was changed to Solvent Blue 104 (Polysynthrene Blue RBL P; manufactured by Clariant), and 2-ethylhexylamine was replaced with 2- (2-methoxyphenoxy) ethylamine for synthesis to obtain a colorant (A2-1-7).

<Method for producing colorant (A3)>
A method for producing the colorants (A3-1-1) to (A3-1-5) is shown below. These specific substance names and chemical structures are shown in Table 4.
The peak wavelength λmax (maximum absorption wavelength) of the colorant (A3) was determined as follows.
[Peak wavelength λmax (maximum absorption wavelength) of colorant (A3)]
The following mixture is stirred and mixed to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250MKII” manufactured by Eiger Japan) at 25 ° C. for 1 hour using zirconia beads having a diameter of 0.5 mm. Using the obtained colorant treatment liquid, a film was formed on a glass substrate by spin coating, and this was the maximum in the visible light region from Absorbance data measured with a spectroscope (absorption spectrophotometer V-570 manufactured by JASCO Corporation). It was determined as the wavelength position of the value.
Since the colorant (A3) strongly shows two absorptions in the visible part, both absorption wavelength positions are shown as a peak wavelength λmax3.

Colorant (A3): 0.2 parts Binder resin solution (B2-1): 50.0 parts Resin-type dispersant: 2.0 parts ("EFKA4300" manufactured by BASF)
Solvent: 50.0 parts (propylene glycol monomethyl ether acetate)

(Colorant (A3-1-1))
Copper phthalocyanine sulfonic acid amide compound: 30 parts of copper phthalocyanine was charged in 300 parts of chlorosulfonic acid and completely dissolved, then 24 parts of thionyl chloride was added, and the temperature was gradually raised and reacted at 101 ° C. for 3 hours. The reaction solution was poured into 9000 parts of ice water, stirred, filtered and washed with water. The obtained press cake was made into a slurry with 300 parts of water, then 15 parts of N, N-dimethylaminopropylamine was added, and the mixture was stirred at room temperature for 3 hours, then at 60 ° C. for 2 hours, filtered, washed with water and dried. , 36 parts of a copper phthalocyanine sulfonic acid amide compound (A3-1-1) was obtained. The obtained copper phthalocyanine sulfonic acid amide compound (A3-1-1) was subjected to a composition analysis using a liquid chromatograph mass spectrometer platform LCZ manufactured by Waters, and it did not include those having three or more substituents. Copper phthalocyanine sulfonic acid amide compound (A3-1-1-D1) having one substituent of the following general formula (14) and copper phthalocyanine sulfonic acid amide compound having two substituents of the following general formula (14) ( A3-1-1 -D2), each having a weight ratio of 85:15.
General formula (14)

(Coloring agents (A3-1-2) to (A3-1-4))
Copper phthalocyanine sulfonic acid amide compound; N, N-dimethylaminopropylamine, which is a raw material used in the method for producing the colorant (A3-1-1), was changed to the raw material shown in Table 4 above, In the same manner as in A3-1-1), colorants (A3-1-2) to (A3-1-4), which are copper phthalocyanine sulfonic acid amide compounds, were obtained.

(Colorant (A3-1-5))
Zinc phthalocyanine sulfonic acid amide compound: 30 parts of zinc phthalocyanine was charged in 300 parts of chlorosulfonic acid and completely dissolved, then 24 parts of thionyl chloride was added, and the temperature was gradually raised and reacted at 101 ° C. for 3 hours. The reaction solution was poured into 9000 parts of ice water, stirred, filtered and washed with water. The obtained press cake was made into a slurry with 300 parts of water, then 15 parts of N, N-dimethylaminopropylamine was added, and the mixture was stirred at room temperature for 3 hours, then at 60 ° C. for 2 hours, filtered, washed with water and dried. Zinc phthalocyanine sulfonic acid amide compound; 36 parts of a colorant (A3-1-5) were obtained. The obtained zinc phthalocyanine sulfonic acid amide compound was subjected to a composition analysis using a liquid chromatograph mass spectrometer platform LCZ manufactured by Waters. The compound having 3 or more substituents was not included, and the following general formula (15) It is a mixture of a colorant (A3-1-5-D1) having one substituent and a colorant (A3-1-5-D2) having two substituents of the following general formula (15), each weight The ratio was 80:20.
General formula (15)
_{ZnPc - (- SO 2 NH -} (- CH 2) 3 -N (CH 3) 2) m
m = 1, 2
Meaning of Abbreviations in General Formula (15) ZnPc: Zinc Phthalocyanine Residue

Meanings of Abbreviations in Table 4 CuPc: Copper phthalocyanine residue ZnPc: Zinc phthalocyanine residue

<Solubility of Colorant (A2) and Colorant (A3)>
The solubility of the colorant (A2) and the colorant (A3) is as follows. First, the colorant (A2) or the colorant (A3) is blended at a ratio of 1 part to 100 parts of the organic solvent (propylene glycol monomethyl ether acetate). Sonication was performed. When completely dissolved, the blending amount of the colorant was increased until precipitation was observed after sonication, and an sonication liquid was prepared. The treated liquid is filtered through a 0.2 micron membrane filter (PTFE), and the weighed filtrate is evaporated to dryness at 200 ° C. for 30 minutes and weighed again. The solubility was calculated as

The obtained results are shown in Table 5 below.

<Method for producing red and green resist materials>
(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-2): 50.0 parts Pigment dispersion (DP-4): 10.0 parts Binder resin solution (B2-1): 11.0 parts Trimethylolpropane triacrylate: 4.2 parts ( Shin-Nakamura Chemical "NK ester ATMPT")
Photopolymerization initiator: 1.2 parts ("Irgacure 907" manufactured by BASF)
Sensitizer: 0.4 parts ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.)
Solvent: 23.2 parts (ethylene glycol monomethyl ether acetate)

(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-3): 45.0 parts Pigment dispersion (DP-5): 15.0 parts Binder resin solution (B2-1): 11.0 parts Trimethylolpropane triacrylate: 4.2 parts ( Shin-Nakamura Chemical "NK ester ATMPT")
Photopolymerization initiator: 1.2 parts ("Irgacure 907" manufactured by BASF)
Sensitizer: 0.4 parts ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.)
Solvent: 23.2 parts (ethylene glycol monomethyl ether acetate)

<Preparation of blue coloring composition>
[Example 1]
(Blue coloring composition (DB-1))
4. The following mixture is stirred and mixed so as to be uniform, and then dispersed for 5 hours with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm. A blue colored composition (DB-1) was produced by filtration through a 0 μm filter.

Pigment dispersion (DP-1): 100.0 parts Resin salt-forming compound (A1-1): 8.0 parts Colorant (A2-1-1): 0.5 parts Binder resin solution (B2-1): 22.0 parts resin-type dispersant: 2.0 parts ("EFKA4300" manufactured by BASF)
Solvent: 54.8 parts (propylene glycol monomethyl ether acetate)

[Examples 2-38]
(Blue coloring composition (DB-2 to 38))
Hereinafter, the pigment dispersion in the blue coloring composition (DB-1), the types of the pigment dispersion, the resin salt-forming compound, the coloring agent (A2), and the coloring agent (A3) shown in Table 6, and the blending amount (weight) Part), a blue colored composition (DB-2 to 38) was obtained in the same manner as the blue colored composition (DB-1) of Example 1 described above.

[Comparative Example 1]
(Blue coloring composition (DB-51))
The following mixture was treated in the same manner as (DB-1) to produce a color filter coloring composition (DB-51). This blending ratio matches the effective pigment component ratio in the resin salt-forming compound (A1-1) in (DB-1) with the dye simple substance ratio in (DB-51), and the side in (A1-1) The solid content of the binder resin solution (B2-1) corresponding to the resin ratio having a cationic group in the chain is increased.

Pigment dispersion (DP-1): 100.0 parts C.I. I. Acid Red 52 (Dye simple substance 1): 2.0 parts Colorant (A2-1-1): 0.6 parts Binder resin solution (B2-1): 52.0 parts Resin-type dispersant: 2.0 parts ( “EFKA4300” manufactured by BASF)
Solvent: 54.8 parts (propylene glycol monomethyl ether acetate)

[Comparative Examples 2 to 6]
(Blue coloring composition (DB-52-55))
Hereinafter, the pigment dispersion in the blue coloring composition (DB-51), the pigment dispersion shown in Table 6, the dye alone or the resin salt forming compound and the coloring agent (A2), the types of the coloring agent (A3), and the blending amount A blue colored composition (DB-52 to 55) was produced in the same manner as the blue colored composition (DB-51) of Comparative Example 1 except that the amount was changed to (parts by weight). The compounding composition of the blue coloring composition (DB-56) other than those described in Table 6 is the same as that of the blue coloring composition (DB-51).

  Moreover, the compounding quantity of the resin salt-forming compound (A1) described in Table 6 or the dye simple substance is for the effective pigment component, and the pigment effective component in the resin salt-forming compound (A1) is 25% by weight, The effective pigment component of the dye alone is 100% by weight.

Abbreviations in Table 6 are shown below.
(A2) / (A1) Effective pigment content (parts by weight)
= Content of colorant (A2) / effective pigment component amount of resin salt-forming compound (A1) (A3) / (A1) effective pigment content (parts by weight)
= Content of colorant (A3) / effective pigment component amount of resin salt-forming compound (A1)

Solubility ratio: Colorant (A2) / Colorant (A3)
The solubility ratio ([A3] / [A2]) of the solubility [A3] of the colorant (A3) in the organic solvent (C) and the solubility [A2] of the colorant (A2) in the organic solvent (C) is the following ( It calculated | required by Formula 1.

[Solubility ratio ([A3] / [A2])]
= [Solubility of Colorant (A3)] / [Solubility of Colorant (A2)] (Formula 1)

<Single dye>
Dye simple substance 1; C.I. I. Acid Red 52
Dye simple substance 2; C.I. I. Acid Red 289

[Evaluation of coloring composition for color filter]
The obtained blue coloring composition is formed on a glass substrate having a thickness of 100 mm × 100 mm and a thickness of 1.1 mm using a spin coater so that each film has a thickness such that y = 0.06 in a C light source. After coating, the substrate was heated at 230 ° C. for 20 minutes. Thereafter, the contrast ratio of the obtained substrate is shown in Table 6.

  In the coloring composition for a color filter of the present invention containing the resin salt-forming compound (A1) and the colorant (A2) as the colorant (A), the resin salt-forming compound (A1) is replaced with a single dye. High contrast ratios were shown for Comparative Examples 1 to 5 and Comparative Examples 5 and 6 not containing the colorant (A2). Especially, the coloring composition for color filters which combined the coloring agent (A3) showed especially high contrast ratio.

  In addition, when the colorant (A2-1-6, 7) or the colorant (colorant (A2-2-6, 7)) is used as the colorant (A2), the result is similar to the result of the example. In addition, the contrast ratio was high.

<Preparation of resist material>
[Examples 101 to 142, Comparative examples 101 to 106]
(Resist material (R-1))
The following mixture was stirred and mixed to be uniform, and then filtered through a 1.0 μm filter to obtain a resist material (R-1).

Blue coloring composition (DB-1): 60.0 parts Binder resin solution (B1-1): 11.6 parts Trimethylolpropane triacrylate: 3.6 parts ("NK ester ATMPT" manufactured by Shin-Nakamura Chemical Co., Ltd.)
Photopolymerization initiator: 1.2 parts ("Irgacure 907" manufactured by BASF)
Sensitizer: 0.4 parts ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.)
Solvent: 23.2 parts (propylene glycol monomethyl ether acetate)

[Examples 102 to 142, Comparative Examples 101 to 106]
(Resist material (R-2 to 42, 51 to 56))
Hereinafter, except that the blue coloring composition (DB-1) and the binder resin solution (B1-1) in the resist material (R-1) are changed to the blue coloring composition and the binder resin solution shown in Table 6, the resist material. In the same manner as (R-1), alkali-developable resist materials (R-2 to 42, 51 to 56) were obtained. Table 7 shows the compositions of the resist materials prepared in Examples 101 to 142 and Comparative Examples 101 to 106.

[Evaluation of resist material]
The color characteristics (brightness), contrast ratio, and heat resistance of the resist materials obtained in Examples and Comparative Examples were evaluated by the following methods. The results are shown in Table 7.

(Evaluation of color characteristics)
Each resist material was coated on a glass substrate to a thickness such that y = 0.06 for the blue resist material in a C light source, and this substrate was heated at 230 ° C. for 20 minutes. Thereafter, the brightness of the obtained substrate was measured with a microspectrophotometer (“OSP-SP200” manufactured by Olympus Optical Co., Ltd.).

(Contrast ratio evaluation)
The contrast ratio was measured using the same substrate on which the color characteristics were measured.

(Method of coating heat resistance test)
A resist material is applied on a transparent substrate so that the dry coating thickness is about 2.5 μm, and UV exposure is performed through a mask having a predetermined pattern, and then an alkali developer is sprayed to remove uncured portions. Thus, a desired pattern was formed. Then, after heating in an oven at 230 ° C. for 1 hour and allowing to cool, the chromaticity 1 (L * (1), a * (1), b * (1)) of the obtained coating film with a C light source is microspectrophotometric. Measurement was performed using a meter (“OSP-SP200” manufactured by Olympus Optical Co., Ltd.). Further, as a heat resistance test, the sample was heated in an oven at 250 ° C. for 1 hour, and chromaticity 2 (L * (2), a * (2), b * (2)) with a C light source was measured.
Using the measured color difference value, a chromaticity change ΔEab * was calculated by the following formula, and the heat resistance of the coating film was evaluated in the following four stages.

ΔE * ab = [[L * (2) −L * (1)] ² + [a * (2) −a * (1)] ² + [b * (2) −b * (1)] ² ] ^1/2
：: ΔE * ab is less than 1.5 ○: ΔE * ab is 1.5 or more and less than 3.0 Δ: ΔE * ab is 3.0 or more and less than 5.0 ×: ΔE * ab is 5.0 or more

Similar to the evaluation results of the colored composition, Examples 101 to 113, 133, and 134 containing the resin salt forming compound (A1) and the colorant (A2) as the colorant (A) are the resin salt forming compounds (A1). High contrast ratios were shown for Comparative Examples 101 to 105 in which the dye alone was replaced, and Comparative Examples 105 and 106 not containing the colorant (A2). Further, Examples 114 to 132 and 135 to 142 in which the colorant (A3) was combined with the colorant (A2) exhibited a higher contrast ratio and good heat resistance.
This is because the anionic dye (a2) is ion-bonded to a pair of molecules for each cationic group of the resin (a1) having a cationic group in the side chain so that each anionic dye does not associate with each other. In the film, it can be uniformly distributed in the resin matrix, and it is considered that the colorant (A2) can directly quench the fluorescence emitted from the anionic dye into the resin matrix. Since the colorant (A2) is easily soluble, it is easily distributed uniformly in the resin matrix, and is suitable for efficiently obtaining this quenching effect.

  On the other hand, since the colorant (A3) is less soluble than the colorant (A2), it is considered that the colorant (A3) is likely to exist in the vicinity of the pigment in the pigment dispersion film. Therefore, it seems that it is suitable for quenching fluorescence emission when it is scattered on the pigment surface in the pigment dispersion film. Since the colorant (A2) and the colorant (A3) having different distributions in the pigment dispersion film can quench the fluorescence emission from the xanthene dye with high synergistic effect with each other, the cross luminance is extremely low. As a result, it is considered that the contrast ratio is improved.

  Furthermore, the solubility ratio ([A3] / [A2]) of the solubility [A3] of the colorant (A3) in the organic solvent (C) and the solubility [A2] of the colorant (A2) in the organic solvent (C) is 10 % Of the coloring compositions for color filters of Examples 114 to 121 and 123 to 132 having a solubility ratio of 10% or more due to the interaction between the coloring agent (A2) and the coloring agent (A3). The result was a higher contrast ratio.

  The color filters of Examples 101 to 105 and 108 to 113 in which the content of the colorant (A2) is 0.03 to 0.5 parts by weight with respect to 1 part by weight of the effective pigment component of the resin salt-forming compound (A1). The coloring composition for coloring has less influence on the color characteristics of the blue coating film of the colorant (A3), and is superior in brightness and heat resistance than Example 107 larger than this range, and Example 106 smaller than this range. As a result, the contrast ratio was high because of its superior ability to suppress fluorescence.

  Furthermore, Examples 114-121, 123, 125, 126 whose content of a coloring agent (A3) is 0.2-1.2 weight part with respect to 1 weight part of effective pigment components of a resin salt-forming compound (A1). The coloring compositions for color filters of Nos. 129 to 132 have a small influence on the color characteristics of the blue coating film of the colorant (A3), and are superior in brightness and heat resistance than Example 128, which is larger than this range. Since the ability to suppress fluorescence was superior to Example 124, which was smaller than the range, the result was a high contrast ratio.

  Moreover, the coloring composition for color filters of Examples 114-121, 123, 125, 126, 129-132 whose weight compounding ratio of a coloring agent (A2) and a coloring agent (A3) is 5: 95-90: 10. Was better than Example 127, which is outside this range, in suppressing fluorescence and having a higher contrast ratio.

  Further, for the color filters of Examples 114 to 121, 123, 125, 126, and 129 to 132 using the binder resin solutions (B1-1) and (B1-2) in which the binder resin component (B) includes a dicyclo ring structure. The coloring composition was superior in heat resistance and lightness from Examples 140 to 142 using the binder resin solutions (B1-3), (B1-4), and (B2-1) not containing this. This is considered to be due to the effect that the dicyclo ring structure in the binder resin has an affinity for the resin salt-forming compound (A1) and makes the pigment dispersion film homogeneous and tight.

  In addition, when the colorant (A2-1-6, 7) or the colorant (colorant (A2-2-6, 7)) is used as the colorant (A2), the result is similar to the result of the example. In addition, the color characteristics (brightness), contrast ratio, and heat resistance were excellent.

  From these results, it has been clarified that the resist material using the colored composition of the present invention can provide excellent quality having all of color characteristics (brightness), contrast ratio, and heat resistance.

<Production of color filter>
[Example 201]
(Color filter (CF-1))
A black matrix is patterned on a glass substrate, and a red resist material is applied on the substrate with a spin coater in a C light source (hereinafter also used for green and blue) to a thickness of x = 0.640 and colored. A film was formed. The film was irradiated with ultraviolet rays of 300 mJ / cm ² 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. Formed. In the same manner, the green resist material is applied to a thickness such that y = 0.600, and the blue resist material (R-1) is applied to a thickness such that y = 0.06. A blue filter segment was formed to obtain a color filter (CF-1).

(Production of liquid crystal display device)
A transparent ITO electrode layer was formed on the obtained 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 manner are arranged to face 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. The liquid crystal display device thus produced was combined with a backlight unit to obtain a liquid crystal panel.

<Production of color filter>
[Examples 202 to 242 and Comparative Examples 201 to 206]
(Color filter (CF-2 to 42, 51 to 56))
Hereinafter, primary color filters (CF-2 to 42, 51 to 56) and a liquid crystal display device were produced in the same manner as the color filter (CF-1) except that the resist material was changed to the resist material shown in Table 8. . The red resist material and the green resist material were fixed conditions.

[Evaluation of color filter]
Thereafter, in the obtained liquid crystal display device, a light source is emitted to display a color image, and in the primary color filter, the brightness of the red, green, and blue filter segment portions is measured with a microspectrophotometer ("OSP-" manufactured by Olympus Optical Co., Ltd.). SP200 "), and the brightness of white display in the color filter was determined from the obtained brightness. In addition, the contrast ratio of the red, green, and blue filter segment portions was measured with a microspectrophotometer ("OSP-SP200" manufactured by Olympus Optical Co., Ltd.), and white display in the color filter was obtained from the obtained contrast ratio. The contrast ratio was determined. Table 8 shows the evaluation results of the color filter. The contrast ratio of the white display of the example shows superior performance compared to the comparative example.

  The color filters of Examples 201 to 242 include a resin salt-forming compound (A1) and a colorant (A2), and further include a colorant (A3) as necessary, and the resin salt-formation compound (A1) or the colorant ( Compared with Comparative Examples 201 to 206 not including A2), the contrast ratio of white display was high and the practical performance was satisfied. This is because the comparative example does not contain the colorant (A2) or because the colorant is not a resin salt compound, the fluorescent component due to the dye exists as leakage light, and as a result, the cross luminance at the time of measuring the contrast ratio increases. This is because the calculated contrast ratio is low.

  From the above, by using the resin salt-forming compound (A1), the colorant (A2), and, if necessary, the colorant (A3), the color characteristics (brightness), heat resistance, and contrast ratio are excellent. It has become possible to obtain a blue coloring composition for color filters and a color filter.

Claims (8)

A color filter coloring composition comprising a colorant (A), a binder resin (B), and an organic solvent (C),
A resin obtained by reacting a vinyl resin (a1) having a structural unit represented by the following general formula (1) having a cationic group in the side chain with an anionic dye (a2) The salt-forming compound (A1) and a colorant (A2-) having a peak wavelength λmax2 on the longer wavelength side of 5 to 100 nm from the peak wavelength λmax1 of the resin salt-forming compound (A1) and represented by the following general formula (2) 1) or a colorant (A2) which is a colorant (A2-2) represented by the following general formula (3).

General formula (1)

[In General Formula (1), R ¹¹ represents a hydrogen atom or a substituted or unsubstituted alkyl group. R ^{12 to} R ¹⁴ each independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group, and R ^{12 to} R ¹⁴ Two of them may be bonded to each other to form a ring. Q represents an alkylene group, an arylene group, —CONH—R ¹⁵ —, —COO—R ¹⁵ —, and R ¹⁵ represents an alkylene group. Y ^- is representative of an inorganic or organic anion. ]
General formula (2)

[In General Formula (2), R ^{21 to} R ²⁸ are each independently, independently of each other, a hydrogen atom, a halogen atom, a hydroxy group, a cyano group, a nitro group, an alkyl group, an amino group, an alkoxyl group, or an aryl group. , an aryloxy group, an arylthio group, an aralkyloxy group, an acyl group, a carboxyl group, a sulfonic acid _{^{group, -SO 3 M b, -SO 3}} R 29, -SO 2 NH 2, -SO 2 NHR 30, or -SO ₂ NR ³¹ R ³² is represented. However, the hydrogen atom contained in the alkyl group, amino group, alkoxyl group, aryl group, aryloxy group, arylthio group, aralkyloxy group is a halogen atom, hydroxy group, cyano group, nitro group, alkyl group, amino group, an alkoxyl group, an aryl group, an aryloxy group, an arylthio group, an aralkyloxy group, an acyl group, a carboxyl group, a sulfonic acid _{^{group, -SO 3 M c, -SO 3}} R 33, -SO 2 NH 2, -SO 2 NHR 34 , or it may be substituted by _-SO 2 ^NR 35 ^{R 36.} R ^{29 to} R ³⁶ each independently represent an alkyl group which may have a substituent. M ^a is a divalent to tetravalent substituent may metal atoms have, M ^b, M ^c is a metal atom to neutral power value of the molecule. The substituents of R ²¹ and R ²² , R ²³ and R ²⁴ , R ²⁵ and R ²⁶ , R ²⁷ and R ²⁸ may be interchanged, or a mixture of isomers having different configurations may be used. ]
General formula (3)

[In General Formula (3), R ^{41 to} R ⁴³ are each independently a hydrogen atom, a halogen atom, a hydroxy group, a cyano group, a nitro group, an alkyl group, an amino group, an alkoxyl group, an aryl group, or an aryloxy group. , an arylthio group, an aralkyloxy group, an acyl group, a carboxyl group, a sulfonic acid _{^{group, -SO 3 M d, -SO 3}} R 44, -SO 2 NH 2, -SO 2 NHR 45, or _-SO 2 ^NR 46 ^{R 47} Represents. However, the hydrogen atom contained in the alkyl group, amino group, alkoxyl group, aryl group, aryloxy group, arylthio group, aralkyloxy group is a halogen atom, hydroxy group, cyano group, nitro group, alkyl group, amino group, an alkoxyl group, an aryl group, an aryloxy group, an arylthio group, an aralkyloxy group, an acyl group, a carboxyl group, a sulfonic acid _{^{group, -SO 3 M e, -SO 3}} R 48, -SO 2 NH 2, -SO 2 NHR 49 , or it may be substituted by _-SO 2 ^NR 50 ^{R 51.} R ⁴⁴ to R ⁵¹ are independently of each other, represent an alkyl group which may have a substituent. M ^d and ^Me are metal atoms that neutralize the valence of the molecule. n1 is an integer of 1 to 8, and m1 is an integer of 0 to 7. When n1 or m1 is plural, each of R ⁴¹ , R ⁴² , and R ⁴³ may have a different structure. ]   The color filter according to claim 1, wherein the content of the colorant (A2) is 0.03 to 0.5 parts by weight with respect to 1 part by weight of the effective pigment component of the resin salt-forming compound (A1). Coloring composition. The colorant (A) contains a colorant (A3) having a peak wavelength λmax3 of 5 to 100 nm longer than the peak wavelength λmax1 of the resin salt-forming compound (A1) and represented by the following general formula (4) The coloring composition for a color filter according to claim 1 or 2, wherein the coloring composition is used.

General formula (4)
P-Lm
[In General Formula (4), P is an m-valent phthalocyanine pigment residue, m is an integer of 1 to 4, and L is General Formulas (5), (6), and (7). Any of the substituents selected from the group shown. The phthalocyanine pigment residue has a metal atom which may have a divalent to tetravalent substituent as a central metal. ]
General formula (5)

General formula (6):

General formula (7)

[In General Formulas (5) to (7), X represents —SO ₂ —, —CO—, —CH ₂ —,
_{-CH 2 NHCOCH 2 -, - CH} 2 NHSO 2 CH 2 -, or a direct bond,
Y ⁰ is —NH—, —O—, or a direct bond,
n is an integer of 1 to 10,
Y ¹ is —NH—, —NR ⁹ —Z—NR ¹⁰ —, or a direct bond;
R ⁹ and R ¹⁰ are each independently a hydrogen atom, an alkyl group having 1 to 36 carbon atoms, an alkenyl group having 2 to 36 carbon atoms, or a phenyl group,
Z represents an alkylene group having 1 to 20 carbon atoms or an arylene group having 1 to 20 carbon atoms.
R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, or a combination of R ¹ and R ² together with further nitrogen, oxygen, Or a heterocycle containing a sulfur atom,
R ³ , R ⁴ , R ⁵ , and R ⁶ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms. ,
R ⁷ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms,
R ⁸ is a substituent represented by the general formula (5) or a substituent represented by the general formula (6),
Q represents a hydroxyl group, an alkoxyl group having 1 to 20 carbon atoms, a substituent represented by the general formula (5), or a substituent represented by the general formula (6). ]   The solubility ratio ([A3] / [A2]) of the solubility [A3] of the colorant (A3) in the organic solvent (C) and the solubility [A2] of the colorant (A2) in the organic solvent (C) is 10%. The coloring composition for a color filter according to claim 3, wherein: The content of the colorant (A3) is 0.2 to 1.2 parts by weight with respect to 1 part by weight of the effective pigment component of the resin salt-forming compound (A1), and the colorant (A2) and the colorant (A3) The color composition for color filters according to claim 3 or 4, wherein the weight blending ratio of the color filter is 5:95 to 90:10.   Furthermore, a photoinitiator (H) is contained, The coloring composition for color filters of any one of Claims 1-5 characterized by the above-mentioned. The colored composition for a color filter according to any one of claims 1 to 6, wherein the binder resin (B) has a dicyclo ring structural unit represented by the following general formula (8).
General formula (8)

[In General Formula (8), Ring A is formed by a bond of any element of hydrogen or carbon which may have a substituent, nitrogen, oxygen or sulfur which may have hydrogen or a substituent. A 10-membered ring structure, and B is formed by a bond of hydrogen or an optionally substituted carbon, hydrogen or an optionally substituted nitrogen, oxygen, or sulfur element 1 It is a linking chain that forms a 6-membered second ring. The general formula (8) may further have a linking chain forming a ring structure. ]   A color filter comprising a filter segment formed on the substrate with the colored composition for color filter according to any one of claims 1 to 7.