JP5215785B2 - Coupler, dye, method for producing the dye, colorant using the dye, and coloring method - Google Patents

Description

  The present invention relates to a compound useful as a coupler (intermediate) that is a raw material for a dye, a pigment, and a dispersant for an organic pigment, and a dye, a colorant, and a coloring method using the coupler.

  A color filter used in a liquid crystal display is formed by applying a coating liquid in which a pigment is dispersed in a photoresist (photosensitive resin liquid) on a color filter substrate by spin coating, coating, or electrodeposition. This is mainly produced by a so-called pigment dispersion method (a method using a pigment as a colorant), in which a colored coating film is developed after exposure through a photomask and developed, and the coating film is patterned to form pixels.

  At that time, as a coloring pigment of the coating liquid used for forming the blue pixel, in addition to ε-type phthalocyanine (CI pigment blue 15: 6) which is a blue pigment, for the purpose of color correction (toning), Purple dioxazine violet pigment (CI Pigment Violet 23) has been formulated and used. In particular, the ratio of dioxazine violet pigment to the ε-type phthalocyanine as a blue pigment is increased in order to make the blue pixel of the color filter for TV monitors, whose demand has been growing significantly in recent years, into a more favorable color quality pixel. It is requested.

  However, when the compounded pigment composed of the ε-type phthalocyanine pigment and the dioxazine violet pigment is dispersed in a dispersion medium such as a photoresist, the compounded pigment is not sufficiently dispersed only by dispersing with a normal disperser. Therefore, when a blue pixel is formed from the obtained coating liquid, the pixel lacks light transmittance, and the light transmittance is insufficient as a blue pixel of the color filter. The coating solution for forming a blue pixel was unsatisfactory.

  On the other hand, as a resin generally used for the photoresist as a dispersion medium of the pigment, an acrylic polymer having a high acid value is mainly used so that a colored coating film after exposure can be developed with an alkaline aqueous solution. It has been adopted. However, in the coating solution composed of the above-mentioned blended pigment and a photoresist containing the above high acid value acrylic resin, the pigment is likely to aggregate and the viscosity of the coating solution tends to increase, and the coating solution increases in viscosity over time. There is a problem that the storage stability of the coating liquid often deteriorates.

  When producing each color pixel of a color filter with a coating solution with the above difficulties, the coating solution to be used is applied to the substrate by spin coating, and then the coating film is patterned by exposure and development. If the coating solution used has a high viscosity, or if the pigment aggregates and exhibits a thixotropic viscosity, the central portion of the colored coating film (before exposure) made of the coating solution will rise, so a large screen color filter should be used. At the time of manufacturing, there is a problem that unevenness and density difference occur in hue between the pixel at the center of the substrate and the pixel at the periphery.

  Therefore, the coating solution for color filters usually has a pigment concentration in the high concentration range of 5 to 20% by mass, but the dispersed state does not aggregate the pigment particles, and a general normal dry paint or baking. The viscosity should be lower than that of the paint (for example, about 5 to 20 mPa · s) and excellent in storage stability.

  In order to satisfy the above-described requirements, conventionally, when the pigment is ε-type phthalocyanine (CI Pigment Blue 15: 6), the above-mentioned pigment using a substituted derivative of phthalocyanine blue or a substituted derivative of dioxazine violet as a dispersant. Or a method of treating the pigment with the derivative is proposed (for example, see Patent Documents 1 to 6).

JP-A-56-167762 Japanese Patent Publication No. 1-334268 JP-A-4-246469 JP-A-6-240161 JP-A-6-240162 Japanese Patent Laid-Open No. 7-188576

  On the other hand, due to the demand for further improvement in the performance of the color filter, it has become necessary to improve the transparency of the colored pixels, increase the contrast of the transmitted light of the colored pixels, and increase the pigment concentration of the colored pixels. However, in the method of using the pigment derivative as a dispersant for dispersing the pigment, the transparency of the colored pixel is improved by improving the dispersibility of the pigment, and the viscosity is increased and the storage stability is lowered by increasing the pigment concentration. It is difficult to prevent, and these improvements are desired.

  The present inventors have solved the above-mentioned problems when the pigment derivative is used as a pigment dispersant in the preparation of a color filter coating solution having a high pigment concentration, and improved the color quality of the color filter coating solution. As a result of diligent research to develop pigment dispersants that enable low viscosity, azo dyes obtained using specific intermediates act as excellent pigment dispersants in smaller amounts, for color filters. The present invention has been completed by finding that the viscosity of the coating liquid can be reduced, the viscosity of the coating liquid during storage can be prevented and gelation can be prevented, and the transparency of the most important colored pixels as a color filter can be improved. It came to do.

This invention provides the pigment | dye characterized by being either of the pigments (1)-(9) represented by the following structural formula .

また、本発明は、上記色素を含むことを特徴とする着色剤、および上記着色剤によることを特徴とする物品の着色方法を提供する。また、本発明は、下記一般式（２）で表されることを特徴とするカップラーを提供する。

（ただし、式中の置換基Ｘは同じでも異なってもよく、ハロゲン原子、ヒドロキシル基、ニトロ基、アルキル基、アルコキシル基またはフタルイミドメチル基を表す。Ｒは水素原子またはＣ ₁ 〜Ｃ ₁₂ のアルキル基を表す。ｍは０〜３の整数である。）ここでｍが０であり、Ｒが水素原子またはＣ ₁ 〜Ｃ ₄ のアルキル基であることが好ましい。 In addition, the present invention is a production method for producing the above-mentioned dye, which is synthesized using a compound represented by the following formula (K-1) or (K-2) as a coupler A manufacturing method is provided.

Also, the present invention may contain coloring agents, characterized in that it comprises the dye, and provides a method of coloring an article, characterized in that by the colorant. Moreover, this invention provides the coupler represented by following General formula (2).

(However, the substituents X in the formula may be the same or different and each represents a halogen atom, a hydroxyl group, a nitro group, an alkyl group, an alkoxyl group or a phthalimidomethyl group. R is a hydrogen atom or a C ₁ -C ₁₂ alkyl group. .m represents a group is an integer of 0-3.) where m is 0, it is preferred that R is a hydrogen atom or an alkyl group C ₁ -C _4.

  The coupler of the present invention is useful as an intermediate for various azo dyes, azo pigments, and organic pigment dispersants. In particular, azo dyes having 1 to 3 sulfonic acid groups, carboxyl groups or salts thereof obtained by using the coupler of the present invention, as organic pigment dispersants, various organic pigments, paints, printing inks, It can be stably dispersed at a high concentration and low viscosity in a dispersion medium such as a color filter coating solution. The dispersion of the organic pigment obtained using the above dispersant is useful as a colorant for the color filter coating solution, and has excellent spectral transmittance characteristics when PB15: 6 and PV23 are combined as the pigment. It is possible to form a blue pixel which has a clear, high transparency, and excellent fastness such as light resistance, heat resistance, solvent resistance, chemical resistance, and water resistance.

Next, the present invention will be described in more detail with reference to preferred embodiments.
The novel couplers represented by the general formula (1) or (2) are 2-hydroxy-, respectively, using thionyl chloride or phosphorus trichloride as a condensing agent in an inert solvent such as toluene, xylene or monochlorobenzene. It can be obtained by a condensation reaction of 3-naphthoic acid (BON acid) or benzacylic acid (HBCC acid) with unsubstituted or substituted 3-aminocarbazole or 3-amino-9-alkylcarbazole. Specific production examples are described in the examples. Examples of the alkyl group include C _{1 to} C ₁₂ alkyl groups, and a methyl group, an ethyl group, a propyl group, and a butyl group are preferable.

  The above couplers can be subjected to coupling reactions with various aromatic primary amine diazonium salts in a conventional manner to obtain various azo dyes and azo pigments. A particularly preferred use of the obtained azo dye is a raw material for a dispersant for an organic pigment. Hereinafter, the use of the coupler of the present invention will be described by giving examples of organic pigment dispersants using the coupler of the present invention.

The organic pigment dispersant obtained by using the coupler of the present invention is represented by the following general formula (3) or (4). In the following general formula (3) or (4), the substituent X is preferably a chlorine atom, a bromine atom or a nitro group.

(In the formula, R _D is at least one selected from the group consisting of 1 to 3 sulfonic acid groups, a metal salt thereof, an ammonia salt, an organic amine salt, and an organic quaternary ammonium compound salt. The substituent Y may be the same or different and represents a halogen atom, a hydroxyl group, a nitro group, an alkyl group, an alkoxyl group, an unsubstituted or substituted phthalimidomethyl group. X, R and m are as defined above, and n is an integer of 0 to 3.)

In order to obtain the compound represented by the general formula (3) or (4), first, the base component (R _D —NH ₂ ) having 1 to 3, preferably 1 sulfonic acid group or carboxyl group ( Aromatic primary amine) is diazo and then coupled to the coupler of the present invention represented by the general formula (1) or (2), respectively, and is represented by the following general formula (5) or (6). Azo dyes are synthesized.

（ただし、式中のＲ_D、Ｒ、Ｘおよびｍは前記と同一意義を有する。）

(However, R _D , R, X and m in the formula have the same meaning as described above.)

  Further, if necessary, the azo dye represented by the general formula (5) or (6) is further subjected to a substitution reaction to introduce a substituent Y, whereby the general formula (3) or (4). It can convert into the dispersing agent of the organic pigment which consists of a compound represented by these.

The base component (R _D —NH ₂ ) having a sulfonic acid group used above is not particularly limited as long as diazotization and a coupling reaction are possible. For example, sulfanilic acid (p-aminobenzenesulfonic acid), 2-methylaniline-4-sulfonic acid, methanylic acid (m-aminobenzenesulfonic acid), 4-chloroaniline-3-sulfonic acid, orternic acid (o-amino) Benzenesulfonic acid), C acid, 2B acid, 2-toluidine-4-sulfonic acid, 4-toluidine-2-sulfonic acid, o-chloromethanilic acid, o-anisidine-p-sulfonic acid, aniline-2,5-disulfone Acid, Naphthonic acid, Lorentzic acid, Brenaric acid, 1,6-Clevic acid, 1,7-Clevic acid, Peric acid, Tobias acid, 2-Naphthylamine-7-sulfonic acid, Darlic acid, S acid, M acid, gamma Acid, J acid, H acid, SS acid, RR acid, R acid, K acid, 2R acid, amino G acid, amino J acid, 1-aminoanthraquinone-5-sulfonic acid, -Aminoanthraquinone-8-sulfonic acid, 1-aminoanthraquinone-2-sulfonic acid, 6- (3-sulfo) benzamido-4-methoxy-m-toluidine, 4- (3-sulfo) benzamido-2,5-dimethoxy Aniline, 4- (3-sulfo) benzamide-2,5-diethoxyaniline and the like can be used. Among the above base components having a sulfonic acid group, particularly preferred are those used in the examples described later.

  In addition, the compound represented by the general formula (3) or (4) can also be used in the state of a free sulfonic acid group, and the sulfonic acid group is a salt with an alkali metal such as lithium or sodium, First, second, third such as salts with polyvalent metals such as calcium, barium, aluminum, manganese, strontium, magnesium, nickel, mono, di, trialkylamine, alkylenediamine, mono, di or trialkanolamine It is also useful as a salt with a quaternary amine compound, and further as a salt with a quaternary ammonium compound such as tetraalkylammonium, benzyltrimethylammonium or trialkylphenylammonium. Particularly useful groups are free sulfonic acid groups or salts thereof with quaternary ammonium compounds.

  The dispersant is useful as a dispersant for various known organic pigments. The dispersant is a substance colored from magenta to purple to blue, and particularly useful organic pigments to be dispersed include dioxazine violet (CI Pigment Violet 23 (hereinafter referred to as “PV23”)), indane. Thoron Blue (CI Pigment Blue 60 (hereinafter referred to as “PB60”)), ε-type phthalocyanine blue (CI Pigment Blue 15: 6 (hereinafter referred to as “PB15: 6”)), Brominated Phthalocyanine Green (C CI Pigment Green 36 (hereinafter referred to as “PG36”)) and carbon black (CI Pigment Black 7 (hereinafter referred to as “PBk7”)), among others, PV23, PB60, PB15: 6, PG36 and PBk7. Is preferred. In the present invention, carbon black is also included in the organic pigment.

  The above dispersant is useful for producing an easily dispersible pigment composition. This easily dispersible pigment composition comprises an organic pigment and the dispersant. The blending ratio of the organic pigment and the dispersant in the easily dispersible pigment composition is preferably about 0.5 to 50 parts by mass, particularly 1 to 30 parts by mass of the dispersant per 100 parts by mass of the organic pigment. When the amount of the dispersant used is less than 0.5 parts by mass, it may be difficult to disperse the easily dispersible pigment composition sufficiently stably in the dispersion medium, while the amount of the dispersant used is 50 masses. Even if it exceeds the part, the dispersibility of the dispersant is saturated, which is disadvantageous in terms of cost.

The method for producing the easily dispersible pigment composition may be simply mixing the organic pigment and the dispersant, but for example, the following method is preferable. In any case, the organic pigments may be used alone or as a mixture of two or more. The same applies to the dispersant.
(1) A method in which an aqueous slurry of an organic pigment and an aqueous slurry of a dispersant are intimately mixed, filtered, washed with water, and dried to form an organic pigment and a dispersant.
(2) Dissolve the organic pigment and the dispersant in concentrated sulfuric acid, inject the concentrated sulfuric acid solution into a large amount of water to precipitate both simultaneously, filter, wash with water, and dry to form a solid solution of the organic pigment and the dispersant. How to make.
(3) A method in which both are wet-ground by a ball mill or the like in the presence of a small amount of liquid to make both fine powder mixtures.

  The above-mentioned easily dispersible pigment composition is effective for coloring various coloring applications, for example, paints, printing inks, natural or synthetic resins, inks for writing instruments, ink-jet inks, etc., and is particularly useful for coloring coating solutions for color filters. It is. Among these, an easily dispersible pigment composition using at least one organic pigment selected from PV23, PB60, PB15: 6, PG36, and PBk7 is useful as a colorant for a coating solution for a color filter.

  The dispersant is useful for producing a pigment dispersion. The preferred organic pigment in the pigment dispersion is the same as described above, and the ratio of the organic pigment and the dispersant used is the same as described above. The pigment dispersion is obtained by dispersing an organic pigment with a dispersant in an arbitrary dispersion medium. Examples of the dispersion method include a method in which the above-described easily dispersible pigment composition is added to a dispersion medium and dispersed, or an organic pigment and a dispersant are added to any dispersion medium, and the dispersion is performed by any disperser or attritor. Can be obtained. The use of such a pigment dispersion is the same as the use of the easily dispersible pigment composition.

  The dispersant is useful for producing a color filter coating solution. The color filter coating solution is obtained by dispersing an organic pigment in a color filter resin varnish with the dispersant. As the resin varnish for the color filter, any of conventionally known photosensitive resin varnish (photoresist) and non-photosensitive resin varnish can be used. The preferred organic pigments used in the coating solution, combinations thereof, and the ratio of use of the organic pigment and the dispersant are the same as those in the above-described easily dispersible pigment composition. Moreover, the manufacturing method of the coating liquid for color filters is the same as that of the said pigment dispersion liquid except that a dispersion medium is the resin varnish for color filters.

  When a blue, green, or black pigment is used in the color filter coating solution, a blue coating solution, a green coating solution, and a black coating solution (for forming a black matrix) are obtained, and the PV23 is used as an organic pigment. When is used, a purple coating solution is obtained. The purple coating solution is not used as a color filter coating solution by itself, but is useful for toning a coating solution using ε-type phthalocyanine blue as a blue pigment. That is, the spectral transmittance characteristic of the colored coating film by the blue coating liquid has the characteristic shown by the curve A in FIG. 1, but as described in the prior art, the color filter used in the current TV monitor As for the spectral transmittance characteristics of the blue pixels, the characteristics shown by the curve C in FIG. 1 are required. The spectral transmittance characteristic A of the colored coating film by the blue coating liquid is obtained by adding an appropriate amount of the purple coating liquid whose spectral transmittance characteristic is indicated by curve B in FIG. 1 to the blue coating liquid. The spectral transmittance characteristic of the coating film made of can be brought close to the characteristic shown by curve C in FIG.

  Further, by dispersing the easily dispersible pigment composition containing PB15: 6 and PV23 in the resin varnish at the same time, or by simultaneously dispersing both in the resin varnish with the dispersant, FIG. It can be set as the coating liquid for color filters which gives the coating film (pixel) which has the spectral transmittance characteristic shown by the curve C of this. In order to obtain such spectral transmittance characteristics, 1 to 100 parts by mass, preferably 3 to 50 parts by mass of PV23 is used per 100 parts by mass of PB15: 6.

  The method for producing a color filter is a method for producing a color filter in which a colored pattern of red, green and blue is formed on a substrate for a color filter. At least the blue pattern is formed using the coating liquid for color filter. It is characterized by forming. A coating solution other than blue may be separately prepared by a conventionally known method, and the green coating solution for a color filter may be used as the green coating solution. The color filter manufacturing method itself may be any conventionally known method.

  The method for producing an azo dye of the present invention is carried out by coupling an aromatic primary amine to the coupler represented by the general formula (1) or (2) in addition to the production of the dispersant. Various azo pigments are obtained. The production conditions for the azo pigment using the above coupler and amine are the same as the production conditions for the dispersant, and an azo pigment having various hues and excellent light resistance is obtained by coupling. These azo pigments are useful as colorants for paints, printing inks, resin colorants, color filter colorants, ink jet recording inks, and the like.

  Examples of the amine include 2,5-dichloroaniline, 4-chloro-2-methylaniline, 2-methyl-5-nitroaniline, 5-chloro-2-methylaniline, 2-methyl-4-nitroaniline, 4-methyl-2-nitroaniline, 4-chloro-2-nitroaniline, 2-methoxy-4-nitroaniline, 2-chloroaniline, 2-methoxy-5-nitroaniline, 2,4,5-trichloroaniline, 2,4-dichloroaniline, 3-amino-N- (4-carbamoylphenyl) -4-methoxybenzamide, 3-amino-N, N-diethyl-4-methoxybenzenesulfamide, methyl 2-aminobenzoate, 3 -Amino-4-methoxy-N-phenylbenzamide, 4-amino-2,5-dichloro-N-methylbenzenesulfur Amide, 4-amino-2,5-dichloro-N, N-dimethylbenzenesulfonamide, butyl 2-aminobenzoate, 4-aminobenzamide, 3-amino-4-methylbenzamide, 3-amino-4-methoxybenzamide, 3-amino-4-chlorobenzamide, methyl 2-amino-4- (2,5-dichlorophenylcarbamoyl) benzoate, 2-methoxy-5- (3- (trifluoromethyl) benzylsulfonyl) aniline, 3-amino-4 -Methoxy-N- (3- (trifluoromethyl) phenyl) benzamide, 3-amino-4-methoxy-N-phenylbenzamide, 1-aminoanthracene-9,10-dione, (z) -3- (4- Aminophenylimino) -4,5,6,7-tetrachloroisoindoline-1 ON, 3-amino-4-chloro-N- (5-chloro-2-methylphenyl) benzamide, 4-nitroaniline, 2-chloro-5- (trifluoromethyl) aniline, 3-nitroaniline, 2-nitro Aniline, N- (4-amino-2,5-dimethoxyphenyl) benzamide, N- (4-amino-5-methoxy-2-methylphenyl) benzamide, 5-aminoisoindoline-1,3-dione (4- Aminophthalimide), 5-amino-1H-benzo [d] imidazol-2 (3H) -one (5-aminobenzimidazolone), and the like.

  Next, the present invention will be described more specifically with reference to examples and comparative examples. “Part” or “%” in the text is based on mass unless otherwise specified.

Example 1
To 700 parts of toluene, 40 parts of 2-hydroxy-3-naphthoic acid and 44.8 parts of 3-amino-9-ethylcarbazole, 13.2 parts of phosphorus trichloride was added at 70 to 75 ° C. over 1 hour, and then the same temperature. After stirring at 107-110 ° C for 20 hours, the alkaline solvent is removed by steam distillation, filtered at 50-60 ° C, dried and the coupler 75.0 of the present invention represented by the following structural formula: Got a part. The coupler is a new material. Results of elemental analysis C: 78.81% (theoretical value: 78.93%), H: 5.30% (theoretical value: 5.30%), N: 7.38% (theoretical value: 7.36%) FIG. 2 shows the ¹ H NMR of the compound, FIG. 4 shows the ¹³ C NMR, FIG. 6 shows the thermal analysis chart, and FIG. 8 shows the infrared absorption spectrum.

Example 2
To 90 parts of monochlorobenzene, 14.2 parts of sodium benzacylate, and 10.0 parts of 3-amino-9-ethylcarbazole, 3.2 parts of phosphorus trichloride was added at 90 to 95 ° C. over 1 hour, After stirring at 128 to 130 ° C for 25 hours, the solvent was removed by steam distillation with alkali, filtered at 50 to 60 ° C, and dried to obtain 21.2 parts of a coupler represented by the following structural formula. The coupler is a new material. The results of elemental analysis are C: 79.50% (theoretical value 79.30%), H: 4.95% (theoretical value 4.94%), N: 8.96% (theoretical value 8.95%). FIG. 3 shows the ¹ H NMR of the compound, FIG. 5 shows the ¹³ C NMR, FIG. 7 shows the thermal analysis chart, and FIG. 9 shows the infrared absorption spectrum.

Application example A-1
Dissolve 12.7 parts of sulfanilic acid in 4.5 parts of sodium carbonate and 120 parts of water, add 23.8 parts of concentrated hydrochloric acid, cool to 20 ° C., add ice to 5 ° C., and add sodium nitrite. 5 parts as a 20% aqueous solution was added at 10 ° C. or less, and the mixture was stirred for 0.5 hour, and excess nitrous acid was decomposed with an aqueous sulfamic acid solution to prepare a diazo solution. On the other hand, 28.0 parts of coupler K-1 (Example 1) were dissolved in 4.4 parts of sodium hydroxide, 8.4 parts of sodium acetate trihydrate and 500 parts of methanol, and the diazo solution was added to this at 10 ° C. or lower. After the dropwise addition, the mixture was further stirred for about 3 hours while controlling to pH 8.5 with sodium acetate trihydrate. After confirming the end point of the reaction, the product is filtered, washed with methanol and water, reslurried in water, hydrochloric acid is added to make it strongly acidic, filtered water is washed and dried, and a red purple dispersion represented by the following structural formula 37.6 parts of agent (1) were obtained.

Application example A-2
Add 48.9 parts (15.0 parts of solid content) of the aqueous paste of the dispersant (1) obtained in Application Example A-1 to 500 parts of water to sufficiently reslurry, and add 9.5 parts of tetraethylammonium chloride. After stirring for 3 hours, the mixture was filtered and washed thoroughly with water to obtain 17.6 parts of a reddish purple dispersant (2) represented by the following structural formula.

Application example A-3
Add 48.9 parts of water paste (15.0 parts of solid content) of the dispersant (1) obtained in Application Example A-1 to 500 parts of water and reslurry sufficiently to prepare aluminum sulfate 14-18 hydrate. After adding 200 parts of a 10% aqueous solution and stirring at 85 to 95 ° C. for 2 hours, the mixture was filtered and sufficiently washed with water to obtain 14.8 parts of a red-purple dispersant (3) represented by the following structural formula.

Application example A-4
In Application Example A-1, naphthoic acid was used instead of sulfanilic acid, and a reddish purple dispersant (4) represented by the following structural formula was obtained in the same manner.

Application example A-5
The dispersant (4) and tetraethylammonium chloride were reacted in the same manner as in Application Example A-2 to obtain a reddish purple dispersant (5) represented by the following structural formula.

Application example A-6
The dispersant (4) and aluminum sulfate 14-18 hydrate were reacted in the same manner as in Application Example A-3 to obtain a reddish purple dispersant (6) represented by the following structural formula.

Application example A-7
A purple dispersant (7) represented by the following structural formula was obtained in the same manner as in Application Example A-1, using sulfanilic acid as the diazo component and K-2 as the coupler.

Application example A-8
The dispersant (7) and aluminum sulfate 14-18 hydrate were reacted in the same manner as in Application Example A-3 to obtain a reddish purple dispersant (8) represented by the following structural formula.

Application example A-9
Using a naphthoic acid as a diazo component and the K-2 as a coupler, a purple dispersant (9) represented by the following structural formula was obtained in the same manner as in Application Example A-1.

Application example A-10
A reddish purple dispersant (10) represented by the following structural formula was obtained in the same manner as in Application Example A-1, using Brenalic acid as the diazo component and K-1 as the coupler.

Application Example A-11
A purple dispersant (11) represented by the following structural formula was obtained in the same manner as in Application Example A-1, using M acid as the diazo component and K-1 as the coupler.

Application example A-12
A purple dispersant (12) represented by the following structural formula was obtained in the same manner as in Application Example A-1, using gamma acid as the diazo component and K-1 as the coupler.

Application example A-13
Using 6- (3-sulfo) benzamido-4-methoxy-m-toluidine as the diazo component and K-1 as the coupler, the purple color represented by the following structural formula was used in the same manner as in Application Example A-1. Dispersant (13) was obtained.

Application example A-14
Using 1-aminoanthraquinone-5-sulfonic acid as a diazo component and K-1 as a coupler, a reddish purple dispersant (14) represented by the following structural formula is obtained in the same manner as in Application Example A-1. Obtained.

Application example B-1
A PV23 press cake (solid content: 26%) is taken so that the pigment content becomes 100 parts, and 2,000 parts of water is added to sufficiently reslurry. To this, press cake (30% solid content) of dispersant (1) is added so that the solid content is 5 parts, and the mixture is stirred at high speed for 1 hour. A 5% aqueous sodium carbonate solution is gradually added dropwise until weakly acidic, and then stirred for 1 hour and filtered. After thoroughly washing with water and drying at 80 ° C., 104 parts of an easily dispersible pigment composition (1) was obtained.

Application example B-2
A PV23 press cake (solid content: 26%) is taken so that the pigment content becomes 100 parts, and 2,000 parts of water is added to sufficiently reslurry. A dispersant (2) press cake (solid content 35%) is added to this so that the solid content becomes 5 parts, and the mixture is stirred at high speed for 1 hour. Filtration, washing with sufficient water, and drying at 80 ° C. yielded 104 parts of an easily dispersible pigment composition (2).

Application example B-3
Similarly to the application example B-2, the dispersant (3) was used instead of the dispersant (2) to obtain an easily dispersible pigment composition (3).

Application example C-1
50 parts of acrylic resin varnish (methacrylic acid / benzyl acrylate / styrene / hydroxyethyl acrylate copolymerized at a molar ratio of 25/50/15/10 (molecular weight 12,000, solid content 40%)) 20 parts, 20 parts of dispersant (1) and 20 parts of a solvent (propylene glycol 1-monomethyl ether 2-acetate) (hereinafter abbreviated as PGMAc) are blended, and after premixing, dispersed with a horizontal bead mill and purple pigment A dispersion was obtained.

Application example C-2
A purple pigment dispersion was obtained in the same manner as in Application Example C-1, except that the dispersant (2) was used instead of the dispersant (1).

Application examples C-3 to C-14
Instead of the dispersant (1), dispersants (3) to (14) were used, respectively, to obtain a purple pigment dispersion in the same manner as in Application Example C-1.

Application examples C-15, 16, 17
Instead of PV23 and the dispersant (1) used in Application Example C-1, easy-dispersible pigment compositions (1), (2), and (3) were used, respectively, in the same manner as Application Example C-1. Three kinds of purple pigment dispersions were obtained.

Comparative Example C-1
A purple pigment dispersion was obtained in the same manner as in Application Example C-1, using a commercially available pigment dispersant (monosulfonated phthalocyanine blue) instead of the dispersant (1) used in Application Example C-1.

Comparative Example C-2
Instead of the dispersant (1) used in Application Example C-1, a commercially available pigment dispersant (quaternary ammonium salt of monosulfonated phthalocyanine blue) was used, and a purple pigment was prepared in the same manner as in Comparative Example C-1. A dispersion was obtained.

  The average particle diameters of the pigments in the purple pigment dispersions of Application Examples C-1 to 17 and Comparative Examples C-1 and C-2 were measured. In order to check the storage stability, the purple pigment dispersion was stored at room temperature for 1 month, and the change in viscosity was measured. The viscosity was measured using an E-type viscometer at a rotor rotation speed of 6 rpm. Further, in order to examine the spectral transmittance characteristics, each of the purple pigment dispersions was applied to a glass substrate with a spinner, and after drying, the maximum transmittance of the coating film at a wavelength of 440 nm was measured. The results are shown in Table 1.

  As is apparent from Table 1, the violet pigment dispersions of application examples C-1 to 17 are compared with the violet pigment dispersions of comparative examples C-1 and C-2. It is clear that the maximum light transmittance is higher and the initial viscosity and the viscosity after storage (after one month) are lower.

Application example D-1
A blue pigment dispersion was obtained in the same manner as in Application Example C-1, except that PB15: 6 was used instead of PV23 used in Application Example C-1. As shown in Table 2, this blue pigment dispersion also had low initial viscosity and low viscosity after storage (after one month), and had excellent properties as a color filter coating solution.

Application example D-2
PG36 was used instead of PV23 used in application example C-1, and a green pigment dispersion was obtained by the same operation as application example C-1. As shown in Table 2, this green pigment dispersion also had low initial viscosity and low viscosity after storage (after one month), and had excellent properties as a color filter coating solution.

Application example D-3
A black pigment dispersion was obtained in the same manner as in Application Example C-1, except that PBk7 was used instead of PV23 used in Application Example C-1. As shown in Table 2, this black pigment dispersion also has low initial viscosity and viscosity after storage (after one month), and has excellent properties as a color filter coating liquid (for black matrix). .

Reference example 1
50 parts of acrylic resin varnish used in Application Example C-1, 17 parts of anthraquinonyl red pigment (CI Pigment Red 177), 3 parts of isoindolinone yellow pigment (CI Pigment Yellow 139) and pigment dispersion 2 parts of 2,4-bis [anthraquinonyl (-1 ′)-amino] -6- (N, N-dimethylamino) ethylamino-s-triazine and 20 parts of PGMAc as an agent, and after premixing, Dispersion was performed using a horizontal bead mill to obtain a red pigment dispersion.

Reference example 2
Instead of the pigment used in Reference Example 1, 17 parts of PG36 and 13 parts of quinophthalone yellow pigment (CI Pigment Yellow 138) were used, and a green pigment dispersion was obtained in the same manner as in Reference Example 1. .

Application example E-1
In order to produce RGB color filters, coating solutions for R, G and B color filters were obtained according to the formulation shown in Table 3 below.

The glass substrate treated with the silane coupling agent was set on a spin coater, and the coating solution of R in Table 3 was first spin-coated at 300 rpm for 5 seconds and then at 1200 rpm for 5 seconds. Next, prebaking was performed at 80 ° C. for 10 minutes, a photomask having a mosaic pattern was brought into close contact, and exposure was performed with an ultrahigh pressure mercury lamp at a light amount of 100 mJ / cm ² . Next, development and washing were performed with a dedicated developer and a dedicated rinse to form a red mosaic pattern (pixel) on the glass substrate.

  Subsequently, a green mosaic pattern and a blue mosaic pattern were formed by applying and baking according to the above method using the coating solutions G and B shown in Table 3 to obtain a color filter having RGB pixels. The obtained color filter had excellent spectral transmittance characteristics, excellent fastness such as light resistance and heat resistance, and exhibited excellent properties as a color filter for liquid crystal color display.

Pigment production example-1
16.2 parts of 2,5-dichloroaniline was dissolved in 22 parts of acetic acid at 40 ° C., and a mixture of 80 parts of 5N hydrochloric acid and 250 parts of water was added to make a fine slurry. 175 parts of ice was added to bring the temperature to 0 ° C. or lower, 14 parts of 50% aqueous sodium nitrite solution was added, and the mixture was stirred for 1 hour. Excess nitrous acid was decomposed with a total liquid volume of 500 parts, followed by filtration using a filter aid to prepare a transparent diazo solution. On the other hand, 8 parts of sodium hydroxide and 40.8 parts of sodium acetate trihydrate were dissolved in 700 parts of methanol, and 38.1 parts of the coupler K-1 was added thereto to prepare a coupler solution. The diazo solution was gradually added to the coupler solution at 5 ° C. or lower, stirred as it was for 30 minutes, and then stirred for 6 hours while adjusting the pH to 8.0 to 8.5 with sodium acetate trihydrate. Filtration, washing with water and drying were carried out to obtain 51.3 parts of dark red pigment having the following chemical structure.

Pigment production example-2
Coupling was carried out in the same manner as in Pigment Production Example-1 except that the coupler K-1 was replaced with the coupler K-2 in Pigment Production Example-1, thereby obtaining a black pigment having the following chemical structure. This pigment was non-infrared absorbing.

Pigment production example-3
In pigment production example-1, 2,5-dichloroaniline was replaced with (z) -3- (4-aminophenylimino) -4,5,6,7-tetrachloroisoindoline-1-one, and coupler K- A black pigment having the following chemical structure was obtained in the same manner as in Pigment Production Example 1 except that 1 was replaced with the coupler K-2. This pigment was non-infrared absorbing.

Pigment production example-4
In Pigment Production Example 1, 2,5-dichloroaniline was replaced with 5-amino-1H-benzo [d] imidazol-2 (3H) -one (5-aminobenzimidazolone), and coupler K-1 was replaced with the coupler. A black pigment having the following chemical structure was obtained in the same manner as in Pigment Production Example 1 except that K-2 was used. This pigment was non-infrared absorbing.

Pigment production example-5
Pigment Production Example 1 except that 2,5-dichloroaniline was replaced with N- (4-amino-2,5-dimethoxyphenyl) benzamide and coupler K-1 was replaced with coupler K-2. In the same manner as in Example 1, a dark blue pigment having the following chemical structure was obtained. This pigment was non-infrared absorbing.

Pigment production examples-6-9
The following pigments were obtained in the same manner as in Pigment Production Examples-1 to 5.

  The coupler of the present invention is useful as an intermediate for various azo dyes, azo pigments, and organic pigment dispersants. In particular, azo dyes having 1 to 3 sulfonic acid groups or salts thereof obtained using the coupler of the present invention are used as organic pigment dispersants for various paints, printing inks and color filters. It can be stably dispersed at a high concentration and a low viscosity in a dispersion medium such as a coating solution. The dispersion of the organic pigment obtained using the above dispersant is useful as a colorant for the color filter coating solution, and has excellent spectral transmittance characteristics when PB15: 6 and PV23 are combined as the pigment. It is possible to form a blue pixel which has a clear, high transparency, and excellent fastness such as light resistance, heat resistance, solvent resistance, chemical resistance, and water resistance.

The figure explaining the spectral transmittance characteristic of a colored coating film. ¹ H NMR spectrum of coupler K-1. ¹ H NMR spectrum of coupler K-2. ¹³ C NMR spectrum of coupler K-1. ¹³ C NMR spectrum of coupler K-2. The thermal analysis chart of coupler K-1. Thermal analysis chart of coupler K-2. Infrared absorption spectrum of coupler K-1 (Nujol method). Infrared absorption spectrum of coupler K-2 (Nujol method).

Claims (6)

A dye characterized by being one of the pigments (1) to (9) represented by the following structural formula .

A colorant comprising any one of the pigments according to claim 1 . A method for coloring an article, characterized by using the colorant according to claim 2 . It is a manufacturing method for manufacturing the pigment | dye of Claim 1, Comprising: It synthesize | combines using the compound represented by a following formula (K-1) or (K-2) as a coupler, Production method.

A coupler represented by the following general formula ( 2).

(Wherein the substituent X in the formula may be the same or different, a halogen atom, a hydroxyl group, a nitro group, an alkyl group, .R alkoxyl Motoma others representing a full barrel imido methyl group is a hydrogen atom or C ₁ ~ Represents an alkyl group of C _12. m is an integer of 0 to 3.) m is 0, coupler according to claim 5 R is a hydrogen atom or an alkyl group C ₁ -C _4.

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