TW201843247A - Pigment composition for color filter and color filter - Google Patents

Abstract

The present invention addresses the problem of providing a pigment composition for obtaining a color filter having improved luminance without increased film thickness. The present invention can provide a pigment composition for a color filter, the composition characterized by containing a zinc halide phthalocyanine pigment and a pigment derivative represented by general formula (1) (in general formula (1), Z1 to Z16 each independently represent a bromine atom, a chlorine atom, a hydrogen atom, or a sulfo group, at least the average number of substituents of the sulfo group is 0.1 to 4, and M represents Al, Si, Sc, Ti, V, Mg, Fe, Co, Ni, Zn, Ga, Ge, Y, Zr, Nb, In, Sn, or Pb). The present invention also provides a color filter having the pigment composition in the pixels thereof.

Description

   Pigment composition for color filter and color filter   

The present invention relates to a pigment composition for a color filter and a color filter.

A color filter used for a liquid crystal display is configured by regularly arranging a plurality of colors on a transparent glass substrate, and transmitting only light in a required wavelength region from white light passing through the backlight to realize the color of the display. Displayed widgets. The colors used therein generally include the three primary colors of red, green, and blue. In order to adjust the transmission spectrum separately, the colorants, resins, and additives used are continuously improved. From the viewpoint of improving the image quality of a display, green colorants for color filters are required to have higher brightness and an expanded color reproduction range.

For high brightness, it is important to select a pigment that has a high transmittance to the light of the backlight, and use Pigment Green 58 as the main pigment to replace the current Pigment Green 36 in order to improve it. In addition, by increasing the brightness due to the improvement of the pigment, the white light of the backlight can be used efficiently, so that energy saving of the display and reduction of manufacturing costs can be achieved.

Regarding the expansion of the color reproduction range, it is necessary to increase the chroma of the coloring material contained in the color filter. In order to produce a coating film with high saturation, there are methods such as increasing the pigment concentration in the coating film, or increasing the thickness of the coating film with the same pigment concentration. However, in any case, it is difficult to ensure the resistance of the coating film. Therefore, compared with the pigment green 36 and pigment green 58 currently used for color filter applications, a specific chromaticity that can be tinted with a yellow colorant is selected. Pigment Green 7, which is a thin film, is used as the main pigment. Although the color reproduction range can also be expanded by thickening the pigment green 36 and pigment green 58, the NTSC ratio of 90% or more cannot be achieved with a practical film thickness of about 3.5 μm, which is why pigment green 7 was selected. For example, it has been proposed to use a green photosensitive resin composition containing Pigment Green 7 and Pigment Yellow 185 to form green pixels, and achieve high color reproduction with a thin film of 2.2 μm or less. However, when compared with Pigment Green 36 and Pigment Green 58, the transmittance of Pigment Green 7 is low, so that there is a problem that the brightness of the obtained display decreases. In addition, the brightness can be compensated by increasing the amount of light in the backlight. However, since a new problem such as an increase in power consumption arises, improvement is required. For this reason, a color filter for a color filter, which has both brightness and color reproducibility, is desired.

In order to solve these problems, it has been proposed that when the main pigment is aluminum phthalocyanin, it contains a phthalocyanin sulfonic acid derivative, which is excellent in color density, color purity, and transparency, and also has good heat resistance and light resistance. Color filter (Patent Document 1). However, the aluminum phthalocyanin pigment, which is a main pigment, may have low heat resistance and light resistance, and may not satisfy the performance required in recent years.

In addition, it has been proposed to use a green pigment composition containing a copper halide phthalocyanin pigment and a low-halogenated copper phthalocyanin sulfonic acid derivative, having an average primary particle diameter of 0.01 to 0.1 μm and an aspect ratio of 1 to 3, to produce A color filter with good contrast (Patent Document 2). However, the copper phthalocyanin pigment, which is a main pigment, may have low brightness and may not satisfy the performance required in recent years.

From this, it can be seen that the current technology is not enough to meet the rapidly increasing demand for performance in order to form a color filter with the purpose of increasing the brightness and expanding the color reproduction range, and still cannot achieve the purpose.

Patent document 1 JP 2011-057910

Patent Document 2 Japanese Patent Application Laid-Open No. 2005-316244

The problem to be solved by the present invention is to provide a pigment composition for obtaining a color filter without increasing the thickness of the film and improving the brightness.

The present inventors conducted an intensive review in view of such a situation, and found that by using a zinc halide phthalocyanine pigment as a main pigment and containing a specific pigment derivative, it is possible to produce a device capable of achieving brightness enhancement without thickening the film. Color filters. That is, the present invention relates to a pigment composition for a color filter and a color filter comprising the pigment composition for a color filter in a pixel portion. The pigment composition for a color filter is characterized by containing A zinc halide phthalocyanin pigment and a pigment derivative represented by the following general formula (1),

(In general formula (1), Z ¹ to Z ¹⁶ each independently represent a bromine atom, a chlorine atom, a hydrogen atom, or a sulfonic acid group, the average number of substituents of the sulfonic acid group is at least 0.1 to 4, and M represents Al, Si, Sc, Ti, V, Mg, Fe, Co, Ni, Zn, Ga, Ge, Y, Zr, Nb, In, Sn or Pb.).

According to the present invention, it is possible to produce a color filter capable of improving brightness without thickening the film.

A form for implementing the invention

The zinc halide phthalocyanin pigment used in the present invention is a zinc metal disposed at the center, and at least one or more of chlorine, bromine, fluorine, and iodine are substituted on a phthalocyanin ring that can be substituted with a substituent other than halogen. The compound of the selected halogen atom has a total of 16 substituents. The part which is not substituted by halogen and a substituent other than halogen means a hydrogen atom.

Among them, from the viewpoint of designing a color filter with a wide color reproduction range, the zinc halide phthalocyanin pigment used in the present invention preferably has an average of 10 to 14 halogen atoms in one molecule, in which the number of bromine atoms is average. 8 to 12, with an average of 2 to 5 chlorine atoms.

The pigment derivative used in the present invention can be represented by the general formula (1).

Among them, from the viewpoint of making the hue of the main pigment of the green color filter and the pigment derivative similar, it is preferable to use the pigment derivative in the aforementioned general formula (1), where Z ¹ to Z ¹⁶ have a bromine atom and chlorine Any one of an atom, a hydrogen atom, or a sulfonic acid group, and based on the average in one molecule, at least Z ¹ , Z ⁴ , Z ⁵ , Z ⁸ , Z ⁹ , Z ¹² , Z ¹³ , Z ¹⁶ Any two or more of them have a chlorine atom.

In addition, from the viewpoint of making the hue of the main pigment and the pigment derivative of the green color filter similar, the pigment derivative is also preferably used in the general formula (1), where Z ¹ to Z ¹⁶ have a bromine atom, Any of a chlorine atom, a hydrogen atom, or a sulfonic acid group, and based on the average in one molecule, at least from Z ¹ , Z ⁴ , Z ⁵ , Z ⁸ , Z ⁹ , Z ¹² , Z ¹³ , Z ¹⁶ Any two or more selected persons having a bromine atom.

In addition, Japanese Patent Application Laid-Open No. 2010-189528 states that if a chlorine atom or a bromine atom enters the positions of Z ¹ , Z ⁴ , Z ⁵ , Z ⁸ , Z ⁹ , Z ¹² , Z ¹³ , and Z ¹⁶ , the hue becomes greenish.

From the viewpoint of making the hue of the pigment derivative more similar to the hue of the main pigment, it is more preferable that, on the average of one molecule, Z ¹ to Z ¹⁶ contain 10 to 14 halogen atoms, 8 to 12 bromine atoms, Those with 2 to 5 chlorine atoms.

The pigment composition of the present invention as described above is not a pigment composition based on a simple combination of a conventional pigment and a pigment derivative of the same system skeleton, but the present invention has been completed based on the following ideas.

(A) First, a general organic pigment-based molecule has a highly conjugated system as a whole, and becomes a planar structural system that is stable in energy. When the planar molecules are stacked (parallel), the π electrons of the conjugated system that are present between the molecules are superimposed, and therefore a more stable state is obtained. Since the pigment derivative represented by the general formula (1) used in the present invention has a phthalocyanine ring, it has a planar structure, and interaction with the planar structure of an organic pigment is likely to occur. In addition, when the main pigment is a halogenated phthalocyanin pigment, it is considered that a halogen-π interaction with a π electron of a derivative is particularly likely to occur. It is considered that if such a specific pigment derivative coexists in the dispersion step of the organic pigment, the derivative is efficiently adsorbed on the active surface of the halogenated phthalocyanin pigment newly generated during the dispersion. In addition, the sulfonic acid group of the polar group can stabilize and disperse the halogenated phthalocyanin pigment in a fine state, and thus can improve brightness. Here, the sulfonated phthalocyanin derivative of the present invention can be added at the time of pigmentation and can also be added at the time of dispersion to exhibit good effects. However, if it is allowed to coexist in the pigmentation step, it can enter the halogenated phthalocyanin pigment. Since the primary particles are kept fine between the molecules of the material, the sulfonated phthalocyanin derivative of the present invention can achieve greater brightness improvement by coexisting it during pigmentation than when it is added during dispersion.

(B) In addition, the present invention is also focused on the manner in which the absorption spectra of pigments and derivatives overlap. In order to obtain a bright and vivid display in the color filters of green pixels, it is particularly preferable to increase the transmittance of 510nm to 560nm. In order to design a color filter that transmits only this narrow wavelength region, a green pigment and a yellow pigment are used in combination. Therefore, it is preferred that the pigment derivative treated in the green pigment has a transmission wavelength of 510 to 560 nm and a green pigment. A similar combination.

(C) In addition, Japanese Patent Application Laid-Open No. 8-240708 states that if the transmittance of 430nm to 460nm is high, the chromaticity y value will be greatly reduced, and the sharpness of green will be greatly damaged. Therefore, the lower the transmittance in this wavelength range, the lower it is good. When the chromaticity y value is low, it is necessary to increase the film thickness to increase the chromaticity y value. However, if the film thickness is increased, the brightness decreases. Therefore, it is necessary to select a pigment derivative whose transmittance is as low as possible, such as 430 nm to 460 nm. In particular, the green pixels of the color filter are generally C.I. Pigment Yellow 138 (Y138) which is a green pigment combined with a quinoline yellow-based yellow pigment. According to Japanese Patent Application Laid-Open No. 2015-26077: Y138 is transferred from the absorption band to the transmission band around 460nm. It can be seen that Y138 can absorb short wavelengths less than 460nm, but it is not suitable for absorption on the long wavelength side. The lower the transmittance of the treated derivative at 460 nm, the better.

From the viewpoints of the aforementioned (B) and (C), the central metal M in the above formula (1) is preferably Al or Zn, and among these, Zn is preferred. To elaborate the viewpoint of (C), in terms of pigment derivatives, the metal M in the above formula (1) has a lower transmittance of 430 nm to 460 nm than that of Al, so that a pigment with high brightness can be produced.组合 物。 Composition.

Such a pigment derivative can be obtained by the following conventionally known method, for example. That is, it can be obtained by dissolving phthalocyanin or halogenated phthalocyanin in sulfuric acid and heating it to 100 ° C. or more, or dissolving in oleum and treating it at a low temperature. When a sulfonic acid group is introduced into a phthalocyanin ring under severe reaction conditions, the phthalocyanin ring is oxidatively decomposed by sulfuric acid or oleum, and the purity of the pigment derivative is lowered. From the viewpoint of using a higher purity pigment derivative, in the aforementioned general formula (1), the average number of substituents of the sulfonic acid group is preferably 0.1 to 4 and more preferably 0.5 to 1 in terms of an average in one molecule. Two.

The sulfonic acid group may be a sulfonic acid or a salt. Examples of salt-forming counter ions include ammonium ions and 1 to 3 valent metal ions (specific examples include lithium ions, sodium ions, potassium ions, calcium ions, magnesium ions, strontium ions, and aluminum Ions, etc.) and organic cations (specific examples include monoalkylammonium ions such as ethylammonium ions and butylammonium ions; dialkylammonium ions such as dimethylammonium ions and diethylammonium ions) ; Trialkylammonium ion such as trimethylammonium ion, triethylammonium ion, etc .; Alkanolammonium ion such as monoethanolammonium ion, diethanolammonium ion, triethanolammonium ion; tetramethylammonium ion, tetramethylammonium ion Guanidine ion, tetramethylphosphonium ion, etc.). In particular, the sulfonic acid group of the pigment derivative in the present invention is preferably a sulfonic acid or an organic cation salt in terms of reducing the elution amount of the pigment derivative in the developing step for producing a color filter.

In the present invention, the average number of halogen atoms of the zinc halide phthalocyanin pigment can be determined by mass analysis. The mass analysis was performed using a matrix-assisted laser desorption ionization time-of-flight mass spectrometer (JMS-S3000 manufactured by Japan Electronics Co., Ltd.). When mass analysis of a known compound having a molecular weight Q was performed, m was detected. / z = Q to set each measurement parameter. In the present invention, when mass analysis of a known compound having a molecular weight of 1840 is performed, the setting of JMS-S3000 is adjusted so that m / z = 1840 is detected. In addition, 1 μL of a suspension in which 0.5 mg of a zinc halide phthalocyanin pigment was dispersed in 1 mL of tetrahydrofuran was used for mass analysis.

In this invention, the average sulfonation ratio of a pigment derivative can be calculated | required with the high-speed liquid chromatography mass spectrometer (LC-MS-8040 by Shimadzu Corporation). The pigment derivative was made to volume with dimethyl sulfene, and a gradient elution profile was obtained using a mixed solvent of 10 mmol / L ammonium bicarbonate aqueous solution / methanol / tetrahydrofuran as a mobile phase. The obtained peaks were qualitatively determined by mass analysis (ionization mode: DUIS), and the sulfonation ratio was calculated from the peak area ratio.

Moreover, the pigment derivative in the present invention, the foregoing general formula ^{(1), Z 1, Z} 4, Z 5, Z 8, Z 9, Z 12, Z 13, Z ¹⁶ is a halogen-substituted radix m, and ^{Z 2, Z 3, Z 6} , Z 7, Z 10, Z 11, Z 14, Z ^{15 is} a halogen-substituted cardinality n, made by decomposition of the pigment-based derivative of terephthalic cerium sulfate acyl imines in Then, the obtained xylylenediamines were analyzed by liquid chromatography to obtain them. Let the total molar concentration of all the xylylenediamines obtained as a result of liquid chromatography be a, and the total molar concentration of the xylylenediamines having a halogen at the 3 or 6 position be set. Is b (in the case of benzodiazepines having halogens at positions 3 and 6, the molar concentration of the benzodiazepines is calculated at twice the actual measurement), and the 4th or 5th place The total molar concentration of halogenated xylylenediamines is c (in the case of xylylenediamines having halogens at the 4 and 5 positions, the molarity of the xylylenediamines When the concentration is calculated based on 2 times the actual measurement), it is calculated as m = 4 × b / a and n = 4 × c / a. Although m and n can be obtained by liquid chromatography analysis, m and n can be determined freely by controlling the input materials. For example, pigment derivative systems obtained by sulfonating tetrachlorozinc phthalocyanin synthesized using 3-chlorophthalic anhydride as a raw material are m = 4 and n = 0. In addition, pigment derivatives based on tetrachlorozinc phthalocyanin synthesized by using 4-chlorophthalic anhydride as a raw material were m = 0 and n = 4.

In the present invention, the average number of halogen atoms of the pigment derivative can be obtained by mass analysis using the aforementioned matrix-assisted laser desorption ionization time-of-flight mass spectrometer.

The pigment derivative of the present invention can be added at the time of synthesis of the crude pigment and after pigmentation, but it can also be pigmented together with the crude pigment at the time of pigmentation. In addition, since the dispersibility of the color filter dispersion liquid and the color filter resist ink is increased and the brightness is increased, a pigment derivative can also be added during dispersion and during the preparation of the resist. The pigment derivative used in the present invention penetrates into the molecules of the zinc halide phthalocyanin pigment and can keep the primary particles fine. Therefore, it is preferable to add the pigment derivative during pigmentation and pigmentation together with the crude pigment.

The pigment composition containing the zinc halide phthalocyanin pigment and the pigment derivative represented by the above formula (1) is contained in a pulverizer such as a mill (Attritor), a ball mill, a vibration mill, or a vibration ball mill as needed Dry grinding is performed, followed by pigmentation using solvent salt milling, solvent boiling, etc., to obtain a green-emitting pigment that is superior in dispersibility, tinting power, and brightness before the pigmentation. .

The ratio of the zinc halide phthalocyanin pigment to the pigment derivative represented by the aforementioned formula (1) is not particularly limited, but it is contained in the formula (1) with respect to 100 parts of the zinc halide phthalocyanin pigment in terms of mass conversion. The pigment derivative represented by 0.1 to 10 parts is preferable when the pigment composition is used as a color filter because the brightness can be increased without thickening the film.

The pigmentation method of the green pigment composition containing the zinc halide phthalocyanin pigment and the pigment derivative represented by the aforementioned formula (1) is not particularly limited. For example, a zinc halide phthalocyanin pigment and The pigment composition of the pigment derivative represented by the aforementioned formula (1) is dispersed in a dispersing medium and pigmented at the same time. Compared with a solvent treatment in which the pigment composition of the pigment derivative is heated and agitated, a solvent salt milling treatment is preferred in that the crystal growth can be easily suppressed and pigment particles having a large specific surface area can be obtained.

This solvent salt milling means a pigment composition containing inorganic halogenated zinc phthalocyanin pigment and a pigment derivative represented by the aforementioned formula (1), which is not pigmented, and is ground immediately after or after the synthesis. Salt and organic solvent are kneaded and ground. As the kneader at this time, for example, a kneader, a Mix Muller, a Trimix, a biaxial extruder, and the like can be used.

As said inorganic salt, a water-soluble inorganic salt can be used suitably, For example, it is preferable to use inorganic salts, such as sodium chloride, potassium chloride, and sodium sulfate. In addition, it is more preferable to use an inorganic salt having an average particle diameter of 0.5 to 50 μm. Such an inorganic salt can be easily obtained by pulverizing a general inorganic salt.

In the present invention, it is preferable to use a pigment composition containing a zinc halide phthalocyanine pigment and a pigment derivative represented by the aforementioned formula (1) with an average primary particle diameter of 0.01 to 0.10 μm for use in a color filter. . In order to obtain the aforementioned preferred particle size in the present invention, it is preferred to increase the amount of inorganic salt relative to the amount of crude pigment in the solvent salt mill. That is, the usage-amount of this inorganic salt becomes like this. Preferably it is 5-20 mass parts with respect to 1 mass part of crude pigments, More preferably, it is 7-15 mass parts.

As the organic solvent, an organic solvent capable of suppressing crystal growth is preferably used. As such an organic solvent, a water-soluble organic solvent can be suitably used, and for example, diethylene glycol, glycerol, ethylene glycol, propylene glycol, and liquid polyethylene can be used. Glycol, liquid polypropylene glycol, 2- (methoxymethoxy) ethanol, 2-butoxyethanol, 2- (isoamyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol- Methyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, 1-methoxy-2-propanol, 1-ethyl Oxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol, and the like. The amount of the water-soluble organic solvent used is not particularly limited, but is preferably 0.01 to 5 parts by mass relative to 1 part by mass of the crude pigment.

In the case of producing a pigment composition containing a zinc halide phthalocyanin pigment and a pigment derivative represented by the aforementioned formula (1) by a solvent salt mill, the zinc halide phthalocyanin pigment and the aforementioned formula (1) may be used. The pigment derivatives represented are separately subjected to solvent salt milling and then combined together, and the zinc halide phthalocyanin pigment and the phthalocyanin pigment derivative represented by the aforementioned formula (1) can also be mixed in the apparatus for solvent salt milling. mill. In the evaluation of the optical characteristics based on the color filter, there is not much difference in terms of which method can improve the brightness.

As described above, the pigment composition of the present invention has a wavelength (Tmax) at which the transmittance of the spectral transmission spectrum at 380 to 780 nm becomes the largest (500 to 525 nm), as with the current zinc halide phthalocyanin pigment, and its transmission curve The full width at half maximum of 110 nm or less is very sharp (this wavelength is not affected by the photosensitive resin described later).

The spectroscopic transmission spectrum in the evaluation of color filters refers to those obtained by the first spectrophotometer in accordance with Japanese Industrial Standard JIS Z 8722 (method of color measurement-color of reflected and transmitted objects). The film is formed into a resin film including a pigment composition having a predetermined dry film thickness, which is obtained by scanning and irradiating light in a predetermined wavelength region, and plotting each transmittance value at each wavelength.

Here, the integral value of the transmittance of 510 nm to 560 nm of a coating film formed using a zinc halide phthalocyanine pigment so that the spectral transmittance of the maximum transmission wavelength becomes 70% is set to D1. (1) The integrated value of the transmittance of 510nm to 560nm of the coating film formed by supporting the derivative support obtained by supporting the pigment derivative shown in (1) on alumina, with the spectral transmittance at a maximum transmission wavelength of 70%. When D2 is used, a pigment composition for a color filter having a spectral characteristic of D1 and D2 (D2 / D1) of 0.7 or more can limit the reduction in the brightness of a green color filter produced by a pigment derivative. To a minimum, it is better. In order to design a brighter green color filter, a pigment composition for a color filter having a spectral characteristic in which the ratio of D1 and D2 (D2 / D1) is 1.0 or more is more preferable, and D1 is more preferable. A pigment composition for a color filter having a ratio (D2 / D1) of D2 to a spectral characteristic of 1.2 or more.

In addition, it has a coating film formed at a wavelength of 460 nm using a derivative support obtained by supporting the pigment derivative represented by the general formula (1) on alumina, and having a spectral transmittance at a maximum transmission wavelength of 70%. The pigment composition for a color filter having a transmittance of 60% or less has a preferable color composition, and a green color filter having high color reproducibility with suppressed decrease in chromaticity y can be produced. In addition, in order to design a green color filter with higher color reproducibility, a pigment composition for a color filter having a spectral characteristic with a transmittance of 460 nm to 55% or less is more preferable, and a transmittance of 460 nm is even more preferable. A pigment composition for a color filter having a spectral characteristic of 50% or less.

The pigment composition of the present invention can be directly used only for manufacturing a green pixel portion of a color filter, but other green pigments can be used in combination as needed.

In addition, in addition to green pigments, yellow pigments are used for color tone in order to develop characteristics. Examples of yellow pigments that can be used in combination here include CI Pigment Yellow 83, Pigment Yellow 110, Pigment Yellow 129, Pigment Yellow 138, Pigment Yellow 139, Pigment Yellow 150, Pigment Yellow 180, Pigment Yellow 185, Pigment Yellow 231, and the like. Yellow organic pigment. The combined ratio of the zinc halide phthalocyanin pigment composition and the yellow pigment of the present invention is 10 to 200 parts by mass relative to 100 parts by mass of the zinc halide phthalocyanin pigment composition.

    (Color filter)    

A color filter can be obtained by forming a green pixel using the pigment composition of the present invention.

    (Manufacturing method of color filter)    

The pigment composition of the present invention can be used to form a pattern of a green pixel portion of a color filter by a known method. Typically, a photosensitive composition for a green pixel portion of a color filter including the present pigment composition and a photosensitive resin as essential components can be obtained.

As a method for producing a color filter, for example, a method called a photolithography method is used: the pigment composition for a color filter of the present invention is dispersed in a dispersion medium containing a photosensitive resin, and then spin-coated Method, roll coating method, slit coating method, inkjet method, etc. are applied to a transparent substrate such as glass, and then the coated film is exposed to a pattern using ultraviolet rays through a photomask, and the unexposed portion is washed with a solvent or the like to obtain a green color. pattern.

As another manufacturing method, for example, a method of forming a pattern of a green pixel portion by a method such as an electrophotographic method, a transfer method, a microelle electrolytic method, or a PVED (Photovoltaic Electrodeposition) method may be used to produce a color filter. Methods etc. Moreover, the pattern of a red pixel part and the pattern of a blue pixel part can also be formed by the same method using a well-known pigment.

For preparing a photosensitive composition for a green pixel portion of a color filter, for example, the pigment composition for a color filter of the present invention, a photosensitive resin, a photopolymerization initiator, and an organic solvent that dissolves the resin are necessary. Ingredients are mixed. More specifically, it is generally a method of preparing a dispersion liquid using the pigment composition of the present invention, an organic solvent, and a dispersant as necessary, and then adding a photosensitive resin to the dispersion liquid to prepare the dispersion liquid.

Examples of the dispersant include: DISPERBYK (DISPERBYK, registered trademark) 130, DISPERBYK 161, DISPERBYK 162, DISPERBYK 163, DISPERBYK 170, DISPERBYK LPN-6919, DISPERBYK LPN-21116, etc., by BYK-Chemie. In addition, a leveling agent, a coupling agent, and a cationic surfactant may be used in combination.

Examples of the organic solvent include aromatic solvents such as toluene, xylene, and methoxybenzene; acetic acids such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate Ester-based solvents; Propionate-based solvents, such as ethoxyethyl propionate; Alcohol-based solvents, such as methanol and ethanol; Butylcellulose, Propylene glycol monomethyl ether, Diethylene glycol ethyl ether, Diethylene glycol Ether solvents such as alcohol dimethyl ether; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; aliphatic hydrocarbon solvents such as hexane; N, N-dimethylformamide , Γ-butyrolactam, N-methyl-2-pyrrolidone, aniline, pyridine and other nitrogen compound-based solvents; γ-butyrolactone and other lactone-based solvents; such as methyl carbamate and ethyl carbamate 48: 52 mixture of carbamate, water and the like. The organic solvent is particularly suitable for polar solvents such as propionate-based, alcohol-based, ether-based, ketone-based, nitrogen compound-based, lactone-based, and water-soluble solvents.

A dispersion liquid can be obtained by stirring and dispersing 300 to 1,000 parts by mass of an organic solvent with respect to 100 parts by mass of the pigment composition of the present invention, and 0 to 100 parts by mass of a dispersant as needed. Next, a photopolymerization initiator of 3 to 20 parts by mass with respect to 100 parts by mass of the pigment composition of the present invention and 0.05 to 3 parts by mass of 1 part by mass of the photosensitive resin can be added to this dispersion. Further, if necessary, an organic solvent is further added, and the mixture is stirred and dispersed in a uniform manner to obtain a photosensitive composition for a green pixel portion of a color filter.

Examples of the photosensitive resin include a polyurethane resin, an acrylic resin, a polyamic acid resin, a polyimide resin, a styrene maleic resin, and a styrene maleic anhydride. Thermoplastic resins such as 1,6-hexanediol diacrylate, ethylene glycol diacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, bis (propyleneoxyethoxyethoxylate) Group) Bifunctional monomers such as bisphenol A, 3-methylpentanediol diacrylate; such as trimethylolpropane triacrylate, pentaerythritol triacrylate, ginseng (2-hydroxyethyl) isocyanate, dipentaerythritol Photopolymerizable monomers such as polyfunctional monomers such as hexaacrylate and dipentaerythritol pentaacrylate.

Examples of the photopolymerization initiator include acetophenone, benzophenone, benzyldimethylketal, benzophenone peroxide, 2-chlorothioxanthone, and 1,3-bis (4'- Azidenzylidene) -2-propane, 1,3-bis (4'-azidobenzylidene) -2-propane-2'-sulfonic acid, 4,4'-diazide-2,2 '-Disulfonic acid and the like.

The prepared photosensitive composition for a green pixel portion of a color filter can be subjected to pattern exposure using ultraviolet rays through a photomask, and then the unexposed portion can be washed with an organic solvent, alkaline water, or the like to obtain a color filter.

    [Example]    

Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In the examples and comparative examples, unless otherwise specified, "parts" and "%" are quality standards.

The measurement methods used in the examples described later are as follows.

    [Evaluation of brightness]    

The chromaticity x, y, and brightness under the C light source of the obtained color filter were measured with a spectrophotometer U-3900 (manufactured by Hitachi High Tech Science Co., Ltd.). The higher the brightness, the better.

    Reference example 1    

Into a 300 ml flask, 90 g of sulfonium chloride (reagent of Wako Pure Chemical Industries), 105 g of aluminum chloride (reagent of Kanto Chemical), 14 g of sodium chloride (reagent of Tokyo Chemical Industry), and zinc phthalocyanin manufactured by DIC Corporation 27g, bromine (reagent of Wako Pure Chemical Industries) 55g. The temperature was raised to 130 ° C, and after being taken out into water, it was filtered, washed with water, and dried to obtain zinc halide phthalocyanin (R1). The zinc halide phthalocyanin (R1) was subjected to mass analysis using JMS-S3000 manufactured by Japan Electronics Co., Ltd., and it was confirmed that the average chlorination rate was 2.9 and the average bromination rate was 9.3. In addition, the Delay Time during mass analysis was 510 ns, the Laser Intensity was 40%, and the Resolving Power Value of the peak at m / z = 1820 to 1860 was 65086.

40 g of the obtained zinc halide phthalocyanin (R1), 400 g of pulverized sodium chloride, and 63 g of diethylene glycol were put into a double-arm kneader and kneaded at 80 ° C. for 8 hours. After kneading, it was taken out in 2 kg of water at 80 ° C. and stirred for 1 hour, and then filtered, washed with hot water, dried, and pulverized to obtain a green pigment composition (RG1). Using 0.3 to 0.4 mm zirconium beads, a paint shaker (Paint Shaker) manufactured by Toyo Seiki Co., Ltd. was used to mix 2.48 g of green pigment composition (RG1) with BYK-LPN6919 1.24 g manufactured by BYK-Chemie, limited by DIC. 1.86 g of UNIDIC ZL-295 manufactured by the company and 10.92 g of propylene glycol monomethyl ether acetate were dispersed together for 2 hours to obtain a colored composition (RMG1). 4.0 g of coloring composition (RMG1), 0.98 g of UNIDIC ZL-295 manufactured by DIC Corporation, and 0.22 g of propylene glycol monomethyl ether acetate were added and mixed with a paint shaker to obtain an evaluation composition (RCG1) . This composition for evaluation (RCG1) was spin-coated on soda glass and dried at 90 ° C for 3 minutes, and then the spectral transmission spectrum was measured with U-3900 manufactured by Hitachi High Tech Science. In addition, by adjusting the number of rotations when performing spin coating, a spectral transmission spectrum with a maximum transmittance of 70% was measured. When measuring the transmission spectrum, the bottom line is corrected using soda glass. The integrated value of the transmittance of 510nm to 560nm is 2511.6, and the transmittance of 460nm is 8.79.

    Reference example 2    

Into a 300 ml flask, 91 g of sulfonium chloride (reagent of Wako Pure Chemical Industries), 109 g of aluminum chloride (reagent of Kanto Chemical), 15 g of sodium chloride (reagent of Tokyo Chemical Industry), and zinc phthalocyanin manufactured by DIC Corporation 30g, bromine (reagent of Wako Pure Chemical Industries) 230g. The temperature was raised to 130 ° C, and after being taken out into water, it was filtered, washed with water, and dried to obtain zinc halide phthalocyanin (R2). The zinc halide phthalocyanin (R2) was subjected to mass analysis using JMS-S3000 manufactured by Japan Electronics Co., Ltd., and it was confirmed that the average chlorination rate was 1.8 and the average bromination rate was 13.2. In addition, the Delay Time during mass analysis was 500 ns, Laser Intensity was 44%, and the Resolving Power Value of the peak at m / z = 1820 to 1860 was 31804.

40 g of the obtained zinc halide phthalocyanin (R2), 400 g of pulverized sodium chloride, and 63 g of diethylene glycol were put into a double-arm kneader and mixed at 80 ° C. for 8 hours. After kneading, it was taken out in 2 kg of water at 80 ° C, and after stirring for 1 hour, it was filtered, washed with hot water, dried, and pulverized to obtain a green pigment composition (RG2). Using 0.3 to 0.4 mm zirconium beads, 2.48 g of green pigment composition (RG2) and BYK-LPN6919 manufactured by BYK-Chemie Co., Ltd. and 1.24 g of UNIDIC manufactured by DIC Corporation were used with a paint shaker manufactured by Toyo Seiki Co., Ltd. 1.86 g of ZL-295 and 10.92 g of propylene glycol monomethyl ether acetate were dispersed together for 2 hours to obtain a coloring composition (RMG2). 4.0 g of coloring composition (RMG2), 0.98 g of UNIDIC ZL-295 manufactured by DIC Corporation, and 0.22 g of propylene glycol monomethyl ether acetate were added and mixed with a paint shaker to obtain an evaluation composition (RCG2) . This composition for evaluation (RCG2) was spin-coated on soda glass and dried at 90 ° C for 3 minutes, and then the spectral transmission spectrum was measured with U-3900 manufactured by Hitachi High Tech Science. In addition, by adjusting the number of rotations when performing spin coating, a spectral transmission spectrum with a maximum transmittance of 70% was measured. When measuring the transmission spectrum, the bottom line is corrected using soda glass. The integrated value of the transmittance of 510nm to 560nm is 2787.8, and the transmittance of 460nm is 3.07.

    Synthesis Example 1    

While cooling 288 g of 98% sulfuric acid and 272 g of 30% fuming sulfuric acid to 10 ° C. while stirring, 70 g of zinc phthalocyanin manufactured by DIC Corporation was added. Then, it stirred at 60 degreeC for 3 hours. The reaction solution was taken out into 1750 g of water, and after stirring for 1 hour, it was filtered, washed with water, and dried to obtain a sulfonated zinc phthalocyanin derivative (S1). The sulfonated zinc phthalocyanin derivative (S1) was measured by LC-MS, and it was confirmed that the average sulfonation ratio was one. 100 g of ethanol was added to 30 g of alumina (AEROXIDE Alu C) manufactured by Japan Aerosil Corporation, and after stirring sufficiently, 2000 g of water was added to prepare a white slurry. 1.5 g of sulfonated zinc phthalocyanin derivative (S1) was added, adjusted to pH 12 with an aqueous potassium hydroxide solution, and stirred at room temperature for 2 hours. The pH was adjusted to 3 with 10% hydrochloric acid, and after further stirring at room temperature for 1 hour, it was filtered, washed with water, dried, and pulverized to obtain a derivative support (A1). Using 0.3 to 0.4 mm zirconium beads, 2.48 g of the derivative carrier (A1) and 1.24 g of BYK-LPN6919 manufactured by BYK-Chemie Co., Ltd. using a paint shaker manufactured by Toyo Seiki Co., Ltd. 1.86 g of UNIDIC ZL-295 and 10.92 g of propylene glycol monomethyl ether acetate were dispersed together for 2 hours to obtain a colored composition (AMG1). 4.0 g of coloring composition (AMG1), 0.98 g of UNIDIC ZL-295 manufactured by DIC Corporation, and 0.22 g of propylene glycol monomethyl ether acetate were added and mixed with a paint shaker to obtain an evaluation composition (ACG1) . This composition for evaluation (ACG1) was spin-coated on soda glass and dried at 90 ° C for 3 minutes, and then the spectral transmission spectrum was measured with U-3900 manufactured by Hitachi High Tech Science. In addition, by adjusting the number of rotations when performing spin coating, a spectral transmission spectrum with a maximum transmittance of 70% was measured. When measuring the transmission spectrum, the bottom line is corrected using soda glass. The integrated value of the transmittance from 510nm to 560nm is 1988.8, and the transmittance of 460nm is 55.27.

    Synthesis Example 2    

Into a 1 L flask, 55 g of 3-chlorophthalic anhydride, 45 g of phthalic anhydride, 20 g of zinc chloride, 116 g of urea, 600 mg of hexaammonium heptamolybdate tetrahydrate, and 250 g of cyclobutane were stirred, and stirred at 190 ° C. for 5 hours. Thereafter, the heating was stopped, and after cooling, the mixture was filtered, and washed with 780 g of 2-propanol, 1000 g of a 1% sodium hydroxide aqueous solution, and 1000 g of 1% hydrochloric acid. After washing with water, the obtained wet cake was dried at 90 ° C. for 12 hours to obtain dichlorozinc phthalocyanin as a blue solid. While cooling 20 g of 95% sulfuric acid and 180 g of 30% oleum sulfuric acid to 10 ° C. while stirring, 20 g of dichlorozinc phthalocyanin was added. Then, it stirred at 80 degreeC for 5 hours. The reaction solution was taken out into 1000 g of water, and after stirring for 30 minutes, it was filtered, washed with water, and dried to obtain a sulfonated zinc phthalocyanin derivative (S2). The sulfonated zinc phthalocyanin derivative (S2) was measured by LC-MS, and it was confirmed that the average sulfonation rate was one and the average chlorination rate was two. 100 g of ethanol was added to 30 g of alumina (AEROXIDE Alu C) manufactured by Japan Aerosil Corporation, and after stirring sufficiently, 2000 g of water was added to prepare a white slurry. 1.5 g of sulfonated zinc phthalocyanin derivative (S2) was added, adjusted to pH 12 with an aqueous potassium hydroxide solution, and stirred at room temperature for 2 hours. The pH was adjusted to 3 with 10% hydrochloric acid, and further stirred at room temperature for 1 hour, and then filtered, washed with water, dried, and pulverized to obtain a derivative support (A2). Using 0.3 to 0.4 mm zirconium beads, 2.48 g of the derivative carrier (A2) and 1.24 g of BYK-LPN6919 manufactured by BYK-Chemie Co., Ltd. using a paint shaker manufactured by Toyo Seiki Co., Ltd. 1.86 g of UNIDIC ZL-295 and 10.92 g of propylene glycol monomethyl ether acetate were dispersed together for 2 hours to obtain a colored composition (AMG2). 4.0 g of coloring composition (AMG2), 0.98 g of UNIDIC ZL-295 manufactured by DIC Corporation, and 0.22 g of propylene glycol monomethyl ether acetate were added and mixed with a paint shaker to obtain an evaluation composition (ACG2) . This composition for evaluation (ACG2) was spin-coated on soda glass and dried at 90 ° C for 3 minutes, and then the spectral transmission spectrum was measured with U-3900 manufactured by Hitachi High Tech Science. In addition, by adjusting the number of rotations during spin coating, a spectral transmission spectrum with a maximum transmittance of 70% was measured. When measuring the transmission spectrum, the bottom line is corrected using soda glass. The integrated value of the transmittance from 510nm to 560nm is 3054.6, and the transmittance of 460nm is 57.47.

    Synthesis Example 3    

Into a 1 L flask, 111 g of 3-chlorophthalic anhydride, 20 g of zinc chloride, 116 g of urea, 600 mg of hexaammonium heptamolybdate tetrahydrate, and 250 g of cyclobutane were stirred, and stirred at 190 ° C. for 5 hours. Thereafter, the heating was stopped, and after cooling, the mixture was filtered, and washed with 780 g of 2-propanol, 1000 g of a 1% sodium hydroxide aqueous solution, and 1000 g of 1% hydrochloric acid. After washing with water, the obtained wet cake was dried at 90 ° C. for 12 hours to obtain tetrachlorozinc phthalocyanin as a blue solid. While cooling 131 g of 30% oleum sulfuric acid to 10 ° C., the mixture was stirred, and 15 g of tetrachlorozinc phthalocyanin was added. Then, it stirred at 90 degreeC for 3 hours. The reaction solution was taken out into 750 g of water, stirred for 15 minutes, and then filtered, washed with water, and dried to obtain a sulfonated zinc phthalocyanin derivative (S3). The sulfonated zinc phthalocyanin derivative (S3) was measured by LC-MS, and it was confirmed that the average sulfonation rate was 1.6 and the average chlorination rate was 4. 100 g of ethanol was added to 30 g of alumina (AEROXIDE Alu C) manufactured by Japan Aerosil Corporation, and after stirring sufficiently, 2000 g of water was added to prepare a white slurry. 1.5 g of sulfonated zinc phthalocyanin derivative (S3) was added, adjusted to pH 12 with an aqueous potassium hydroxide solution, and stirred at room temperature for 2 hours. The pH was adjusted to 3 with 10% hydrochloric acid, and the mixture was further stirred at room temperature for 1 hour, and then filtered, washed with water, dried, and pulverized to obtain a derivative support (A3). Using 0.3 to 0.4 mm zirconium beads, 2.48 g of the derivative carrier (A3) and 1.24 g of BYK-LPN6919 manufactured by BYK-Chemie Co., Ltd. using a paint shaker manufactured by Toyo Seiki Co., Ltd. 1.86 g of UNIDIC ZL-295 and 10.92 g of propylene glycol monomethyl ether acetate were dispersed together for 2 hours to obtain a colored composition (AMG3). 4.0 g of colored composition (AMG3), 0.98 g of UNIDIC ZL-295 manufactured by DIC Corporation, and 0.22 g of propylene glycol monomethyl ether acetate were added and mixed with a paint shaker to obtain an evaluation composition (ACG3) . This composition for evaluation (ACG3) was spin-coated on soda glass and dried at 90 ° C for 3 minutes, and then the spectral transmission spectrum was measured with U-3900 manufactured by Hitachi High Tech Science. In addition, by adjusting the number of rotations when performing spin coating, a spectral transmission spectrum with a maximum transmittance of 70% was measured. When measuring the transmission spectrum, the bottom line is corrected using soda glass. The integrated value of the transmittance from 510nm to 560nm is 3065.8, and the transmittance of 460nm is 53.41.

    Synthesis Example 4    

Into a 300 ml flask, 54 g of sulfonium chloride (reagent of Wako Pure Chemical Industries), 63 g of aluminum chloride (reagent of Kanto Chemical), 8.6 g of sodium chloride (reagent of Tokyo Chemical Industry), and sulfonated zinc phthalocyanin derivative ( A) 17 g, bromine (reagent of Wako Pure Chemical Industries) 87 g. The temperature was raised to 130 ° C, and after being taken out into water, it was filtered, washed with water, and dried to obtain a sulfonated zinc phthalocyanin derivative (S4). For the sulfonated zinc phthalocyanin derivative (S4), mass analysis using JMS-S3000 manufactured by Japan Electronics Co., Ltd. was performed, and it was confirmed that the average sulfonation rate was 1, the average chlorination rate was 2.2, and the average bromination was performed. The rate was 10.8. In addition, the Delay Time during mass analysis was 275 ns, the Laser Intensity was 42%, and the Resolving Power Value of the peak at m / z = 1820 to 1860 was 42559. 100 g of ethanol was added to 30 g of alumina (AEROXIDE Alu C) manufactured by Japan Aerosil Corporation, and after stirring sufficiently, 2000 g of water was added to prepare a white slurry. 1.5 g of sulfonated zinc phthalocyanin derivative (S4) was added, adjusted to pH 12 with an aqueous potassium hydroxide solution, and stirred at room temperature for 2 hours. The pH was adjusted to 3 with 10% hydrochloric acid, and the mixture was further stirred at room temperature for 1 hour, and then filtered, washed with water, dried, and pulverized to obtain a derivative support (A4). Using 0.3 to 0.4 mm zirconium beads, 2.48 g of the derivative carrier (A4) and 1.24 g of BYK-LPN6919 manufactured by BYK-Chemie Co., Ltd. using a paint shaker manufactured by Toyo Seiki Co., Ltd. 1.86 g of UNIDIC ZL-295 and 10.92 g of propylene glycol monomethyl ether acetate were dispersed together for 2 hours to obtain a colored composition (AMG4). 4.0 g of coloring composition (AMG4), 0.98 g of UNIDIC ZL-295 manufactured by DIC Corporation, and 0.22 g of propylene glycol monomethyl ether acetate were added and mixed with a paint shaker to obtain an evaluation composition (ACG4) . This composition for evaluation (ACG4) was spin-coated on soda glass and dried at 90 ° C for 3 minutes, and then the spectral transmission spectrum was measured with U-3900 manufactured by Hitachi High Tech Science. In addition, by adjusting the number of rotations when performing spin coating, a spectral transmission spectrum with a maximum transmittance of 70% was measured. When measuring the transmission spectrum, the bottom line is corrected using soda glass. The integrated value of the transmittance of 510nm to 560nm is 3273.1, and the transmittance of 460nm is 42.89.

    Synthesis Example 5    

60 g of phthalonitrile, 300 g of 1-chloronaphthalene, and 16 g of aluminum chloride were put into a 1 L flask, and stirred under reflux for 6 hours. After that, the heating was stopped, and the mixture was cooled to 200 ° C. and then filtered under heat, and washed with 600 g of hot toluene and 300 g of acetone. The obtained wet cake was dispersed in 250 g of toluene and stirred under reflux for 3 hours. Filtration was performed again under heat, and after washing with 600 g of hot toluene and 300 g of acetone, the mixture was dispersed into 1500 g of ion-exchanged water, and heated and stirred at 60 ° C for 60 minutes. After filtration and washing with water, vacuum drying was performed at 50 ° C to obtain aluminum phthalocyanin (AlPc-C1) as a blue solid. While maintaining the temperature at 5 ° C, 30 g of aluminum phthalocyanin (AlPc-C1) was slowly dissolved in 1200 g of concentrated sulfuric acid, and stirred at this temperature for 1 hour, while injecting it while stirring so that the temperature did not exceed 5 ° C. It was made to 6000 g of ice water, and it stirred for 1 hour after completion | finish of injection. After filtration and washing with water, it was dispersed again into 6500 g of ion-exchanged water and filtered again. After washing with water, the wet cake was dispersed again to 2500 g of 4% ammonia water, and stirred under reflux for 6 hours. After filtration, the cake was washed with ion-exchanged water, and then vacuum-dried at 50 ° C to obtain aluminum phthalocyanin (AlPc-OH) as a blue solid. While cooling 288 g of 98% sulfuric acid and 272 g of 30% oleum sulfuric acid to 10 ° C. while stirring, 70 g of aluminum phthalocyanin (AlPc-OH) was added. Then, it stirred at 60 degreeC for 3 hours. The reaction solution was taken out into 1750 g of water, and after stirring for 1 hour, it was filtered, washed with water, and dried to obtain a sulfonated aluminum phthalocyanin derivative (S5). The sulfonated aluminum phthalocyanin derivative (S5) was measured by LC-MS, and it was confirmed that the average sulfonation ratio was one. 100 g of ethanol was added to 30 g of alumina (AEROXIDE Alu C) manufactured by Japan Aerosil Corporation, and after stirring well, 2000 g of water was added to prepare a white slurry. 1.5 g of a sulfonated aluminum phthalocyanin derivative (S5) was added, adjusted to pH 12 with an aqueous potassium hydroxide solution, and stirred at room temperature for 2 hours. The pH was adjusted to 3 with 10% hydrochloric acid, and the mixture was further stirred at room temperature for 1 hour, and then filtered, washed with water, dried, and pulverized to obtain a derivative support (A5). Using 0.3 to 0.4 mm zirconium beads, 2.48 g of the derivative carrier (A5) and 1.24 g of BYK-LPN6919 manufactured by BYK-Chemie Co., Ltd. using a paint shaker manufactured by Toyo Seiki Co., Ltd. 1.86 g of UNIDIC ZL-295 and 10.92 g of propylene glycol monomethyl ether acetate were dispersed together for 2 hours to obtain a colored composition (AMG5). 4.0 g of coloring composition (AMG5), 0.98 g of UNIDIC ZL-295 manufactured by DIC Corporation, and 0.22 g of propylene glycol monomethyl ether acetate were added and mixed with a paint shaker to obtain an evaluation composition (ACG5) . This composition for evaluation (ACG5) was spin-coated on soda glass and dried at 90 ° C for 3 minutes, and then the spectral transmission spectrum was measured with U-3900 manufactured by Hitachi High Tech Science. In addition, by adjusting the number of rotations when performing spin coating, a spectral transmission spectrum with a maximum transmittance of 70% was measured. When measuring the transmission spectrum, the bottom line is corrected using soda glass. The integrated value of the transmittance from 510nm to 560nm is 2757.5, and the transmittance of 460nm is 64.24.

    Synthesis Example 6    

100 g of ethanol was added to 30 g of alumina (AEROXIDE Alu C) manufactured by Japan Aerosil Corporation, and after stirring sufficiently, 2000 g of water was added to prepare a white slurry. 1.5 g of Solsperse 12000 (sulfonated copper phthalocyanin derivative manufactured by Lubrizol Co., Ltd., Japan) was added, the pH was adjusted to pH 12 with a potassium hydroxide aqueous solution, and the mixture was stirred at room temperature for 2 hours. The pH was adjusted to 3 with 10% hydrochloric acid, and the mixture was further stirred at room temperature for 1 hour, and then filtered, washed with water, dried, and pulverized to obtain a derivative support (A6). Using 0.3 to 0.4 mm zirconium beads, 2.48 g of the derivative carrier (A6) and 1.24 g of BYK-LPN6919 manufactured by BYK-Chemie Co., Ltd. using a paint shaker manufactured by Toyo Seiki Co., Ltd. 1.86 g of UNIDIC ZL-295 and 10.92 g of propylene glycol monomethyl ether acetate were dispersed together for 2 hours to obtain a colored composition (AMG6). 4.0 g of coloring composition (AMG6), 0.98 g of UNIDIC ZL-295 manufactured by DIC Corporation, and 0.22 g of propylene glycol monomethyl ether acetate were added and mixed with a paint shaker to obtain an evaluation composition (ACG6) . This composition for evaluation (ACG6) was spin-coated on soda glass and dried at 90 ° C for 3 minutes, and then the spectral transmission spectrum was measured with U-3900 manufactured by Hitachi High Tech Science. In addition, by adjusting the number of rotations when performing spin coating, a spectral transmission spectrum with a maximum transmittance of 70% was measured. When measuring the transmission spectrum, the bottom line is corrected using soda glass. The integrated value of the transmittance from 510nm to 560nm is 1303.8, and the transmittance of 460nm is 64.19.

    Synthesis Example 7    

15 g of cyclobutane, 10 g of titanium tetrachloride, 200 g of dimethyl phthalate, 100 g of sodium 4-chlorophthalate, and 31 g of 20% oleum sulfuric acid were charged into a 1 L flask. After heating at 170 ° C for 30 minutes, urea was added. 150g, copper (I) chloride 9.5g. It was further heated at 150 ° C for 1 hour, 170 ° C for 1 hour, and 190 ° C for 8 hours. After cooling to 80 ° C, it was taken out into 700 g of water in which 60 g of sodium hydroxide was dissolved. After stirring at 85 ° C for 1 hour, it was poured into 2300 g of water while stirring, and further stirred at 80 ° C for 2 hours. After filtering and washing with hot water, the slurry was reslurried in 2300 g of water in which 140 g of 35% hydrochloric acid was dissolved, and heated at 70 ° C. for 1 hour while stirring. After filtering, washing with hot water, and drying at 80 ° C. for 17 hours, tetrachlorocopper phthalocyanin was obtained as a blue solid. While cooling 131 g of 30% fuming sulfuric acid to 10 ° C., the mixture was stirred, and 15 g of tetrachlorocopperphthalocyanin was added. Then, it stirred at 90 degreeC for 3 hours. The reaction solution was taken out into 750 g of water, stirred for 15 minutes, and then filtered, washed with water, and dried to obtain a sulfonated copper phthalocyanin derivative (S7). The sulfonated copper phthalocyanin derivative (S7) was measured by LC-MS, and it was confirmed that the average sulfonation rate was one and the average chlorination rate was four. 100 g of ethanol was added to 30 g of alumina (AEROXIDE Alu C) manufactured by Japan Aerosil Corporation, and after stirring sufficiently, 2000 g of water was added to prepare a white slurry. 1.5 g of sulfonated copper phthalocyanin derivative (S7) was added, adjusted to pH 12 with an aqueous potassium hydroxide solution, and stirred at room temperature for 2 hours. The pH was adjusted to 3 with 10% hydrochloric acid, and further stirred at room temperature for 1 hour, and then filtered, washed with water, dried, and pulverized to obtain a derivative support (A7). Using 0.3 to 0.4 mm zirconium beads, 2.48 g of the derivative support (A7) and 1.24 g of BYK-LPN6919 manufactured by BYK-Chemie Co., Ltd. using a paint shaker manufactured by Toyo Seiki Co., Ltd. 1.86 g of UNIDIC ZL-295 and 10.92 g of propylene glycol monomethyl ether acetate were dispersed together for 2 hours to obtain a colored composition (AMG7). 4.0 g of coloring composition (AMG7), 0.98 g of UNIDIC ZL-295 manufactured by DIC Corporation, and 0.22 g of propylene glycol monomethyl ether acetate were added and mixed with a paint shaker to obtain an evaluation composition (ACG7) . This composition for evaluation (ACG7) was spin-coated on soda glass and dried at 90 ° C for 3 minutes, and then the spectral transmission spectrum was measured with U-3900 manufactured by Hitachi High Tech Science. In addition, by adjusting the number of rotations when performing spin coating, a spectral transmission spectrum with a maximum transmittance of 70% was measured. When measuring the transmission spectrum, the bottom line is corrected using soda glass. The integrated value of the transmittance of 510nm to 560nm is 1401.9, and the transmittance of 460nm is 64.60.

    Manufacturing example 1    

Put 36 g of zinc phthalocyanin (R1), 4 g of sulfonated zinc phthalocyanin derivative (S1), 400 g of pulverized sodium chloride, and 63 g of diethylene glycol into a dual-arm kneader and knead at 80 ° C. 8 hour. After kneading, it was taken out in 2 kg of water at 80 ° C., and after stirring for 1 hour, it was filtered, washed with hot water, dried, and pulverized to obtain a green pigment composition (G1).

    Manufacturing example 2    

A green pigment composition (G2) was obtained in the same manner except that the sulfonated zinc phthalocyanin derivative (S1) was replaced with the sulfonated zinc phthalocyanin derivative (S2) in Production Example 1.

    Manufacturing example 3    

A green pigment composition (G3) was obtained in the same manner except that the sulfonated zinc phthalocyanin derivative (S1) was replaced with the sulfonated zinc phthalocyanin derivative (S3) in Production Example 1.

    Manufacturing Example 4    

A green pigment composition (G4) was obtained in the same manner except that the sulfonated zinc phthalocyanin derivative (S1) was replaced with the sulfonated zinc phthalocyanin derivative (S4) in Production Example 1.

    Manufacturing Example 5    

A green pigment composition (G5) was obtained in the same manner except that the sulfonated zinc phthalocyanin derivative (S1) was replaced with the sulfonated aluminum phthalocyanin derivative (S5) in Production Example 1.

    Manufacturing Example 6    

A green pigment composition (G6) was obtained in the same manner except that the sulfonated zinc phthalocyanin derivative (S1) was replaced with the sulfonated copper phthalocyanin derivative (S7) in Production Example 1.

    Manufacturing Example 7    

38 g of zinc phthalocyanin (R1), 2 g of sulfonated zinc phthalocyanin derivative (S1), 400 g of pulverized sodium chloride, and 63 g of diethylene glycol were put into a dual-arm kneader and kneaded at 80 ° C. 8 hour. After kneading, it was taken out in 2 kg of water at 80 ° C., and after stirring for 1 hour, it was filtered, washed with hot water, dried, and pulverized to obtain a green pigment composition (G7).

    Manufacturing Example 8    

A green pigment composition (G8) was obtained in the same manner except that the sulfonated zinc phthalocyanin derivative (S1) was replaced with the sulfonated zinc phthalocyanin derivative (S2) in Production Example 7.

    Manufacturing Example 9    

A green pigment composition (G9) was obtained in the same manner except that the sulfonated zinc phthalocyanin derivative (S1) was replaced with the sulfonated zinc phthalocyanin derivative (S3) in Production Example 7.

    Manufacturing Example 10    

Put 36 g of zinc phthalocyanin (R2), 4 g of sulfonated zinc phthalocyanin derivative (S3), 400 g of pulverized sodium chloride, and 63 g of diethylene glycol into a dual-arm kneader and knead at 80 ° C. 8 hour. After kneading, it was taken out of 2 kg of water at 80 ° C., and after stirring for 1 hour, it was filtered, washed with hot water, dried, and pulverized to obtain a green pigment composition (G10).

    Manufacturing Example 11    

A green pigment composition (G11) was obtained in the same manner except that the sulfonated zinc phthalocyanin derivative (S3) was replaced with the sulfonated zinc phthalocyanin derivative (S4) in Production Example 10.

    Manufacturing Example 12    

A green pigment composition was obtained in the same manner as in Production Example 10 except that the sulfonated zinc phthalocyanin derivative (S3) was replaced with Solsperse 12000 (sulfonated copper phthalocyanin derivative manufactured by Japan Lubrizol Co., Ltd.). (G12).

    Manufacturing Example 13    

Using 0.3 to 0.4 mm zirconium beads, using a paint shaker manufactured by Toyo Seiki Co., Ltd., 1.65 g of pigment yellow 138 (CHROMOFINE yellow 6206EC manufactured by Daiichi Seika Co., Ltd.) and 3.85 g of DISPERBYK-161 (made by BYK-Chemie) were used. 11.00 g of propylene glycol monomethyl ether acetate were dispersed together for 2 hours to obtain a colored composition (MY1). 4.0 g of coloring composition (MY1), 0.98 g of UNIDIC ZL-295, and 0.22 g of propylene glycol monomethyl ether acetate were added and mixed with a paint shaker to obtain a composition for coloring (TY1).

    Example 1    

Using 0.3 to 0.4 mm zirconium beads, 2.48 g of green pigment composition (G1) and BYK-LPN6919 1.24 g by BYK-Chemie Co., Ltd. and UNIDIC manufactured by DIC Co., Ltd. using a paint shaker manufactured by Toyo Seiki Co., Ltd. 1.86 g of ZL-295 and 10.92 g of propylene glycol monomethyl ether acetate were dispersed together for 2 hours to obtain a colored composition (MG1). 4.0 g of coloring composition (MG1), 0.98 g of UNIDIC ZL-295 manufactured by DIC Corporation, and 0.22 g of propylene glycol monomethyl ether acetate were added and mixed with a paint shaker to obtain a color filter. Evaluation composition (CG1) for a green pixel portion. The coating liquid obtained by mixing the composition for coloring (TY1) and the composition for evaluation (CG1) produced in Production Example 13 was spin-coated on soda glass, dried at 90 ° C for 3 minutes, and then produced under a C light source. Chroma (x, y) = (0.250, 0.615) coating film. The brightness was measured using U-3900 manufactured by Hitachi High Tech Science, and the film thickness was measured using white interference microscope VS1330 manufactured by Hitachi High Tech Science.

    Example 2    

Except having replaced the green pigment composition (G1) with the green pigment composition (G2) in Example 1, it carried out similarly, and obtained the composition for evaluation (CG2). The coating liquid obtained by mixing the composition for coloring (TY1) and the composition for evaluation (CG2) produced in Production Example 13 was spin-coated on soda glass, dried at 90 ° C for 3 minutes, and then produced under a C light source. Chroma (x, y) = (0.250,0.615). The brightness was measured with U-3900 manufactured by Hitachi High Tech Science, and the film thickness was measured with white interference microscope VS1330 manufactured by Hitachi High Tech Science.

    Example 3    

Except having replaced the green pigment composition (G1) with the green pigment composition (G3) in Example 1, it carried out similarly, and obtained the composition for evaluation (CG3). The coating liquid obtained by mixing the toning composition (TY1) and the evaluation composition (CG3) produced in Production Example 13 was spin-coated on soda glass, and dried at 90 ° C for 3 minutes, and then produced under a C light source. Chroma (x, y) = (0.250,0.615). The brightness was measured with U-3900 manufactured by Hitachi High Tech Science, and the film thickness was measured with white interference microscope VS1330 manufactured by Hitachi High Tech Science.

    Example 4    

Except having replaced the green pigment composition (G1) with the green pigment composition (G4) in Example 1, it carried out similarly, and obtained the composition for evaluation (CG4). The coating liquid obtained by mixing the toning composition (TY1) and the evaluation composition (CG4) produced in Production Example 13 was spin-coated on soda glass, and dried at 90 ° C for 3 minutes, and then produced under a C light source. Chroma (x, y) = (0.250,0.615). The brightness was measured with U-3900 manufactured by Hitachi High Tech Science, and the film thickness was measured with white interference microscope VS1330 manufactured by Hitachi High Tech Science.

    Example 5    

Except having replaced the green pigment composition (G1) with the green pigment composition (G5) in Example 1, it carried out similarly, and obtained the composition for evaluation (CG5). The coating liquid obtained by mixing the toning composition (TY1) and the evaluation composition (CG5) produced in Production Example 13 was spin-coated on soda glass, and dried at 90 ° C for 3 minutes, and then produced under a C light source. Chroma (x, y) = (0.250,0.615). The brightness was measured with U-3900 manufactured by Hitachi High Tech Science, and the film thickness was measured with white interference microscope VS1330 manufactured by Hitachi High Tech Science.

    Example 6    

Except having replaced the green pigment composition (G1) with the green pigment composition (G7) in Example 1, it carried out similarly, and obtained the composition for evaluation (CG7). The coating liquid obtained by mixing the composition for coloring (TY1) and the composition for evaluation (CG7) produced in Production Example 13 was spin-coated on soda glass, dried at 90 ° C for 3 minutes, and then produced under a C light source. Chroma (x, y) = (0.250,0.615). The brightness was measured with U-3900 manufactured by Hitachi High Tech Science, and the film thickness was measured with white interference microscope VS1330 manufactured by Hitachi High Tech Science.

    Example 7    

Except having replaced the green pigment composition (G1) with the green pigment composition (G8) in Example 1, it carried out similarly, and obtained the composition for evaluation (CG8). The coating liquid obtained by mixing the toning composition (TY1) and the evaluation composition (CG8) produced in Production Example 13 was spin-coated on soda glass, and dried at 90 ° C for 3 minutes, and then produced under a C light source. Chroma (x, y) = (0.250,0.615). The brightness was measured with U-3900 manufactured by Hitachi High Tech Science, and the film thickness was measured with white interference microscope VS1330 manufactured by Hitachi High Tech Science.

    Example 8    

Except having replaced the green pigment composition (G1) with the green pigment composition (G9) in Example 1, it carried out similarly, and obtained the composition for evaluation (CG9). The coating liquid obtained by mixing the toning composition (TY1) and the evaluation composition (CG9) produced in Production Example 13 was spin-coated on soda glass, and dried at 90 ° C for 3 minutes, and then produced under a C light source. Chroma (x, y) = (0.250,0.615). The brightness was measured with U-3900 manufactured by Hitachi High Tech Science, and the film thickness was measured with white interference microscope VS1330 manufactured by Hitachi High Tech Science.

    Example 9    

Using 0.3 to 0.4 mm of zirconium beads, 2.23 g of green pigment composition (RG1) and 0.25 g of sulfonated zinc phthalocyanine derivative (S1) were produced with a paint shaker manufactured by Toyo Seiki Co., Ltd. and manufactured by BYK-Chemie 1.24 g of BYK-LPN6919, 1.86 g of UNIDIC ZL-295 manufactured by DIC Corporation, and 10.92 g of propylene glycol monomethyl ether acetate were dispersed together for 2 hours to obtain a colored composition (MG10). 4.0 g of coloring composition (MG10), 0.98 g of UNIDIC ZL-295 manufactured by DIC Corporation, and 0.22 g of propylene glycol monomethyl ether acetate were added and mixed with a paint shaker to obtain a color filter. Evaluation composition (CG10) for a green pixel portion. The coating liquid obtained by mixing the toning composition (TY1) and the evaluation composition (CG10) produced in Production Example 13 was spin-coated on soda glass, and dried at 90 ° C for 3 minutes, and then produced under a C light source. Chroma (x, y) = (0.250,0.615). The brightness was measured with U-3900 manufactured by Hitachi High Tech Science, and the film thickness was measured with white interference microscope VS1330 manufactured by Hitachi High Tech Science.

    Example 10    

A composition for evaluation (CG11) was obtained in the same manner as in Example 9 except that the sulfonated zinc phthalocyanin derivative (S1) was replaced with the sulfonated zinc phthalocyanin derivative (S2). The coating liquid obtained by mixing the toning composition (TY1) and the evaluation composition (CG11) produced in Production Example 13 was spin-coated on soda glass, and dried at 90 ° C for 3 minutes, and then produced under a C light source. Chroma (x, y) = (0.250,0.615). The brightness was measured with U-3900 manufactured by Hitachi High Tech Science, and the film thickness was measured with white interference microscope VS1330 manufactured by Hitachi High Tech Science.

    Example 11    

A composition for evaluation (CG12) was obtained in the same manner as in Example 9 except that the sulfonated zinc phthalocyanin derivative (S1) was replaced with the sulfonated zinc phthalocyanin derivative (S3). The coating liquid obtained by mixing the composition for coloring (TY1) and the composition for evaluation (CG12) produced in Production Example 13 was spin-coated on soda glass, dried at 90 ° C for 3 minutes, and then produced under a C light source. Chroma (x, y) = (0.250,0.615). The brightness was measured with U-3900 manufactured by Hitachi High Tech Science, and the film thickness was measured with white interference microscope VS1330 manufactured by Hitachi High Tech Science.

    Example 12    

Except having replaced the green pigment composition (G1) with the green pigment composition (G10) in Example 1, it carried out similarly, and obtained the composition for evaluation (CG13). The coating liquid obtained by mixing the toning composition (TY1) and the evaluation composition (CG13) produced in Production Example 13 was spin-coated on soda glass, and dried at 90 ° C for 3 minutes, and then produced under a C light source. The chromaticity (x, y) = (0.275,0.570) of the coating film. The brightness was measured with U-3900 manufactured by Hitachi High Tech Science, and the film thickness was measured with white interference microscope VS1330 manufactured by Hitachi High Tech Science.

    Example 13    

Except having replaced the green pigment composition (G1) with the green pigment composition (G11) in Example 1, it carried out similarly, and obtained the composition for evaluation (CG14). The coating liquid obtained by mixing the toning composition (TY1) and the evaluation composition (CG14) produced in Production Example 13 was spin-coated on soda glass, and dried at 90 ° C for 3 minutes, and then produced under a C light source. The chromaticity (x, y) = (0.275,0.570) of the coating film. The brightness was measured with U-3900 manufactured by Hitachi High Tech Science, and the film thickness was measured with white interference microscope VS1330 manufactured by Hitachi High Tech Science.

    Comparative Example 1    

Except having replaced the green pigment composition (G1) with the green pigment composition (G6) in Example 1, it carried out similarly, and obtained the composition for evaluation (CG6). The coating liquid obtained by mixing the toning composition (TY1) and the evaluation composition (CG6) produced in Production Example 13 was spin-coated on soda glass, and dried at 90 ° C for 3 minutes, and then produced under a C light source. Chroma (x, y) = (0.250,0.615). The brightness was measured with U-3900 manufactured by Hitachi High Tech Science, and the film thickness was measured with white interference microscope VS1330 manufactured by Hitachi High Tech Science.

    Comparative Example 2    

Except having replaced the green pigment composition (G1) with the green pigment composition (G12) in Example 1, it carried out similarly, and obtained the composition for evaluation (CG12). The coating liquid obtained by mixing the composition for coloring (TY1) and the composition for evaluation (CG12) produced in Production Example 13 was spin-coated on soda glass, dried at 90 ° C for 3 minutes, and then produced under a C light source. The chromaticity (x, y) = (0.275,0.570) of the coating film. The brightness was measured with U-3900 manufactured by Hitachi High Tech Science, and the film thickness was measured with white interference microscope VS1330 manufactured by Hitachi High Tech Science.

As shown in Tables 1 and 2, it was confirmed that the sulfonated zinc phthalocyanin derivative and the sulfonated aluminum phthalocyanin derivative had higher brightness than the sulfonated copper phthalocyanin derivative. In addition, those with a thinner film thickness than 3.4 μm were determined as ◎, those with a film thickness of 3.4 μm or more and 3.6 μm or less were determined as ○, and those with a film thickness ratio of 3.6 μm or more were determined as ×. Or sulfonated aluminum phthalocyanin derivative is ◎ or ○.

In the present invention, a pigment derivative having a higher D2 / D1 than the currently used sulfonated copper phthalocyanin (SOLSPERSE12000, sulfonated copper phthalocyanin derivative (S7)) is selected for use, and therefore has high brightness. In addition, in the present invention, a pigment derivative having a transmittance of 460 nm that is lower than that of the currently used sulfonated copper phthalocyanin (SOLSPERSE12000, sulfonated copper phthalocyanin derivative (S7)) is used, and therefore the film thickness is thin.

Claims (13)

A pigment composition for a color filter, comprising a zinc halide phthalocyanin pigment and a pigment derivative represented by the following general formula (1), (In general formula (1), Z ¹ to Z ¹⁶ each independently represent a bromine atom, a chlorine atom, a hydrogen atom, or a sulfonic acid group, the average number of substituents of the sulfonic acid group is at least 0.1 to 4, and M represents Al, Si, Sc, Ti, V, Mg, Fe, Co, Ni, Zn, Ga, Ge, Y, Zr, Nb, In, Sn or Pb).     The pigment composition for a color filter according to claim 1, wherein the zinc halide phthalocyanin pigment is used to form a coating film having a transmittance at a maximum transmission wavelength of 70% and a transmittance of 510 nm to 560 nm. The integrated value of D1 is 510 nm to 560 nm of a coating film formed using a derivative support obtained by supporting the pigment derivative on alumina, and having a spectral transmittance at a maximum transmission wavelength of 70%. When the integrated value of the transmittance is D2, it has a spectral characteristic in which the ratio (D2 / D1) of D1 and D2 is 0.7 or more.     The pigment composition for a color filter according to claim 1 or 2, wherein the pigment derivative is in the formula (1), and Z ¹ to Z ¹⁶ are any of a bromine atom, a chlorine atom, a hydrogen atom, or a sulfonic acid group. One, and based on the average in one molecule, at least derived from any two or more pigments having a chlorine atom selected from Z ¹ , Z ⁴ , Z ⁵ , Z ⁸ , Z ⁹ , Z ¹² , Z ¹³ , Z ¹⁶ Thing. The pigment composition for a color filter according to claim 1 or 2, wherein the pigment derivative is in the formula (1), and Z ¹ to Z ¹⁶ have any of a bromine atom, a chlorine atom, a hydrogen atom, or a sulfonic acid group. One, and based on the average of one molecule, at least derived from any two or more pigments having a bromine atom selected from Z ¹ , Z ⁴ , Z ⁵ , Z ⁸ , Z ⁹ , Z ¹² , Z ¹³ , and Z ¹⁶ Thing. The requested item 1 to 4, the color filter according to any one of the pigment composition, wherein the pigment derivative-based molecule in an average amount, (1), Z ¹ - Z ¹⁶ of the formula 10 to 14 Pigment derivatives with 8 halogen atoms, 8-12 bromine atoms, and 2-5 chlorine atoms.     The pigment composition for a color filter according to any one of claims 1 to 5, further comprising a yellow pigment.         A color filter characterized in that the pixel portion contains the pigment composition for a color filter according to any one of claims 1 to 6.     A color filter comprising a zinc halide phthalocyanin pigment and a pigment derivative represented by the following general formula (1), (In the general formula (1), Z ¹ to Z ¹⁶ each independently represent a bromine atom, a chlorine atom, a hydrogen atom, or a sulfonic acid group, the average number of substituents of the sulfonic acid group is at least 0.1 to 4, and M represents Al, Si, Sc, Ti, V, Mg, Fe, Co, Ni, Zn, Ga, Ge, Y, Zr, Nb, In, Sn or Pb).     For example, as for the color filter of claim 8, the integrated value of the transmittance of 510nm to 560nm of the coating film formed by using the zinc halide phthalocyanin pigment so that the spectral transmittance of the maximum transmission wavelength becomes 70% is set. D1, the integral of the transmittance of 510nm to 560nm of the coating film formed by using a derivative support obtained by supporting the pigment derivative on alumina and forming a spectral transmittance at a maximum transmission wavelength of 70% When the value is set to D2, it has a spectral characteristic in which the ratio (D2 / D1) of D1 and D2 is 0.7 or more.     The color filter according to claim 8 or 9, wherein the pigment derivative is in the formula (1), and Z ¹ to Z ¹⁶ are any of a bromine atom, a chlorine atom, a hydrogen atom, or a sulfonic acid group, and Based on an average of one molecule, at least any two or more pigment derivatives having a chlorine atom selected from Z ¹ , Z ⁴ , Z ⁵ , Z ⁸ , Z ⁹ , Z ¹² , Z ¹³ , and Z ¹⁶ . The color filter according to claim 8 or 9, wherein the pigment derivative is in the formula (1), Z ¹ to Z ¹⁶ have any of a bromine atom, a chlorine atom, a hydrogen atom, or a sulfonic acid group, and Based on an average of one molecule, at least any two or more pigment derivatives having a bromine atom selected from Z ¹ , Z ⁴ , Z ⁵ , Z ⁸ , Z ⁹ , Z ¹² , Z ¹³ , and Z ¹⁶ . The color filter according to any one of claims 8 to 11, wherein the pigment derivative is an average in one molecule, and Z ¹ to Z ¹⁶ in the formula (1) contain 10 to 14 halogen atoms, Pigment derivatives with 8 to 12 bromine atoms and 2 to 5 chlorine atoms.     The color filter according to any one of claims 8 to 12, further comprising a yellow pigment.