KR101319070B1 - Azo pigments, coloring compositions, coloring method and colored articles - Google Patents

Abstract

This invention is represented by the following general formula (I), It is a dark color azo pigment characterized by the above-mentioned. According to the present invention, it is possible to provide a dark-based azo pigment having the property of reflecting or transmitting infrared rays or heat rays of sunlight as optical properties, and having excellent fastness as a pigment property, particularly excellent heat resistance.

Description

Azo pigments, coloring compositions, coloring methods and colored articles {AZO PIGMENTS, COLORING COMPOSITIONS, COLORING METHOD AND COLORED ARTICLES}

The present invention relates to novel dark to black (hereinafter referred to as dark color) azo pigments, coloring compositions, coloring methods and colored articles. More specifically, diazo is used as the coupling component, 2-hydroxy-11H-benzo [a] carbazole-3-carboxy-N-benzimidazolone-5-amide, which is a novel specific coupling component. A novel dark-based azo pigment obtained by both coupling reactions using a well-known diazo compound as a component, the coloring composition containing it, the coloring method using them, and a coloring article.

Conventionally, as a black pigment, carbon black has been generally used, and iron oxide black (iron trioxide), a black complex oxide pigment, etc. have been used in addition. Since these pigments show black and absorb the light of the wavelength from a visible region to a far infrared region, articles, such as a coating film colored with these pigments, tend to become high temperature by absorption of sunlight. In addition, since carbon black has conductivity, articles colored with carbon black have a property of lacking electrical insulation.

In recent years, in the field of electronic devices and optical devices, due to the use of infrared laser radiation and the development of sensors corresponding thereto, black pigments such as carbon black, which are generally used in the past, are required. There are many fields. For example, in infrared communication, infrared camouflage, optical filters and the like, oil-soluble dyes have been used as coloring materials for infrared-transmitting filters. However, in order to color synthetic resin materials with these oil-soluble dyes, heat resistance, solvent resistance, light resistance, etc. There is a problem in durability, and therefore, a dark-based pigment that has excellent durability and is excellent in infrared transmission is required. In addition, from the viewpoint of energy saving, heat-shielding coating that reflects sunlight is desired. Heat-reflecting materials therefor are used for heating the roof and walls of structures, road pavement, exterior and interior of automobiles, etc. There is a demand for heat ray reflecting materials, such as heat shields, for use as sex materials and for agriculture.

As a means to solve these problems, as a black pigment having infrared reflectance, as a coupling component, a conventionally known color index (CI) coupling component 25 (2-hydroxy-11H-benzo [a] carbazole-3-carboxy -(2'-methyl) -p-anisidide) or CI Although there are black azo pigments using coupling component 13 (2-hydroxy-11H-benzo [a] carbazole-3-carboxy-p-anisidide), these coupling components are diazo components combined with this. Accordingly, pigment physical properties such as heat resistance and solvent resistance are insufficient, and heat resistance is insufficient for coloring of plastics, especially kneading during coloring of high-performance plastics. Accordingly, there is a demand for dark pigments having the above optical and electrical properties and excellent pigment properties such as heat resistance and solvent resistance.

Accordingly, it is an object of the present invention to provide a dark color azo pigment which has a property of reflecting or transmitting a heat ray of infrared rays or solar light as an optical property, and having excellent fastness as a pigment property, particularly excellent heat resistance.

MEANS TO SOLVE THE PROBLEM The present inventors earnestly researched in order to solve the said subject, and as a coupling component, 2-hydroxy-11H-benzo [a] carbazole-3-carboxylic acid-N-benzimidazol-5-amide The dark azo pigment obtained by the coupling reaction with a suitable diazo component exhibits a sufficient dark color with excellent heat resistance, and in particular, by making the particle diameter from the submicron to the nano-sized ultrafine pigment, It is possible to increase the light transmittance of the light, and to reflect the infrared reflectance by reflecting the infrared ray transmitted through the colored layer by the dark-based pigment on a white background (in the present invention, this is referred to as "infrared reflectivity"). It is possible to obtain a dark-based azo pigment having excellent pigment properties such as excellent infrared transmittance and infrared reflectance optical properties and heat resistance. To find that, thus completing the present invention.

That is, this invention provides the dark-based azo pigment, coloring composition, coloring method, and coloring article which are represented by following General formula (I).

[Wherein n in the formula is 1 or 2, X represents a hydrogen group or a substituent, and the substituent is a halogen group, an alkyl (C _{1 to} C ₂₀ ) group, an alkoxyl (C _{1 to} C ₂₀ ) group, or a phthal At least one selected from the group consisting of a midmethyl group and a sulfonic acid group, and at least one substituent, and Ar is selected from the group consisting of a phenyl group, naphthyl group, anthryl group, and 9,10-anthraquinonyl group which may be introduced with a substituent. It is.

In the present invention, the substituent of Ar is an alkyl group (C _{1 to} C ₂₀ ), an alkoxyl group (C _{1 to} C ₂₀ ), a fluoroalkyl group (C _{1 to} C ₂₀ ), a halogen group, a carboxyl group, an ester group, oxy Carbonyl (ester) group, carbamide group, aminocarbonyl group, iminodicarbonyl ring group, imidazolone ring group, nitro group, alkyl (C _{1 to} C ₂₀ ) sulfonyl group, phenylmethylsulfonyl group, alkyl (C _{1 ~} C ₂₀₎ amino-sulfonyl group, a benzoyl group, a phenyl group and at least one member selected from the group consisting of a phenyl ether, at least one first individual; It is preferable that the average particle diameter of a dark color azo pigment is 20 nm-1,000 nm.

Moreover, this invention provides the coloring composition containing the pigment component containing the dark-based azo pigment of the said invention in a liquid dispersion medium or a solid dispersion medium. In the coloring composition of the said invention, the said pigment component is at least selected from the group which consists of the dark-based azo pigment of this invention alone, or the said pigment-based azo pigment and other chromatic pigment, white pigment, another black pigment, and a sieving pigment. Being a mixture with one species; The liquid dispersion medium comprising, as a film forming material, at least one selected from a liquid polymer which may have a reactive group, a liquid oligomer which may have a reactive group, and a liquid monomer which may have a reactive group; And it is preferable that the said solid dispersion medium contains at least 1 sort (s) chosen from a thermoplastic resin, a thermosetting resin, wax, fatty acid amide, and fatty acid metal soap.

The coloring composition of the said invention is useful as a coloring agent for paints, plastics, textiles, printing ink, image recording, image display, or pigment printing agent.

Moreover, this invention provides the coloring method of the article characterized by coloring an article using the coloring composition of the said invention. In the said coloring method, the said article consists of infrared ray high permeability resin, and colors the surface or the inside of the said article; It is desirable to color the infrared reflective article itself or the infrared reflective layer formed on the article surface. Moreover, this invention provides the coloring article characterized by obtained by the method of the said invention.

Conventionally, articles colored with black pigments, such as carbon black, are easy to absorb infrared rays, tend to become high temperature by direct sunlight, etc., and lower the electrical resistance. Therefore, they are not suitable for use in electrical insulation. There was a problem.

Moreover, although the coloring article by the black azo pigment which used the conventionally well-known CI coupling component 25 and CI coupling component 13 as a coupling component has infrared reflectivity and electrical insulation, the said pigment is used for the diazo component used therein. Therefore, pigment physical properties such as heat resistance and solvent resistance were insufficient, and heat resistance was insufficient at the time of kneading coloring of plastics.

On the other hand, this invention which uses the amide of benzimidazolone which has a ureylene group which is a polar group as a coupling component as an arylamide of 2-hydroxy-11H-benzo [a] carbazole-3-carboxylic acid The dark azo pigments of the pigments exhibit sufficient black color and have fastness such as heat resistance and solvent resistance as pigments, and polyethylene terephthalate (molding temperature: about 270 ° C.), polybutylene terephthalate ( Molding temperature: about 250 degreeC), polycarbonate (molding temperature: about 280 degreeC), etc. It is used also for the use with high kneading process temperature, such as coloring.

In addition, the azo pigment of the present invention, by controlling the particle diameter of the ultra-fine particles of submicron to nano size, has excellent optical properties, such as infrared high transparency, so that the inside of the remote controller using infrared of the electronic device is not visible. It is effective as a light-transmitting window material of dark color, and the coating of the dry matter by reflecting daylight utilizing the reflecting effect to the white infrared reflecting ground, the metal surface, or the mixed white pigment, extender pigment, or metal foil pigment It has excellent features and effects in energy-saving applications such as heat shield packaging, automotive exterior, interior, textile, textile heat shield, etc. In the above, the azo pigment of the present invention is not only used as a dark color pigment alone, but also gray in combination with a white pigment, and in combination with a pigment pigment, low brightness such as dark red, dark blue, dark brown, dark green, etc. Used for coloring purposes of color tone.

EMBODIMENT OF THE INVENTION Next, this invention is demonstrated in detail, taking the form for implementing this invention as an example.

The azo pigment of the said general formula (I) used by this invention and mainly characterizing this invention is a coupling component which represents the diazo component which is an aromatic amine represented by the following general formula (II) by the following general formula (III). It can obtain by the method of coupling in accordance with a conventional method.

In addition, X, n, and Ar in said formula are the same as the above.

The coupling component represented by General formula (III) used by this invention is 2-hydroxy-11H-benzo [a] carbazole-3-carboxylic acid, its salt or reactive derivatives, such as an acid halide and a lower fatty acid ester. And 5-aminobenzimidazone which may have a substituent can be obtained by making it react. As the substituent (X), at least one selected from the group consisting of a halogen group, an alkyl (C _{1 to} C ₂₀ ) group and an alkoxyl (C _{1 to} C ₂₀ ) group, a phthalimide methyl group and a sulfone group, at least one Can be mentioned.

As the aromatic amine represented by the general formula (Ⅱ), and may have a substituent conventionally known a phenyl group, a naphthyl group, an anthryl group, or a group of 9,10-anthraquinone CUNAULT, the substituent alkyl group (C _{1 ~} C _20), an alkoxy group (C _{1 ~} C _20), the fluoroalkyl group (C _{1 ~} C _20), a halogen group, a carboxyl group, an ester group, an oxycarbonyl (ester) group, Carbamide group, an amino group, an imino-dicarbonyl From the group consisting of ventilation, imidazolone ring group, nitro group, alkyl (C _{1 to} C ₂₀ ) sulfonyl group, phenylmethylsulfonyl group, alkyl (C _{1 to} C ₂₀ ) aminosulfonyl group, benzoylamino group, phenylamino group and phenylether group At least 1 sort (s) chosen and at least 1 sort (s) are mentioned.

As aromatic amines, for example, aniline, 2-chloroaniline, 3-chloroaniline, 4-chloroaniline, 2,5-dichloroaniline, 2-methyl-3-chloroaniline, 2-methyl-4-chloroaniline, 2-methyl-5-chloroaniline, 2-methoxy-5-chloroaniline, 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 2-methyl-5-nitroaniline, 2-methyl-4-nitro Aniline, 2-nitro-4-methylaniline, 2-methoxy-4-nitroaniline, 2-methoxy-5-nitroaniline, 2-nitro-4-methoxyaniline, 2-nitro-4-chloroaniline, 2- (4'-Chlorophenoxy) -5-chloroaniline, 2-methoxy-5-butylaminosulfonylaniline, 2-methoxy-5-diethylaminosulfonylaniline, 2-methoxy-5- Aniline such as methyl-4-benzoylaminoaniline, 2,5-dimethoxy-4-benzoylaminoaniline, 2-chloro-4-benzoylamino-5-methoxyaniline, 1-aminoanthracene, 1-aminoanthraquinone and the like, or Aniline Derivatives, Naphthyl Amine It may be a conductor, an amino or amino-anthracene, anthraquinone and the like. In the general formula (I), examples of the aromatic amine when n = 2 include 4,4′-dichlorobenzidine, 4,4′-dimethylbenzidine, 4,4′-dimethoxybenzidine, 4,4 ＇-Diaminodiphenylmethane, 4,4'-diamino-3,3'-dichlorodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylsulfone, etc. are mentioned. Can be.

As the method for diazotizing the aromatic amine, a conventional diazotization method of the aromatic amine can be used as it is. For example, sodium nitrite solution is added to the cold water solution of the mineral acid salt of the aromatic amine, and the mixture is stirred for a while and then diazotized. And a diazoamino compound with a method of obtaining an aqueous solution of a diazonium salt, a stabilizing double salt with zinc chloride, or an amino compound such as sarcosine (N-methylglycine).

The dark azo pigment of the present invention is a diazonium salt of an aromatic amine represented by General Formula (II), a double salt thereof, or a derivative such as a diazoamino compound (hereinafter referred to collectively as a diazonium salt); The coupling component represented by Formula (III) can be obtained by coupling according to the manufacturing method of the azo pigment conventionally performed. In addition to using one type of diazonium salt, it is also preferable to use together 1 or more types of other diazonium salts according to the purpose of control of the color tone of a pigment, control of a crystal, particle diameter, storage stability, etc. In the coupling component, for the same purpose, in addition to the coupling component represented by the general formula (III) of the present invention, other known coupling components may be used in combination.

That is, the coupling component is added to an aqueous alkali solution to dissolve it by heating, and then the solution is cooled to near 25 ° C., and a buffer is added thereto to further adjust the pH, after which the diazonium salt of the aromatic amine is added thereto. The aqueous solution was added dropwise to perform a coupling reaction at low temperature (below 10 DEG C) in an alkali state, to produce a crude azo pigment, which was then filtered, washed with water and dried to further control of the process or pigment as needed. The azo pigment of this invention can be obtained through the pigmentation process aimed at adjustment of the particle diameter by a micronization process, etc.

Further, in the present invention, the coupling reaction can be carried out in a hydrophilic organic solvent such as methanol, ethanol, methyl ethyl ketone, dimethylformamide, dimethyl sulfoxide, or a lipophilic organic solvent such as toluene, o-dichlorobenzene or nitrobenzene. Can be.

The azo pigment of the present invention prepared as described above is a pigment exhibiting a dark color such as black to dark purple, dark brown, dark green and the like, solvent resistance, light resistance, heat resistance, water resistance, chemical resistance is also good, coloring power is high, especially heat resistance Although it is a pigment which shows the outstanding property, by making it further microparticles | fine-particles, the color with more clarity, clearness, and transparency is provided to a pigment. The average particle diameter of the micronized pigment is 20 nm to 1,000 nm, particularly 20 nm to 300 nm is preferred for obtaining high transmittance in the infrared region, and 20 nm to 100 nm for use in optical devices such as color filters. desirable.

Although some methods are illustrated below about the pigmentation method of a pigment, this invention is not limited to these methods. The most preferred method is

(1) It is a solvent salt milling method for grinding pigments, and the pigments are put into the kneader at an appropriate ratio by adding water-soluble inorganic salts such as sodium chloride and sodium sulfate and water-soluble organic solvents such as ethylene glycol, diethylene glycol, polyethylene glycol, and controlling the temperature. After compression kneading the contents for a time, the kneaded product is poured into a warm diluted sulfuric acid aqueous solution, stirred, filtered and washed with water to remove the water-soluble inorganic salt and the water-soluble organic solvent, and then dried by warm air or the like. In addition, a dry milling method using a ball mill or a vibration mill is also effective. In this method, grinding media such as steel balls and steel rods are used, and inorganic salts are used as grinding aids as necessary. As a grinding aid used by this method, in addition to sodium chloride and sodium sulfate, aluminum nitrate etc. are mentioned as mentioned above.

(2) A method of dissolving the crude pigment in a good solvent such as sulfuric acid or polyphosphoric acid and injecting this solution into a poor solvent such as water to reprecipitate the pigment, that is, a method called an acid paste method. have. The desired micronized pigment can be obtained only by sufficiently washing the obtained pigment in this manner. However, the desired pigment can be reliably obtained by performing the pigmentation with a suitable organic solvent or the like to prepare the particle diameter.

(3) In the above method, when the diazo component and the coupling component of an aromatic amine are subjected to a coupling reaction, two or more kinds of diazo components are used or one or more other coupling components are used together to produce a pigment. The method of manufacturing a refined pigment is mentioned by inhibiting the growth of a particle | grain. Although the desired refinement | miniaturization pigment may be obtained only by this method, Preferably, it is more preferable to use the solvent salt milling method of said (1) together by the method of said (3).

The dark color azo pigment of this invention has the property to reflect or transmit infrared rays or the heat ray of sunlight as an optical characteristic, and has outstanding fastness and especially excellent heat resistance as a pigment characteristic. The dark color azo pigment of this invention is a coloring agent of the coloring composition for paints, the coloring composition for plastics, the coloring composition for textiles, the coloring composition for printing inks, the coloring composition for image recording, the coloring composition for image display, or the coloring composition for pigment printing agents. Used. These coloring compositions are used as a coloring composition which disperse | distributes and contains the pigment component containing the dark-based azo pigment of this invention in a liquid dispersion medium or a solid dispersion medium according to a use and a use form.

As said pigment component, the dark colored azo pigment of this invention is used independently as a coloring agent of a black or dark pigment composition, or the chromatic pigment, white pigment, and other black which are different from the dark colored azo pigment of this invention according to the objective. By using together at least 1 sort (s) of pigment chosen from the group which consists of a pigment and a sieving pigment, it is used as a pigment composition of the achromatic color of pale black, gray etc. of the chromatic colors, such as dark red, dark blue, dark green, brown, dark purple.

As said chromatic pigment, white pigment, another black pigment, a sieving pigment, etc., a conventionally well-known organic pigment, an inorganic pigment, a sieving pigment are used. For example, soluble and insoluble azo pigments, polymer azo pigments, quinacridone pigments, anthraquinone pigments, diketopyrrolopyrrole pigments, quinophthalone pigments, phthalocyanine pigments, dioxazine pigments, perylene pigments, perinone pigments, iso Organic pigments such as indolinone pigments, indigo-thioindigo pigments, metal complex pigments, and inorganic pigments such as iron oxide pigments and titanium oxide pigments, and extender pigments such as calcium carbonate and silica.

As the organic pigment, for example, as a yellow pigment, CI pigment yellow (abbreviated as PY) -74, 83, 93, 94, 95, 97, 109, 110, 120, 128, 138, 139, 147, 150, 151, 154, 155, 166, 175, 180, 181, 185, 191 and the like, CI pigment orange (PO abbreviation) -61, 64, 71, 73 and the like as the orange pigment, CI pigment as a red pigment Red (abbreviated as PR) -4, 5, 23, 48: 2, 48: 4,57: 1, 112, 122, 144, 146, 147, 150, 166, 170, 177, 184, 185, 202, 207, 214, 220, 221, 242, 254, 255, 264, 272 and the like as CI pigment blue (abbreviated as PB) -15: 1, 15: 2, 15: 3, 15: 4, 15: 5, 15: 6, 16, 17: 1, 60, 80, aluminum phthalocyanine blue and the like as CI pigment green (abbreviated as PG) -7, 36, poly (13-16) bromphthalocyanine As a violet pigment, CI pigment violet (it abbreviates as PV) -19, 23, 37, etc. are mentioned.

As a liquid dispersion medium of the pigment composition of this invention, it contains the polymer which may have a reactive group, the oligomer which may have a reactive group, and the film forming material which is at least 1 sort (s) chosen from the monomer which may have a reactive group, and is itself a liquid, Or a mixture of two or more kinds of components selected from an organic solvent and water, and used in the form of a solution, a dispersion or an emulsion.

As the organic solvent, for example, aliphatic, alicyclic, aromatic hydrocarbons, halogenated hydrocarbons, esters, ketones, glycol ethers, alcohols, and the like are used, but are not particularly limited. As the vehicle for the paint, the varnish for the printing ink, and the vehicle for the coating agent, a conventionally known oily to aqueous binder material is used according to each use. For example, modified alkyd resins such as long whey, medium whey and short whey, phenol-modified alkyd resins, styrenated alkyd resins, amino alkyd resins, oil-free alkyd resins, acrylic resins for baking, acrylic Lacquer resin, acrylic polyol resin, polyester resin, epoxy resin, butylated melamine resin, methylated melamine resin, urea-melamine resin, phenol resin, rosin modified phenol resin, rosin modified maleic acid resin, polyurethane resin, styrene resin, styrene acrylic Resin, styrene diene copolymer, vinyl chloride copolymer, vinyl acetate resin, vinyl acetate copolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl acetate copolymer, butyral resin, petroleum resin, rosin ester, marinization Modified resins, such as rosin ester, dry oil, voile oil, etc. are mentioned.

Examples of the energy ray-curable photosensitive resins such as ultraviolet rays and electron beams include photosensitive cyclized rubber resins, photosensitive phenolic resins, photosensitive polyacrylate resins, photosensitive polyamide resins, photosensitive polyimide resins, and the like. Ester resins, polyester-acrylate resins, polyepoxy-acrylate resins, polyurethane-acrylate resins, polyether-acrylate resins, polyol-acrylate resins, and the like. Various monomers can be added as a diluent.

As a solid dispersion medium of the pigment composition of this invention, at least 1 sort (s) chosen from a thermoplastic resin, a thermosetting resin, wax, fatty acid amide, and fatty acid metal soap is mentioned. Color television The dispersion liquid used for the color filter used for the colored window of the remote controller of various electronic apparatuses usually consists of the organic solvent containing a film formation resin, a pigment dispersing agent, etc.

As an example of the thermoplastic resin used here, for plastic moldings, various plastics, for example, polyethylene resin, polypropylene resin, polyvinyl chloride resin, styrene resin, acrylonitrile-styrene resin, polyester resin, acrylic resin, Methacryl-styrene resin, ABS resin, etc. are mentioned. For synthetic fibers, fiber raw materials such as nylon, polyethylene terephthalate, polybutylene terephthalate, polypropylene, polyimide and the like can be given.

The coloring method of the article of this invention is a method of coloring an article using said coloring composition, and when an article is an infrared high permeability resin, surface coloring or an inside of an infrared high permeability resin using the coloring composition of this invention. By coloring, the infrared reflective coloring is applied, printed, printed, or printed using the coloring composition of the present invention on the basis of the method of coloring the infrared transmissive color and the infrared reflecting property of the article or formed in advance. How to do this. Moreover, according to this invention, the coloring article obtained by the coloring method of said article is provided.

[Example]

Next, the present invention will be described in more detail with reference to Synthesis Examples, Examples and Comparative Examples. In addition, in a sentence, "part" or "%" is a mass reference | standard unless there is particular explanation.

Synthesis Example 1

(a) Synthesis of coupling component "coupler-K"

80-85 in a mixture of 2,000 ml of chlorobenzene, 170.5 g (0.57 mol) of 2-hydroxy-11H-benzo [a] carbazole-3-carboxylic acid and 56.7 g (0.38 mol) of 5-aminobenzimidazolone After adding 52.4 g (0.38 mol) of phosphorus trichloride at < RTI ID = 0.0 > C < / RTI > over 1 hour, the mixture was stirred for 2 hours at the same temperature for 25 hours at 128 to 130 ° C, and then the solvent was removed by steam distillation in an alkaline state. It filtered and dried at 50-60 degreeC, and the preparation of 2-hydroxy-11H-benzo [a] carbazole-3-carboxy-N-benzimidazol-5-amide was obtained. This preparation was dissolved in 3,000 ml of methanol dissolved in 23 g of sodium hydroxide, and the insoluble fraction was filtered off, and 68 g of acetic acid was added thereto to precipitate (twice). The precipitate was filtered, washed with methanol, washed with water and dried to obtain a coupler (hereinafter referred to as "coupler-K") (melting point 449 ° C).

(b) Synthesis of Black Azo Pigment

1.38 g (0.01 mol) of 4-nitroaniline was suspended in 11.3 g of glacial acetic acid, and 3.7 g of concentrated hydrochloric acid was added thereto and stirred. 2.6 g of water was added thereto, the temperature was maintained at 0 to 5 ° C., 2.0 g of 40% aqueous sodium nitrite solution was added thereto, and the mixture was stirred at the same temperature for about 30 minutes to obtain a solution of diazonium salt. 4.8 g of sodium acetate trihydrate was added thereto to prepare a solution of diazonium salt.

On the other hand, 4.08 g (0.01 mol) of the coupler-K was dissolved in 250 g of methanol, in which 0.6 g of sodium hydroxide was dissolved, and the diazonium salt solution was added at 0 to 10 ° C. to maintain the temperature at 15 ° C. or lower. It adjusted to 7.0, coupling was performed, and the azo pigment of the following formula was obtained. The azo pigment is black. Hereinafter, it is called "black pigment-1."

[Comparative Synthesis Example 1]

Instead of "coupler-K" of Synthesis Example 1, 2-hydroxy-11H-benzo [a] carbazole-3-carboxy- (2′-methyl) -p-anisidide (CI coupling component 25 (hereinafter referred to as 4.20 g (0.01 mol) was used in the same manner as in Synthesis Example 1 to couple to 1.38 g (0.01 mol) of 4-nitroaniline to obtain a black pigment of the following formula. Refer to "Comparative Black Pigment-1".

[Synthesis Example 2]

2.23 g (0.01 mol) of 1-aminoanthraquinone as an aromatic amine was suspended in 11.3 g of glacial acetic acid, and 3.7 g of concentrated hydrochloric acid was added thereto and stirred. To this, 2.6 g of water was added and kept at a temperature of 0 to 5 ° C., 2.0 g of 40% aqueous sodium nitrite solution was added thereto, and stirred at the same temperature for about 30 minutes to obtain a solution of a yellow diazonium salt. 4.8 g of sodium acetate trihydrate was added to this to prepare a solution of diazonium salt. In the same manner as in Synthesis Example 1 (b), coupling was carried out with 4.08 g (0.01 mol) of Coupler-K to synthesize a black azo pigment of the following formula. Hereinafter, it is called "black pigment-2."

[Comparative Synthesis Example 2]

4.20g (0.01mol) of Coupler-25 was used instead of Coupler-K of the synthesis example 2, and it couples with 2.23g (0.01mol) of 1-aminoanthraquinone similarly to the synthesis example 2, and the black pigment of following formula is obtained. Got it. Hereinafter, it is called "comparative black pigment-2."

[Measurement of Thermal Properties of Black Pigments]

The thermal property in the air of the black pigment obtained by the said synthesis example and the comparative synthesis example was measured, and the result was shown in Table 1. Comparing pigments using the same aromatic amine, the black azo pigment using the coupler-K of the present invention as the coupling component showed much higher thermal stability than the known black azo pigment using the coupler-25.

In the black pigment-1 of the present invention using 4-nitroaniline as the aromatic amine, it is about 80 ° C higher than the comparative black pigment-1, and is about 300 ° C at the loss start temperature, and the black of the present invention using 1-aminoanthraquinone In Pigment-2, the weight loss start temperature is increased by about 170 ° C from Comparative Black Pigment-2, and is about 360 ° C. The dark-based azo pigment of the present invention is sufficient at the processing temperature near 300 ° C when kneading the resin. It appeared to withstand it.

Example 1 (alkyd baking paint)

(a) Preparation of black alkyd baking paint

Alkyd melamine calcined paint containing each of the black pigments 1 and -2 obtained in Synthesis Examples 1 and 2, and an oil-modified alkyd resin (33% whey, 60% pure) and a butylated melamine resin (50% pure) It mix | blended according to the compounding prescription of Table 2 below, and added the glass bead according to the conventional method, and disperse | distributed using the paint shaker, and prepared two types of paints (The thing using black pigment-1 was used as the coating material-1, and black. What used Pigment-2 was made into the coating material-2).

(b) Measurement of transmittance in the near infrared region

The optical characteristics of the paint-1 and -2 using the black pigment-1 and -2 obtained by the said synthesis examples 1 and 2 were measured. Each paint was applied to a quartz glass plate with a 2 mil applicator, respectively, and dried in accordance with a conventional method. The transmittance | permeability of the visible part and near-infrared was measured with the 330-type magnetic spectrophotometer (the Hitachi make), and the measurement result was shown in Table 3. Each black paint exhibited a large transmittance in the near infrared region of 800 nm or more.

(c) measuring reflectance

Subsequently, the 330 type magnetic spectrophotometer (manufactured by Hitachi, Ltd.) used the respective coated glass plates obtained above, and the reflectance and black plate (carbon black) on a white background on which the white plate (magnesium oxide plate) was placed on the back of each glass plate. The reflectance on the black background under the plate was measured. The reflectance of the white background is the sum of the reflection of the coating film and the reflection from the white background surface of the light passing through the coating film, and the reflectance of the black background represents the reflection of the coating film only.

Table 4 shows the measurement results. Although all black coating films showed that the reflectance was low on a black background and the reflectance was low as a coating film, the same result as the high transmittance | permeability of a coating film was shown. In the white background, the background reflection effectively showed high reflectance in the near-infrared region of each coating.

Example 2 (acrylic constant dry paint)

17 parts of black pigment-1, 70 parts of thermoplastic acrylic resins, and 13 parts of mixed solvents (toluol: xylol: butanol: cellosolve = 6.8: 3.2: 2.2: 0.8) were dispersed by a ball mill to obtain a black paint. Prepared. This was apply | coated to the steel plate previously apply | coated with the white paint containing a titanium oxide white pigment and an extender pigment, and the black coating film was formed. This black coating material is effective as a heat shielding coating material, reflecting infrared rays of sunlight, in addition to the reflection effect from the background of light transmitted through the upper coating film, and the temperature increase was suppressed more than the black coating material using a carbon black pigment. In addition, black pigment-2 was used instead of black pigment-1, and black paint was prepared like above, and it applied to the steel plate. As mentioned above, it was effective as a thermal insulation paint of sunlight.

Example 3 (paint for metal products)

45 parts of ethyl acetate solutions (solid content: 50%) of the reactive acrylic styrene resin which consists of 5 parts of black pigment-2, the methacrylic acid alkylester-styrene copolymer which has a hydroxyl group and a carboxyl group, a methoxymethylmelamine crosslinking agent (solid content: 50 %) 5 parts, the antifouling agent 0.1 part, and 44.9 parts of xylene were prepared the acrylic styrene coating material for black metal products. The coating material was spray-coated to the metal product using the obtained coating material, followed by baking to give a beautiful black coating to the metal product. Furthermore, in combination with alumina powder, beautiful black coating was possible as an acrylic baking paint for metal products. These black coatings reflected the heat rays of sunlight and were effective as heat shielding coatings by the background reflective effect, and the temperature rising was suppressed more than the black coatings using carbon black pigments. In the same manner as described above, a black paint was prepared using black pigment-1 instead of black pigment-2, and applied to a steel sheet. As mentioned above, it was effective as a thermal insulation coating of sunlight.

Example 4 (molding resin plate)

5 parts of black pigment-2, 20 parts of titanium oxide white pigments, and 75 parts of polyethylene resin powders as a pigment dispersant were mixed with a Henschel mixer (powder high speed mixer) to obtain a powder colorant (dry color). Next, 1.0 part of the powder coloring agent obtained was mix | blended with 100 parts of polybutylene terephthalate (PBT) resin pellets, it mixed with the Henschel mixer, and it was set as black resin pellets with an extruder. The obtained black pellet was shape | molded at 240 degreeC with the in-line screw injection molding machine, and the black PBT resin molded board excellent in pigment dispersibility was obtained. By the infrared ray permeability of a black pigment and the reflection effect of the light ray of a titanium oxide white pigment, the heat ray of sunlight was reflected, and the temperature increase prevention property was shown. In addition, the above-mentioned black pigment-1 was used instead of black pigment-2, and the pale black PBT resin molded board was obtained similarly. As mentioned above, the temperature rise prevention of sunlight was shown.

Example 5 (transparent molded plate)

Acrylic resin (polymethyl methacrylate) containing 20% of black pigment-1 2 parts of black master batches were mix | blended with 100 parts of acrylic resin pellets, it mixed with the Henschel mixer, and it was set as black resin pellets by the extruder. The obtained black resin pellet was shape | molded by the in-line screw injection molding machine, and the black acrylic resin molded board excellent in pigment dispersibility was obtained. This molded plate was used as a black acrylic resin infrared color filter that shields visible light and transmits only infrared light. This molded plate is useful as color filter plates, such as an infrared radiation remote controller. In addition, instead of the black pigment-1 used above, the black pigment-2 was similarly obtained and the black transparent molded board excellent in infrared rays permeability was obtained.

Example 6 (transparent molded plate)

2 parts of polycarbonate (PC) resin black masterbatch pellets containing 20% of black pigment-2 were mix | blended with 100 parts of PC resin pellets, it mixed with the Henschel mixer, it knead | mixed at 280 degreeC with the extruder, and it was set as black resin pellets. The obtained black resin pellet was shape | molded at 280 degreeC with the in-line screw injection molding machine. The visible light was shielded and a black PC resin infrared color filter plate transmitting only infrared light was obtained. This molded plate is useful as a color filter plate of an obstacle detection system of an infrared radial remote controller and an infrared radial vehicle. Moreover, instead of the said black pigment-2, the black pigment-1 was similarly obtained and the black transparent molded board excellent in infrared rays permeability was similarly obtained.

Example 7 (stock color spinning)

50 parts of black pigment-2 and 50 parts of ethylene bis stearic acid amide powder as a pigment dispersant were mixed with a Henschel mixer to obtain a dry color having a pigment content of 50%. Subsequently, 1.0 part of the obtained dry color was mix | blended with 99.0 parts of polypropylene resin pellets, it mixed with the Henschel mixer, it knead | mixed at the temperature of 200-220 degreeC as extrusion conditions with the vent type 40m / m extruder, and it was set as 0.5% black resin pellets. The obtained black resin pellet was spun at a temperature of 220-240 degreeC as a spinning condition with the melt spinning machine, and the black polypropylene undiluted | dyed colored yarn of fineness 10 denier was obtained. The woven fabric showed the temperature increase prevention by sunlight. In addition, black pigment-1 instead of black pigment-2 was used, and the black polypropylene undiluted | stock coloring yarn which was similarly excellent in the temperature rising prevention property of sunlight was obtained.

Example 8 (vinyl chloride coating agent)

A mixture of 0.5 parts of black pigment-2 and 1.0 part of adipic acid ester plasticizer was mixed with 50 parts of polyvinyl chloride resin compound, and rolled with a 6 inch roll at 155 to 160 ° C. for 3 minutes to form a sheet. The black sheet obtained above as a skin layer on a separately prepared white base sheet, or a white compound using the above black compound and titanium oxide white pigment, a phthalocyanine blue pigment (CI pigment blue (PB) 15: 3), quinacridone pigment ( PV19), obtained by kneading with a colored compound using a dioxazine violet pigment (PV23) and a cyanine green pigment (PG36), laminating a gray sheet or a dark colored colored sheet by press molding to a thickness of 5 mm at a pressure of 50 kg at 170 ° C. The multi-layered sheet thus reflected a heat ray of sunlight and exhibited a temperature increase prevention action. In addition, the black pigment-1 was used instead of the black pigment-2 in the above, and the black- or dark-colored multilayer sheet of the sunlight-proof temperature rising prevention color was obtained similarly.

Example 9 (Polyurethane Coating)

100 parts of milky white methyl ethyl ketone dispersions of solid ether polyol-diphenylmethane diisocyanate-based polyurethane having a carboxyl group (solid content: 30%), methyl ethyl ketone solution of polyether polyol-diphenylmethane diisocyanate-based polyurethane (solid content) : 50%) 5 parts and 2.5 parts of polycarbodiimide type crosslinking agents (solid content: 20%) were fully mixed. 1 part of black pigment paste which kneaded 0.5 part of black pigment-2 and 1.0 part of adipic acid ester plasticizers was added there, and it mixed sufficiently, and prepared the black polyurethane coating liquid. It was coated with about 200 g / m <^2> on the polyester woven fabric surface, and it dried, and obtained the black fiber processing product. This black polyurethane sheet showed the temperature rising prevention property with respect to the heat ray of sunlight. The gray sheet and the dark colored pigment sheet obtained by kneading by adding a white pigment paste or a blue, red, green and brown colored pigment paste to the black pigment paste also exhibited a temperature-preventing effect against sunlight. In addition, the black pigment-1 was used instead of the black pigment-2 in the above, and the temperature increase prevention black of sunlight, or the pigment sheet of the chromatic color of a gray or dark system was obtained.

Example 10 (offset ink)

15 parts of black pigment-2, 83 parts of combination varnishes for offset flatbed inks, 0.2 parts of 5% cobalt dryers, 1.0 parts of 8% manganese dryers and 0.8 parts of ink absorbers were sufficiently mixed to obtain an offset printing ink. Beta printing on good quality paper with this printing ink. The combination varnish for offset flat ink used above was obtained by mixing 35 parts of rosin-modified phenol resin, 10 parts of dry oil-modified isophthalic acid alkyd, 35 parts of dry oil, 29.5 parts of ink absorber, and 0.5 parts of aluminum chelate. White ink or blue, red, green, and brown color ink were added to the black ink to obtain gray ink or color ink of a dark color, and a gray print or a color color printed material of a dark color was obtained.

Example 11 (aqueous gravure ink)

15 parts of black pigment-1, 60 parts of polyurethane aqueous resin (solid content: 30%) containing a carboxyl group obtained from polycarbonate polyol and aliphatic isocyanate, 5 parts of water-dispersible wax (solid content: 30%), antifoaming agent 1 part, poly 5 parts of carbodiimide crosslinking agents (solid content: 50%) and 14 parts of water were mix | blended and the black aqueous gravure ink was prepared. Similarly, in 100 parts of each color ink, blue, red, yellow containing 15 parts of phthalocyanine blue pigment (PB15: 3), 15 parts of insoluble azo red pigment (PR5) and 8 parts of disazo yellow pigment (PY74), respectively. 100 parts of aqueous gravure inks were prepared. Using the obtained four-color printing ink, it printed on transparent colorless plastic films, such as polyethylene, a polypropylene, polyester, and nylon. Printing using black ink had high infrared transmittance like other color printing. In addition, black color ink and the three color chromatic color inks were prepared to prepare a dark color colored color ink, and dark color colored color printing with high infrared transmission was performed on the plastic film. Black ink-2 was prepared like the above using black pigment-2 instead of black pigment-1 in the above, and prepared black ink.

Example 12 (woven fabric for woven fabric)

25 parts of black pigment-1, 20 parts of nonionic pigment dispersants, 20 parts of aqueous pigment dispersions consisting of 1% of antifoaming agents, 64% of water, 25 parts of reactive alkyl acrylate esters (40% solids), 0.5 parts of antifoaming agents, dispersant 1 3 parts of the dispersion stabilizer for oil-in-water emulsification, 38 parts of mineral tapene, 12.5 parts of water, and black paste of 1% of epoxy type crosslinking agent were used together with the black paste of the paste state in which the azo pigment was dispersed in the above-mentioned formulation. Prepared. The black printed matter was obtained by printing on a polyester-cotton blended foam by a silk screen process, and performing a 15 minute curing at 120 degreeC. This printed material showed the performance which moderates the heat of sunlight. In the same manner as described above, black printing paste was prepared using black pigment-2 instead of black pigment-1 above to obtain a black printed matter.

Synthesis Examples 3-12

In the same manner as in Synthesis example 1, the dark-based azo pigment of this invention shown in following Table 5 was obtained using another aromatic amine. Thermal properties were also measured in the same manner as in Synthesis example 1.

The dark color azo pigment of the present invention, in particular, the pigment whose particle diameter is adjusted to micronization at the submicron to nanometer level, has the advantage of high coloring power as a colorant, and because it is an organic pigment, solvent resistance, light resistance, heat resistance, water resistance, Pigment physical properties, such as chemical resistance, are especially excellent in heat resistance. In addition, it is an ultra-fine particle pigment, and has optical characteristics having a high optical transmittance near the near infrared compared to the pigment of coarse particles, and is useful as an optical filter of infrared communication, infrared camouflage, and infrared irradiation sensor, in which a oil-soluble dye is conventionally used. Do.

The dark color azo pigment of the present invention, on the contrary, has low reflectivity because the near-infrared region is highly transparent. However, for example, in a heat shielding paint, by devising a coating method, such as coating on a white background coating, a high heat shielding property can be expected rather than using the pigment of coarse particle with high reflectivity. It is useful as heat shielding paints for buildings such as buildings, houses and warehouses, for exterior painting of automobiles, for coating materials for raising the temperature of interior materials, for pigment printing for cold use of agriculture, for colorants for fibrous solution colorants and for coating of electronic parts. In addition, since the dark azo pigment of the present invention has good solvent resistance, light resistance, heat resistance, water resistance, and chemical resistance as a dark organic pigment, and has a high coloring power and is an azo pigment, It is used together and it is used as coloring agents, such as a gray or dark colored pigment paint, pigment printing agent, the coloring composition for fibers, the coloring composition for plastics, printing ink, the coloring composition for image recording, and the coloring composition for image display.

Claims (12)

A dark color azo pigment represented by the following general formula (I).

[Wherein n is 1 or 2 in the formula, X represents a hydrogen group or a substituent, and the substituent is a halogen group, an alkyl (C _{1 to} C ₂₀ ) group, an alkoxyl (C _{1 to} C ₂₀ ) group, or a phthal At least one selected from the group consisting of a midmethyl group and a sulfonic acid group, and at least one substituent, and Ar is selected from the group consisting of a phenyl group, naphthyl group, anthryl group, and 9,10-anthraquinonyl group which may be introduced with a substituent. Wherein the substituent is an alkyl group (C _{1 to} C ₂₀ ), an alkoxyl group (C _{1 to} C ₂₀ ), a fluoroalkyl group (C _{1 to} C ₂₀ ), a halogen group, a carboxyl group, an ester group, oxycarbonyl ( ester) group, Carbamide group, an amino group, an imino-dicarbonyl group, imidazolonyl group, a nitro group, an alkyl (C _1~ C ₂₀₎ alkylsulfonyl group, phenyl methyl sulfonyl group, an alkyl (C _1~ C ₂₀ A group consisting of an aminosulfonyl group, a benzoylamino group, a phenylamino group and a phenyl ether group At least one member selected from, at least one substituent.] delete The dark color azo pigment according to claim 1, wherein the average particle diameter is 20 nm to 1,000 nm. The coloring composition containing the dark-based azo pigment of Claim 1 or 3 in a liquid dispersion medium or a solid dispersion medium, The coloring composition characterized by the above-mentioned. The dark-color azo pigment alone or a mixture with the dark-color azo pigment and at least one selected from the group consisting of other chromatic pigments, white pigments, other black pigments and sieving pigments. Phosphorus coloring composition. delete The coloring composition of Claim 4 in which the said solid dispersion medium contains at least 1 sort (s) chosen from a thermoplastic resin, a thermosetting resin, a wax, a fatty acid amide, and a fatty acid metal soap. The coloring composition according to claim 4, which is for paint, plastic, textile, printing ink, image recording, image display or pigment printing agent. An article is colored using the coloring composition according to claim 4. 10. The method of coloring an article according to claim 9, wherein the article is made of an infrared high permeability resin and colors the surface or the inside of the article. 10. The method of claim 9, wherein the article is colored on the infrared reflective article itself or on an infrared reflective layer formed on the surface of the article. It obtained by the method of Claim 9, The coloring article characterized by the above-mentioned.