TW201241098A - Black azo pigment and process for production thereof, colored composition, coloring method, and colored articles - Google Patents

Abstract

The present invention is a black azo pigment which has both of the optical properties of a visible light shielding property and an infrared ray transmitting property, and which has a structure that has, in the molecule thereof, at least two azo bonds and at least one 2-hydroxy-11H-benzo[a]-carbazole-3-carboxylic acid amide residue derived from a coupling component, wherein the black azo pigment is characterized by having an average particle diameter of 10-200 nm. The present invention enables the provision of: a black pigment which exhibits excellent physical properties and color fastness as a pigment, can be used in various use applications, and exhibits both of the optical properties of a visible light shielding property and an infrared ray transmitting property; a process for producing the pigment; a colored composition containing the pigment; and a coloring method and a colored article, in each of which the colored composition is used.

Description

201241098 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a black azo dye, a method for producing the same, a coloring composition, a coloring method, and a colored article. More specifically, 'the use of the phenomenon of absorbing and containing the visible light region and further penetrating in the infrared region, and showing the optical properties useful for the use of infrared rays, having a specific configuration of black A polyazo dye, and a method for producing the same, a coloring composition, a coloring method thereof, and a colored article. [Prior Art] A black pigment used as a coloring agent for paints, printing inks, or plastics is generally a carbon black pigment or an iron oxide black pigment. These black pigments appear black by absorbing light from all wavelength regions of light. In the solar-ray electromagnetic wave, the light system in the region of about 380 nm to 78 〇 nm is regarded as visible S, and the light in the region of Q 々 m 2 2.5 qing which is longer than the visible light is near-infrared. The black system absorbs light in the wavelength range of visible light, and the carbon black pigment is concluded to absorb not only visible light but also light in the near-infrared region. The near-infrared rays in the light are different from the short-wavelength light such as ultraviolet rays, and have little adverse effect on the human body, and are safe light. Therefore, in recent years, there have been many electronic devices for irradiation and reception using infrared rays. For example, infrared remote control conveyors and their body receivers are popular in electrical appliances, care tools, warm toilet seats, county machines, even car shackles, engine starters, 100149099 201241098 garage switches, heads or buildings. (4) Infrared rays to prevent external surveillance cameras and other daily life I {machine Ge Hongzhao ^ can be read in 1 , taste (4) equipped with (four) correcting the car before... the light is seen, the car is used to confirm the obstacles in front For the vehicle, see the light and penetrate the infrared ray, and use the night vision equipment for the infrared ray filter used as the infrared camera or the infrared camera of the receiver. It is expected that the second & In addition, in the recent years, the solar power generation system has been attracting attention as a clean energy, and it has been widely used as a clean energy. The solar power modules that make up the solar energy (four) system are installed in places where sunlight can be directly irradiated, especially in the roof or roof of outdoor open space or outdoor buildings. However, the light-receiving system of the solar light causes the solar power generation module to heat up and the output of the power generation unit to be lowered. In addition, depending on the manner in which the appearance or the dirtyness of the power module is not conspicuous, from the face (4), the color, the color, and the color, depending on the situation, this will become the cause of the apparent temperature rise. Therefore, regarding the solar power generation, even if the color is black 4, it is expected that the coloring can be suppressed only by the temperature rise. A fresh plate for solar cells containing a garden pigment has been proposed (Patent Document 2). In recent years, in view of the improvement, optimization, and energy saving of the living environment, it is desirable to have a frequency coating according to the reflection of sunlight, and accordingly, the above-mentioned desired heat ray reflective material for various applications of 100149099 201241098 is desired. Development. For example, there may be a roof, a building, a warehouse, a warehouse, a roof, a building, a roof, a wall, a road, a road, a car, a car, a car, a wall, or a ship. It is expected to use heat-shielding materials for agriculture, and the like, and heat-releasing materials such as electronic parts are also desired. In addition, in the field of information technology, with the recent rapid development of information technology machines, liquid money (hereinafter also referred to as "LCD") is used as an information display component and is used in many ways for televisions, projectors, and individuals. Computer I mobile information machine b, surveillance H, car guide wire, mobile phone, motor or electronic secret display (four) face, information disclosure board, 丨 钱 money, money, digital camera or camera photographic pictures machine. With this phenomenon, the improvement of the quality of the mouth and the reduction of the cost, the color of the light is: the quality of the product is "% of the situation", cost reduction. = CF, also requires fineness, color Excitability, light wear = color characteristics and material secrets in the image of the coffee and the like are superior to the contrast quality, and it is desirable to have a material that can correspond to the characteristics of the requirements, and the color pixels are listed as Strand, mosaic, three) color), so that the R, G, B pixel penetration = two back (four) back source color, as an image. Then 'in each pixel around the grid; = 仃 emit color matrix (The following is also referred to as "BM" for short). The masking does not need to be black 100149099 201241098 or prevent 4 red color pigments, green pigments, blue pigments, yellow (four) or purple pigments in terms of color pixels. However, each of them has been improved and applied to the BM. As a light-shielding material for completely shielding the light in the visible light region of the backlight, the problem is that the size of the substrate is large or the % of the complex compound is burdened. Metal chromium film Move to a resin black pigment of ΒΜ. The backlight is also replaced by a cold cathode fluorescent tube to a light-emitting diode (cafe), and thus is associated with an increase in color purity and an increase in color reproduction area. The red region is proposed to have a clear light of about 600 to 620 nm in the backlight of the cold cathode fluorescent tube, and as the light from the red light emitting portion in the backlight of the LED, and at the maximum emission wavelength. In the vicinity of 64 〇 nm, bright light having an emission wavelength range of approximately 540 to 800 nm is used (Patent Document 3). Therefore, as the BM, it is possible to sufficiently block the light system on the long wavelength side of visible light. Further, various improvements have been proposed regarding the display method of the pixels of CF, so that the improvement of BM and even the improvement of the light-shielding black pigment used in B 亦 are also in progress. For example, in order to improve the wide viewing angle as a weak point of the LCD in the prior art, a transverse electric field effect conversion method (IPS method) in which an electric field is applied in parallel to a substrate to convert a liquid crystal layer to display a pixel is proposed. Further, a matrix black matrix method (BOA method) or a matrix color filter method (c〇A method) in which BM is formed on a thin film transistor (TFT) is capable of increasing a pixel area because of a high aperture ratio, and In the operation step, the fitting step 100149099 201241098 can also be upgraded and rationalized. Further, in order to achieve such improved methods (especially the IPS method), it is necessary to maintain the interval (cell gap) of the substrate sandwiching the liquid crystal layer with high precision. However, in the manner in which the bead spacers are dispersed in the prior art, it is difficult to adjust the cell gap to be certain. As a method for realizing a uniform cell gap due to the spacer formed thereby, it is proposed to increase the thickness of the BM itself or to superimpose the spacer layer such as the colored layer or the photoresist layer on the BM. Further, by not using the bead spacers, it is possible to improve the deterioration of display quality due to scattering or penetration of light by using the bead spacers (Patent Documents 4 and 5). According to the IPS method, the BOA method, the C0A method, etc. described above, the method of forming the chest on a wire element such as a TFT is of course a problem that the TFT causes an erroneous operation when the insulating property is insulated. The carbon black pigment generally used as the black pigment is a low resistance value = and is not suitable for the light-shielding silk which is used as the light-shielding black pigment used in these methods, and is desired to have high electrical insulating properties. On the other hand, there is a proposal for covering a stone black pigment which is defined by the amount of oxygen in a high-insulating resin film to make the carbon black pigment which is electrically grown (Patent Document 6)' or It is related to the use of insulating carbon black pigment or covered by resin to read the selected pigment, so that the formation of insulating BM is suitable for the static c ... For the disclosure of the C〇A method (Patent Document 100149099 201241098 2 and the 'carbon black pigment is originally a material having conductivity, even if it is covered with a resin as described above, it is difficult to complete the insulation. In addition, the use of BM for preventing the light from the adjacent light-emitting elements and improving the sharpness of the light-emitting surface has been proposed (Patent Document 8). [Patent Document 1] [Patent Document 1] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. [Patent Document 4] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. 2, No. [Patent Document 7] Japanese Patent Publication No. 4 338 479 [Patent Document 8] Japanese Patent Laid-Open Publication No. Hei No. Hei. No. Hei. Make The superior physical properties and robustness of the pigments are expected to develop black pigments that exhibit both optical properties of visible light blocking and infrared penetrating properties, which are useful for various applications. Specifically, for example, it can be used for: masking is not required. Visible light rays, which are used for infrared filters for electronic devices that penetrate and utilize infrared signals; or 100149099 8 201241098 to suppress sunlight due to the distribution of black or dark colored light rays that constitute a solar power generation system The temperature rises, and the infrared light is provided on the reflective substrate of the solar light. The plurality of layers of the transparent black layer are m or relatively cf, and even in the case of a wide LED backlight of the light-emitting wavelength region, the entire surface can be shielded. Light in the visible light region, and even if BM is formed on the active active component, it can maintain two electrical insulation properties, and there is no use of the TFT to cause the wrong block action, and also suitable for the visible light shading of the BM of the organic EL display. High use, etc., and also as a black pigment which is superior in physical properties and firmness of the pigment. The purpose of the present invention is to provide a black pigment which exhibits superior physical properties and robustness as a pigment, and which is applicable to the above various applications, and which exhibits both optical properties of visible light blocking property and infrared penetrating property, a method for producing the pigment, and a method for producing the pigment. A coloring composition containing the pigment, a coloring method using the same, and a colored article. (Means for Solving the Problem) The present inventors have carefully studied and reviewed the chemical structure of the black organic pigment in order to achieve the object of the present invention. As a result, it was found that the black polyazo pigment having a specific structure absorbs light at a high level of absorption in a wavelength range of about 4 〇〇 to 750 nm in the almost full region of the visible light region, and further 'at about 900 〜 l5 〇. On the long wavelength side of the infrared region of 〇nm, it shows that the local penetrating property is even finer and pigmented in such a manner that its average particle diameter becomes 1 〇ηιη~2〇〇nm. 100149099 9 201241098 In order to solve the above problems and complete the present invention β, that is, the present invention provides a A black azo pigment which exhibits two optical characteristics of visible light ray blocking property and infrared ray penetrating property, and is characterized in that it is a black polyazo pigment having the following structure in a molecule, and has two or more azo Bonding and at least one 2-based thiol-hydrazinyl-benzo[3-]-carbazolyl-3-carboxylic acid decylamine residue introduced by the coupling component; and having an average particle diameter of i〇nm~2〇 〇nm. As a preferred aspect of the present invention, the following black azo pigments are exemplified. a black azo pigment, wherein the visible light-shielding property of the black azo pigment comprising a black azo pigment on a transparent substrate exhibits a spectral separation of about 5% or less in a wavelength range of about 4 Å to 75 nm in the visible light range. Transmittance; the above infrared ray penetration (4) The black colored film exhibits a transmittance of about 100 or more in the wavelength range t of 900 to 15 GGnm in the infrared region. A black azo pigment, wherein the polyazo pigment has at least one of the following structures (1) to (4): " (1) can be used; | The amine (representative formula: H2N-Ar-NH2) is given #气化&#. The weight of the material J 卞Μ is diazotized (d touch η -, and the salt will be used as the coupling component of the (four) base seven:

The structure of the guanamine (abbreviated as hbc) is formed by azo/coupling I according to [Nengyang N_Ar_NlHBC]. (2) using a diazo component having two or more amine groups (representing formula (10) bribe 2) to be diazotized to form a salt, which will be used as an even synthesis component of 9 M-, and the milk is present and the 2·subtractive H H-benzo[a]+sodium (tetra) acid aryl 100149099 201241098 base amide (abbreviated as HBC) and other coupling components (expressed as Cp) of the compound are formed by azo/coupling (3) In its molecular towel, hiding (4) ^ 2··_πη• benzo[a]· The singular component (abbreviated as HBC-HBC) referred to as __) is subjected to heavy gasification using a compound having an amine group as a diazo component (denoted as Ab NH2), and is formed by argon/coupling. The structure shown by [Ar-N=N_HBC-HBC-N=N-Ar]. (4) In its molecule, for bismuth 2-hydroxy·11H-benzo[a]-carbazolylcarboxylate An even component (indicated as HBC_Cp) of an amine residue (abbreviated as HBC-) and a residue other than the compound (expressed as Cp-), using a compound having an amine group as a diazo component (represented Re-I for Ar marriage 2) to make azo/even The structure represented by [Ar-N=N-HBC-Cp-N=N-Ai·] is formed by chemical synthesis. In the above description, "Ar" is representative of aromatic compounds and heterocyclic compounds. The residue of the compound may be the same or different in the case of two or more in the formula. Further, "Ar-N=N-" or "N_Ar_N=N\" in the formula means The "aryl azo residue" after coupling of the heavy DL salt of the diazo component is the same as the following. As another embodiment of the present invention, a method for producing a black azo pigment is provided for obtaining The above-described method for producing a black azo pigment of the present invention is a production method having a step of synthesizing a black polyazo pigment and a step of miniaturizing the Guhai 100149099 201241098 pigment as required, wherein (i) the above black The method for synthesizing a polyazo pigment can be classified into any one of the following four types. In the case where the polyazo pigment synthesized by the methods is coarse, the average of the pigments is obtained by any of the following methods. a step of finely reducing the particle diameter to 10 nm to 200 nm. As another aspect of the present invention The present invention provides a coloring composition comprising a black azo pigment of the present invention described above or a black azo pigment obtained by the above production method in a liquid dispersion medium or a solid dispersion medium. According to another embodiment of the present invention, there is provided a method for coloring an article, which is characterized in that the coloring is performed when the article is colored black or dark by coloring of the surface of the article or coloring of the article itself. Composition. According to still another embodiment of the present invention, there is provided a colored article characterized by being subjected to a coloring method of the above article. Another embodiment of the present invention provides a solar power generation module back cover plate which is attached to a light-reflective sheet and has a plurality of layers of black or dark colored infrared penetrating layers. The infrared penetrating layer has a structure in which two or more azo bonds in the molecule and less than one 2-hydroxy-11H-benzo[a]-carbazolyl-3- introduced by the even component are added. a structure of a carboxylic acid hydrazine residue (abbreviated as HBC-); and a black polyazo pigment having an average particle diameter of 1 Onm to 200 nm. According to still another embodiment of the present invention, there is provided a method of manufacturing a cover sheet after a solar power generation module 100149099 12 201241098, characterized in that a substrate having a light reflectivity as a light reflective sheet is used, or a use is provided in advance. The substrate of the light-reflective substrate is formed as a light-reflective sheet, and has a structure on the surface of the substrate or the light-reflective substrate: having two or more azo bonds in the molecule and a structure of at least one 2-hydroxy-11H_ benzo(9)oxazolyl-3-carboxylic acid decylamine residue (abbreviated as HBC-); a black polyazo pigment having an average particle diameter of 10 nm to 200 nm The coloring composition is applied by coating, coating, attaching, dissolving, laminating, printing, inkjet printing, electrophotographic printing or xerographic printing, and exhibiting a reflective color in the infrared region 'will be black or dark The colored infrared penetrating layer is laminated on the light reflective sheet. According to another embodiment of the present invention, a color display panel is provided, wherein a black matrix (BM) formed on a color filter (CF) substrate or an organic EL light-emitting substrate has the following structure: in a molecule a structure having two or more azo bonds and at least one 2-hydroxyl_11H·benzo[a]-carbazolyl-3-carboxylic acid decylamine residue (abbreviated as HBC_) introduced by the azo compound; And it contains a black polyazo pigment having an average particle diameter of from 10 nm to 200 nm. (Effect of the Invention) According to the present invention, the black colored film containing the black azo pigment exhibits almost complete absorption in a wavelength range of about 400 to 750 nm including the visible light range on the transparent substrate. Then, in the infrared region of the long wavelength, high transmittance is exhibited on the transparent substrate, and it is shown that the useful optical characteristics of both visible light blocking property and infrared penetrating property are shown in 100149099 201241098. Because of such characteristics, the black azo pigment of the present invention can effectively utilize an infrared filter as an infrared remote controller and a body receiver. Further, the black azo pigment of the present invention can also be used as an infrared filter which is an infrared sensing device for detecting/recognizing obstacles on the road of an automobile or the like which has been used. Further, since the black azo pigment of the present invention exhibits optical characteristics including a visible light region and even a long wavelength side, the light-shielding black material which is a BM of CF, for example, will correspond to a red pixel from an LED. The wavelength region of the light of the red light-emitting portion of the backlight is sufficiently absorbed to be a light-blocker. The color system of the LCD can of course be colored black, and the color can be made more vivid than other colored ones. Even in the improved method of forming various CFs of BM on an active device such as a TFT, for example, a BM or IPS method or a COA method for maintaining the thickness of the liquid crystal layer can be suitably formed instead of the spacer. A light-shielding black pigment of CF BM. In particular, it is the best light-shielding black pigment for IPS-based liquid crystal panels using LED backlights and organic EL displays. In addition, since it penetrates the infrared ray sufficiently, it is reflected by the white pigment or the body pigment added to the base or the coating material, and is used as a viewpoint of improvement, comfort, and energy saving in recent years. A material for preventing temperature rise of direct sunlight for the painting of houses, buildings, etc., road paving, and even the decking and exterior decoration of ships. In addition, in the solar power generation system, it is also possible to use a rear cover H which can form a plurality of layers of black or color infrared (four) transparent layers on the reflective substrate layer due to temperature rise caused by sunlight. It can also be used in the military for camouflage coloring materials or camouflage prevention. [Embodiment] Hereinafter, the present invention will be described in further detail by way of the best mode for carrying out the invention. According to the invention, the black subtraction (four) of the bribe is not optically characteristic and contains and absorbs the visible New Zealand domain, especially in the wavelength range of the long wavelength side, and shows almost in the near infrared region. High penetration rate. Specifically, the spectral transmittance of the black colored film on the transparent substrate is about 5% or less in the wavelength range of about 400 to 750 nm in the visible range, and is displayed in the wavelength range of the infrared region of about 900 nm to 1500 nm. It is about 3〇〇/0 or more. Further, as electrical characteristics, it exhibits an extraordinary electrical insulation property. The inventors of the present invention have conducted a review on a pigment having a plurality of chromophores in a molecule, and even a pigment which resonates with each other as a black pigment exhibiting the optical characteristics of the above characteristics, and as a result, the ease of synthesis is particularly high. A stable production process was developed, and a black polyazo pigment having two or more azo bonds in a molecule and having a specific chemical structure was developed. Further, since the infrared ray region is particularly required to be highly permeable, the black polyazo pigment is preferably a pigment having a fine particle diameter, and the pigment ruthenium particle size is required to be about 1 〇 nm to 2 〇〇 nm. Yu Jinyi 100149099 15 201241098 In the case of high penetration rate, the ultra-fine black polyazo pigment with an average particle size of about 10 nm to 50 nm is used, or in the coloring processing step, the molecule is given in the medium. Dispersed dispersion of _ nature of the black azo pigment. In the present invention, the so-called polyazo pigment is a bis-ring material or an azo pigment having two or more oxime bonds in the molecule. As a polyazo pigment, the chemical structure of black is shown. The inventors have found that there are two or more azo bonds in the molecule, and at least one 2-hydroxy-11Η-stup is introduced by its even component. The chemical structure of a]-carbazolyl-3-carboxylic acid decylamine residue (refer to the following formula).

The method for producing the polyazo pigment is required to give two or more azo bonds in the molecule, and examples thereof include two or more diazo components having different amine groups on the diazonium salt group. The method of performing the azo couple α as the diazo component or the method of performing azo or coupling using the even component having two or more coupling positions of the coupling component. The details of this aspect are as follows: 100149099 201241098 The black azo pigment of the present invention is preferably one having the following structures (1) to (4). (1) A diazonium formed by diazotizing a compound having two or more amine groups (representative formula: H2N-Ar-NH2) as a diazo component, and using the salt as an even component [HBC-N=N-Ar-N formed by azo/coupling of 2-yl-1H-benzo[a]-carbazolyl-3-carboxylic acid aryl decylamine (abbreviated as HBC) Black polyazo pigment of the structure shown by =N-HBC]. As an example of the black polyazo pigment having the structure (1) represented by [HBC-N=N-Ar-N=N-HBC], as described below, there are two or more amine groups used in the diazo component. A structural example of the case of benzidine or phenyldiamine.

100149099 17 201241098 (2) A diazonium salt formed by diazotizing a compound having two or more amine groups (representative formula: H2N-Ar-NH2) which is a diazo component, and the salt will be used as a coupling Component 2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxylic acid aryl decylamine (abbreviated as HBC) and other coupling components other than the compound (expressed as Cp) are azo/coupled The black polyazo pigment having the structure shown by [HBC-N=N-Ar-N=N-Cp] was formed. Examples of the black polyazo pigment having the structure (2) represented by [HBC-N=N-Ar-N=N-Cp] include, as described below, two or more amine groups used for the diazo component. For the benzidine or phenylenediamine, a structural example is used as the other coupling component of 2-hydroxy-3-naphthoquinone decylamine.

100149099 18 201241098 (3) In its molecule, for the coupling component having two or more 2-hydroxy-11H-benzo[ap carbazolyl-3-carboxylic acid decylamine residues (abbreviated as HBC-) (expressed as HBC-HBC), which is formed by using a compound having an amine group as a diazo component (not represented by Ar-NH2) to form a gasification to form an anodic/coupling [Ar-N=N-HBC A black polyazo pigment of the structure shown by -HBC-N=N-Ar]. Examples of the black polyazo pigment having the structure (3) represented by [Ar-N=N-HBC-HBC-N=N-Ar] can be exemplified for the passage of a phenyl group or a biphenyl group. HBC-HBC with two couplings of 2-hydroxy-11H-benzo[a]-carbazolyl-3-storied amine residues, using a strepamine with one amine as diazo A structural example in the case where the component is formed by diazotization.

X

100149099 19 201241098 X X_

(4) in its molecule, for a residue having a 2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxylic acid decylamine (abbreviated as HBC-) and other coupling residues other than the compound The coupling component (denoted as Cp-) (denoted as HBOCp) is diazotized using a compound having an amine group as a diazo component (denoted as Ar-NH2) to form an azo/coupling. Ar-N=N-HBC-Cp-N=N-Ar] The black azo pigment of the configuration shown. Examples of the black polyazo pigment having the structure (4) represented by [Ar-N=N-HBC-Cp-N=N-Ar], as described below, may be exemplified for the passage of a phenyl group or a phenyl group. And the 2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxylic acid decylamine residue is bonded to the 2-hydroxy-3-naphthoquinone aryl hydrazine which is other than the compound. The HBC-Cp of the coupling of the amine residue is a structural example in the case where aniline having one amine group is used as a diazo component and diazotization is carried out. 100149099 20 201241098

The above black azo pigment of the present invention can be easily obtained by a method for producing a black azo pigment of the present invention having the following steps: a synthetic step of a polyazo pigment having the above-exemplified structure; and, if necessary, The step of adjusting the particle diameter of the pigment particles to be fined. Hereinafter, a method for producing the black azo pigment of the present invention will be described. The method for synthesizing the black polyazo pigment constituting the method for producing the black azo pigment of the present invention is selected by the following methods (1) to (4). (1) A method for diazotizing a compound having two or more amine groups (representative formula: H2N to Ar-NH2) to form 2-hydroxy-11H-benzo[a]- A method for synthesizing azo/coupling of carbazolyl-3-carboxylic acid aryl decylamine (abbreviated as HBC). The black polybutene 100149099 21 201241098 nitrogen pigment obtained by the synthesis method of (1) is a structure having the structure shown by [HBC-N=N-Ar-N=N-HBC] described previously. (2) The method of synthesizing a polyazo pigment having the following structure: the structure is formed by diazotizing a compound having two or more amine groups (representative formula: H^-Ar-NH2) a diazonium salt, a structure in which a hydroxybenzo[a]-carbazolylcarboxylic acid aryl decylamine (abbreviated as HBc) and other coupling components other than the compound (expressed as Cp) are subjected to a ligand/coupling; a compound of two or more amine groups (representative formula: H2N-Ar-NH2) is subjected to diazotization to form a diazonium salt, and an even component (Cp) of the same molar or less is subjected to azo/coupling, as needed. Two or more coupling components (Cp) are obtained by subjecting the coupled poly-JU materials to time separation and removal, and then subjecting the above-mentioned coupling component (HBC) to azo/coupling in the uncoupled diazonium salt group. The black polyazo pigment obtained by the synthesis method of (2) has a structure represented by [HBC-N=N-Ar-N=N-Cp]. The method of (3) is the method of the following (34) 4 (3-2). The black polyazo pigment obtained by the synthesis methods of (3_丨) and (3-2) has the previously described [Ar-N=N-HBC-HBC-N=N-Ar] The structure of the display. (3-1) an even synthesis component (expressed as HBC-) having two or more 2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxylic acid decylamine residues (abbreviated as HBC-) in the molecule. HBC) A method for synthesizing an azo/coupling of a diazo component formed by diazotizing a compound having one amine group (Ar-NH2). (3-2) diazotizing a compound having a 100149099 22 201241098 amine group (denoted as Ar-NH 2 ) for 2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxylic acid The formed diazonium salt is subjected to azo/coupling, followed by condensation of a carboxylic acid of an azo dye with an arylpolyamine to prepare a polycarboxylate. The method of (4) is the method of the following (44) or (4-2). The black polyazo pigment obtained by the synthesis methods of (4-1) and (42) has the previously described [Ar'N==N-HBC-Cp-N=N-Ar] The structure of the display. (4·=· 1) for the ^ ^ ~ molecule having 2-hydroxy-11Η-benzo[a]-oxazolyl carboxyl residue amine residue (abbreviated as HBC-) and other couplings other than the compound The coupling group of the base (not Cp_) (expressed as HBC_Cp), the compound of the amine group (not shown as Ar-NH2) is diazotized to form a new _ synthesis of the oxime (10) combination (4- 2) For the component of the acid-lowering miH_benzo[a] succinic acid and other couplings, the diazonium is used to make the compound having an amine group (expressed as Ar_NH2) Nitrogen/coupling, followed by condensation of the dyed amine of the obtained amine with aryl polyamine to form Polylin's "oT", which is described in the above-mentioned various synthetic methods. (Α) Specific examples are given for the pigeons. (8) As the coupling component (HBc), for example, 2_hydroxy·UH·stupyl-3-indole, ^λ8·Α-yl- 11Η-stupid [a]-carbazolyl-3-naphthyl anthracene Amines and other specialties are called j>, . The substituent of the derivative is, for example, an alkane (carbon number 〇~1〇) 100149099 23 201241098 group, an alkoxy group (carbon number 1 to 10) group, a trifluoromethyl group, a ii group, an alkyloxycarbonyl group, a cyclic imine dioxy group, an alkylsulfonyl group, an aminocarbonyl group, a benzoguanamine group, an alkylaminocarbonyl group, an anilinocarbonyl group, a cyclic ureido group, a carboxyoxy group, an alkylimino group, etc. Or an even component of the above. Specific examples thereof include 2-hydroxy-11H-benzo[a]-carbazolyl-3-aniline, 2-hydroxy-11H-benzo[a]-oxazolyl-3-carboxy-p-fennel Annisidide, 2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxy-(2-indolyl)-p-anisidine, 2-hydroxy-11H-benzo[a]-carbazole Alkyl-3-carboxy-N-benzimidazolone-5-decylamine, 2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxy-naphthyldecylamine, and the like. (b) as a coupling component (HBC-HBC), for example, phenyl-bis(2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxylic acid decylamine), extended biphenyl-double (2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxylic acid decylamine), stilbene-bis(2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxylate The acid amide and the derivative y 乍 are substituents of the derivative, for example, a known substituent is introduced into the aryl group, for example, a calcination (carbon number 1 to 10) group, an alkoxy group (carbon number 1 to 10) An even component of one or more of a group, a trifluoromethyl group, a halogen group, or the like. Specifically, for example, phenyl-(M-)bis(2.hydroxy-11H-benzo[a]-myristyl-3-carboxylic acid decylamine), 2-gas-extended phenyl-(1) , 4-) bis(2-hydroxy-11H-benzo[a]-flavoryl-3-tagamic acid decylamine), 2,5-dichloro-phenylene-(1,4-)bis (2) -hydroxy-11H-benzo[a]-carbazolyl-3-carboxylic acid decylamine), 2·methyl_phenylene bis(2-carbyl-11H-benzo[a]-carbazolyl] 3_carboxylic acid decylamine), extended biphenyl _ (4,4, _) bis (2-carbyl-11H-benzo[a]-isoxazolyl-3-carboxylic acid decylamine), 3,3 ,_二气_伸联100149099 24 201241098 Phenyl-(4,4^) bis(2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxylic acid decylamine), anthranyl-( 1,5 =) bis(2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxylic acid decylamine) and the like. (c) Examples of the above-mentioned coupling component (Cp) include 2-hydroxy-3-naphthoquinone aryl decylamine, 2-hydroxy-6-naphthoquinone aryl decylamine, and 2-hydroxy-3-hydrazine. Carboxylic acid decylamine, 2-hydroxy-3-dibenzofurancarboxylic acid aryl decylamine, 2-hydroxy-1-oxazolylcarboxylic acid aryl decylamine, and the like, and derivatives thereof. For example, CI azo ink couples are divided into 2, 4, 6, 7, 8, 10, 11, 12, 14, 17, 18, 19, 20, 21, 22, 23, 24, 27, 28, 29, 31, 32,37,41,45,46,111,112,113,15,16,36,2-hydroxy-3-naphthoquinone-N-benzimidazolone-5-decylamine, 2-hydroxy-3-naphthoquinone Acid-N-phthalimide-4-chamarin or the like. (d) As the above-mentioned coupling component (HBC_Cp), a carboxylic acid which is an amino group of an HBC residue and a Cp residue bonded to a guanamine may, for example, be 2-hydroxy-3-naphthoic acid or 2-hydroxy-6- Naphthoic acid, 2-hydroxy-3-indolecarboxylic acid, 2-hydroxy-3-dibenzofurancarboxylic acid, 2-hydroxy-1-oxazolylcarboxylic acid, and the like. For example, phenyl (-1)-(2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxylic acid decylamine) (-4)_(2-hydroxy-3-naphthoate bismuth Amine), phenyl (-1 > (2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxylic acid decylamine) (-4)_(2-hydroxy-3-naphthoic acid Indoleamine, (2-mercapto-)phenyl (-1)-(2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxylic acid decylamine) (-4)-(2 -hydroxy-3-naphthoquinone decylamine), extended biphenyl (-4)-(2-carbyl-11H-benzopyrazine-3-decanoic acid amine) (-4')-(2 -Bisyl-3-naphthoquinone decylamine), etc. (B) Specific examples of the diazo component (a) A compound having two or more amine groups as the above diazo component (representing 100149099 25 201241098 Formula: H2N- Ar-NH2) 'is, for example, an aniline naphthalene, a diamino fluorenone, a diamino-benzoic acid: a bis-biphenyl, a derivative of the second. As a substituent of the derivative, for example, === (4) The substituent such as 'burning (carbon number 1 to (9) group, calcining gas (carbon number 2) group = fluorenyl group, halogen group or the like, one or more diazonium components.) The base difluoride is specifically, for example, List 丨, ^ phenyl diamine, W two gas · phenyl diamine, 2 qi, = stupid T storm-1 4-secret cage | diamine, 2,5-dimercapto-indole phenylene diamine, 2, phenyl phenyl phenyl diamine, 4-phenylene phenyl diamine, 4 _ Methoxy group, aryl group, fluorenyl group, 3, phenylenediamine, 4·gas·1,2·extended base diamine, 4 5 —didecyl-1,2-phenylene Amine, "Schocchi·u•Phenyl diphenyl, ""^!L· _4,4'·benzidine, 2,2,,5,5'-four gas·4,4,_benzidine, 3,3, dimethyl A 4 4, benzidine, 3,3'-dimethoxyoxy-4,4,-benzidine; i,5-diaminopurine 3 ...... aminonaphthalene; 1,2-diaminofluorenone, anthracene, 5-diaminofluorenone; 3,4-diamine acetonone; 2,6-diaminopyridine, etc. (b) as the above diazo component a compound having an amine group (denoted as Ar-NH2), for example, an aniline, a naphthylamine, an amino fluorenone, a stupidoxy amide, a stupid imino aniline, etc., and derivatives thereof. The substitution is, for example, the introduction of a known substituent to the group, for example, a hexyl group (carbon number 1 to 1 fluorene) group, an alkoxy group (carbon number 1 to 10) group, a trifluoromethyl group, a halogen group, a nitrate Base, phenyl ether group, phenylimido group, stupid methyl hydrazide A diazonium component of one or more of a group, an anilinocarbonyl group, a cyclic ureido group, etc. Specifically, for example, CI azo 100149099 26 201241098 ink diazo component 5, 8, 9, 10, 32, 33 , 34 35, 36, 37, 4i, 42, 43, 47, etc. In the case of the method for producing a black azo pigment constituting the present invention, a step of adjusting the particle size of the pigment particles of the "fine pigment" and the field micro-fine pigment will be described. In the black money (4) of the present invention, the polyazo pigment obtained by the above-mentioned synthetic method is finely sized to about 1 Å by the method of any one of the following (1) or (7) when the particle diameter is coarse. Obtained from nm~2〇〇nm. That is, in order to increase the infrared transmittance of the coating using the polyazo pigment obtained by the above-mentioned synthetic method, it is necessary that the particle diameter of the dispersed pigment is small, in terms of frequency, average particle It is necessary to become about 10 nm to 2 〇 Onm. Therefore, when the black oleophobic pigment of the present invention is coarsened in the pigment synthesized by the above method, in order to adjust the average granule of the pigment to the desired particle diameter, f is required to carry out the following fine-graining of the known pigment. The steps to make a fine pigment. Specifically, 'the pigment finening step selected by the following method is carried out: (1) using ball milling, sanding, grinding machine (a her (6), horizontal continuous media disperser, kneading machine, continuous single-reduction a method of miniaturizing any of the pigment grinders or pigment dispersers selected from the group consisting of a machine, a continuous two-axis kneading machine, a three-parent and an open-roller continuous kneading machine, or (7) in a kneading machine, with a water-soluble salt Classes, water-soluble organic refrigerants required for mixing - solvent salt milling for mixing/grinding (four) vent salt supplements (4) method to prepare an average particle size of about 1 〇 to ~200 dirty. In addition, in further expectation, 'outside line In the case of the two transmittances, it is preferred to prepare an ultrafine pigment having an average particle diameter of about 100149099 27 201241098 10 nm to 50 nm. The particle size of the pigment can be adjusted according to the use used. It is controlled with respect to the salt amount ratio of the pigment and the kneading time. In the use of an infrared color ray-receiving sheet requiring high transmittance, the pigment particles are preferably smaller, for example, preferably 1 〇 nm. Minor of ~5〇nm The pigment particles, even the dispersed state of the ultra-fine pigment particles of lOnm~3〇nmi, and in some cases, it is desired to dissolve the molecular dispersion in a dispersion carrier such as a plastic medium. On the other hand, the shading property of visible light is required. In terms of the BM-like use of CF, it is preferably about 5 〇 nm to 1 〇〇 nm which is slightly larger than the penetrating use. Further, in terms of applications requiring infrared reflectivity, it is preferred that the substrate has a reflection f. In addition, larger pigment particles (l〇〇nm~2〇〇nm) can also be used. In the above-mentioned solvent salt milling method, the pigment is more grated than the desired pigment particle size. Adding water-soluble inorganic _ several times (specifically, 3 to 2 times) of the pigment, and further adding a water-soluble organic solvent having a viscosity such as ethylene glycol, diethylene glycol or polyethylene glycol And the mixed (four) crushing. As the water-soluble inorganic salt used in the grinding auxiliary material, chlorinated steel or sulphuric vanname or the like may be used. After grinding, it is added to dilute sulfuric acid, water, etc. to make the mill The crushing aid is cold-dissolved and subjected to hydrazine and water washing to obtain a pigment. Filtration, preparation (pressing cake). The pressed cake is dispersed in the wet disperser as it is, or processed to oily colorant by flash steaming, or after drying by hot air. The pulverizer is pulverized into powder (4), and even 100149099 28 201241098 can be sterilized by various chrominants in the above-mentioned _ readings and scales. Dispersion-treated pigments or edging pigments. The enamel resin treatment is also used in the liquid pigment dispersion when the black azo pigment of the present invention is used as a coloring agent, and is also black (4), especially in sexual or cationic properties. As the material (four) material ion method, it can be based on: in the synthesis of the above pigments, the secret ion is divided into or evenly synthesized, and the Wei coupled method is used to guide the mosquito; the other is a pigment derivative having an ionic group. It is a pigment derivative which is obtained by a known method such as microparticle formation or preparation of pigment dispersion (4) to a mosquito, and can be used in addition to black, and also includes yellow, blue, red, and the like. (Iv) biological hue adjustment. Here, the spectral transmittance of the coating film is numerically different depending on the black pigment component or the coating film thickness contained in the coating film, but in the relationship with the wavelength, it can be confirmed in the absorption wavelength. Both show a tendency to absorb, while in the wavelength of penetration, a tendency to penetrate is exhibited. In Table 2 and Table 2, the black disazo pigment ("black pigment-1") obtained by the following production example of the present invention is shown, and contains the black pigment prepared according to the following examples. The light transmittance (%) of the visible light region and the infrared region of the coated film of 1. The results are as shown in Table 1. Regarding the coating film containing black pigment-1, the transmittance was 100149099 29 201241098 0% in the full wavelength region spanning 400 to 750 nm of visible light, and it was confirmed that it was not displayed in the visible light region. Penetration. On the other hand, as shown in Table 2, in the infrared region of 900 nm, there is a penetration of 34%, and on the longer wavelength side, the transmittance is slowly increased, and in addition, it is expected to be at a higher wavelength. It will also show high penetration. 100149099 30 201241098 Table 1: Spectral transmittance of visible light region of black pigment-1 Wavelength transmittance Wavelength transmittance Wavelength transmittance (nm) (%) (nm) (%) (nm) (%) 400 0 550 0 700 。 0 0 0 0 0 0 0 0 0 0 0 0 0 Nm) (%) (nm) (%) 800 0 1050 48 1300 64 850 19 1100 51 1350 67 900 34 1150 55 1400 69 950 40 1200 58 1450 72 1000 44 1250 61 1500 74 Also, regarding the black couple containing the present invention The electrical insulating properties of the coating film of the nitrogen pigment were similarly as shown in the following Example 1, and the volume specific resistance of the coating film containing the black pigment-1 was 1 〇 14 Ω · cm, which confirmed that good electrical insulation was exhibited. Sex. The black pigment-1 which is a black azo pigment of the present invention is an optical device which has light which penetrates the infrared ray region and completely shields the light in the visible light region, and is therefore found in an electronic device using the above infrared ray. The infrared filter is used or used as a BM for CF. For example, when the black azo pigment of the present invention is applied to a BM of CF, the light in the visible light region of the backlight can be completely shielded and exhibits superior electrical insulation. The black azo pigment of the present invention is a colored composition which can be made into a dark colored colored color, an achromatic dark color or a black colored color when used, and can be formed according to the purpose of coloring, use, use method, etc. Black azo pigment 100149099 31 201241098 The pigment component of the material is used in various forms including a liquid coloring composition in a liquid dispersion medium or a solid coloring stage composition contained in a solid dispersion medium. The black azo 1 coating of the present invention can be used alone as a black azo pigment of the component _ or a color pigment, a white pigment, other black (four) and «_ which can be used as one of a plurality of pigment components in combination with a target color. One or two or more types may be selected and may be used in combination with the above. In order to correct the color of the black even material, the blending ratio of the colored pigment, the white pigment, the other black pigment or the extender pigment of the black pigment-reducing pigment of the present invention is not particularly limited, and the use of the computer and the color of the money (four) is better. The method to determine is also a preferred form. As the pigment to be used in combination with the black azo pigment of the present invention, a known pigment can be used without particular limitation. For example, an onion ketone pigment, a shirt = pigment = diketone scale pigment, a smock pigment, a fine pigment: a material, a phthalocyanine pigment, a linden pigment, an iso zinc azo pigment, or a second can be used.呀 pigments, 嗤__ pigments, azo pigments, high molecular weight (four) Γ gas pigments, soluble aniline 11 series pigments, azo f azo black pigments, this month's female black pigments and other organic pigment materials, iron oxide Pigment, titanium oxide and: black pigment and composite oxide type pigments, pigments and other inorganic pigments selected from at least one == above pigments of the compound, mixed crystal pigment. 100149099 乍 is an organic pigment', for example, CI. Pigment Yellow having a yellow pigment (Jane 201241098 is ΡΥ> 74, 83, 93, 94, 95, 97, 109, 110, 120, 128, 138, 139, 147, 150, 151, 154, 155, 166, 175, 180, 181, 185, 191, etc. CI pigment orange of orange pigment (abbreviated as Ρ〇)-61,64,71,73, etc., CI pigment red of red pigment (abbreviated as PR)-4,5,23,48 : 2,48 : 4, 57 : 1,112,1.22,144,146,147, 150J66,170,177,184,185,202,207,214,220,221,242,254,255, 264,272, etc. Also, a blue pigment of CI Pigment Blue (abbreviated as PB)-15: 1,15:2, 15: 3,15 : 4,15 : 5,15 : 6,16,17 : 1,60,80, Ming phthalocyanine blue, green pigment pigment green (abbreviated as PG)-7,36,58, poly (13-16 ) bromophthalocyanine, etc., purple pigment CI. Pigment Violet (abbreviated as PV)-19, PV-23, PV-37, etc., black pigment aniline black pigment, carbon black pigment, titanium oxide black pigment, etc., especially For the BM of CF, as a user of the black azo pigment to be blended with the present invention, it is preferred to carry out surface treatment and to improve the carbon black pigment and titanium oxide black. When the black azo pigment of the present invention is used in combination with an infrared reflective pigment such as a white pigment, the method proposed in Japanese Patent No. 4097926 or Japanese Patent Laid-Open Publication No. Hei No. 2005-330466 can be used. It is also preferable to apply a method in which the infrared ray-soluble black azo pigment of the present invention substantially covers the periphery of an infrared reflective pigment such as a white pigment to improve the reflection efficiency of infrared rays. The black azo containing the present invention is also preferred. The liquid coloring composition formed by the pigment is mainly used as a coloring agent for coating, impregnating, drawing, printing, etc. on the surface of the article, and can be used for coatings, coating agents, plastic coloring, fiber coloring, and the like. For various applications such as printing ink, stationery, image recording, and image display, the dispersion medium in which the black azo pigment of the present invention is dispersed may also contain a reactive film as a film forming material (or a coating film forming material). Reactive or non-reactive polymer, oligomer with reactive groups or non-reactive Oligomer and a monomer having a reactive group or the non-reactive monomer having a reactive group or the like of the selected at least one kind, and may also for the liquid itself or may further contain a solvent and / or by water. Further, when the liquid coloring composition is prepared, if a high-concentration pigment processing product in which the pigment used is finely dispersed in the dispersion medium in advance is prepared in advance, the processed product can be used to easily produce the coloring agent. The liquid high agronomic pigment dispersion is called "base color" or "base ink". Further, the solid coloring composition comprising the black azo pigment of the present invention is mainly used as a coloring agent for coloring inside a plastic or synthetic fiber, for example, a host powder depending on the concentration of the pigment in the cerium concentration, and the main body is resistant. It is used in the shape of a known product such as colored particles which are colored as a whole. As the solid dispersion medium, at least one selected from the group consisting of a thermoplastic resin, a thermosetting resin, a wax, a fatty acid decylamine, and a fatty acid metal fertilizer can be used. When the article is colored by using the above coloring agent, appropriate coloring can be performed according to the optical purpose of the visible light region and the infrared region. When performing coloring to absorb the visible light region and penetrate the infrared ray region, the substrate of the article is made transparent, and the coloring composition is used, by painting and coating 100149099 34 201241098

Cloth, dyeing, printing 'notes, drawings, inkjet printing, electronic photo printing I electrostatic printing or photolithography printing, etc. for the transparent substrate to be two or four colors, or by kneading or impregnating the transparent substrate Coloring the composition and arranging ^ Set the internal coloring. In this case, by using the black azo pigment of the present invention, the obtained article is one which exhibits the following superior optical characteristics. That is, the black azo pigment of the present invention can exhibit high absorbance, visible light shading, high wavelength of about 900 nm to 150 〇 nm or more, particularly in the wavelength range of 400 to 750 nm in the visible light region. The infrared port shows a highly penetrating color. When the coloring of the visible light-receiving region and the reflection of the infrared ray region is performed, it is achieved by using a material having light reflectivity or a predetermined light-reflective substrate on which the coloring composition of the present invention is applied. The ocean of this σ is described later. At this time, the coloring method is performed by a known method, for example, painting, coating, coloring of a stock solution, dyeing, printing, drawing, drawing, inkjet printing, electronic photo printing, or xerographic printing. It exhibits high absorbency in the visible light region and high reflectivity in the near-infrared region. —, shows The spectral reflectance of the above black pigment-1 was measured, and the results are shown in Table 3. The test sample of Test I was coated on a white color spread paper and coated with coated paper (hereinafter referred to as black stretch paper). 100149099 35 201241098 Table 3: Spectral reflectance of black pigmented paper of black pigment-1 Wavelength reflectance Wavelength reflectance Wavelength reflectance (nm) (%) (nm) (%) (nm) (%) 400 6 800 12 1200 80 450 5 850 47 1250 82 500 5 900 70 1300 82 .550 5 950 76 1350 80 600 5 1000 79 1400 74 650 5 1050 80 1450 71 700 5 1100 82 1500 69 750 6 1150 81 — — as shown in Table 3 The coating film containing the black pigment-1 absorbs from the visible light region to about 750 nm and exhibits only a reflectance of 5% before and after. From about 800 nm to 900 nm, the reflectance sharply rises, and on the longer wavelength side. In the infrared region, the reflectance is maintained at about 80%, and it is expected that the infrared region of the higher wavelength above it also exhibits high reflectance. This means that the light that has penetrated the black coating film is reflected on the white paper of the substrate. By using a highly reflective substrate or a reflective material such as a white pigment or an extender pigment, it is not only from the surface of the black pigment but also through the light. Re-reflection is performed to exhibit high efficiency and high reflectance. The resin binder which acts as a coating film forming material (film forming material) used in the present invention (referred to as "vehicle" or "varnish" depending on the use) can be suitably used without reaction. A non-reactive, normally-temperature-drying type or a reactive type of a resin adhesive and a photosensitive resin binder. Examples of the resin adhesive for a room temperature drying type or a drying type are, for example, dyeing agents, paints, coating agents, or image recording materials such as printing inks, stationery, inkjet printing, electrophotographic printing, and electrostatic printing. Use 100149099 36 201241098 Resin adhesive, etc. In addition, examples of the photosensitive resin adhesive include photosensitive resin adhesives used in various coating materials, coating agents, printing inks, inkjet inks, and photolithography technologies, such as rabbit external curability or electron beam curing. Agent. Specific examples of the resin binder of the room temperature drying type or the drying type which can be used in the present invention include, for example, a synthetic rubber resin, an acrylic resin, a styrene (co)polymer, and polyvinyl butyral. a vinyl resin such as a resin; a polyester resin, an amine resin modified polyester resin, a polyamino phthalate resin, an acrylic polyol ethyl phthalate resin, a soluble polyamine resin; Soluble polyimide resin, soluble polyamidoximine resin, soluble polyester quinone resin, alkyd resin, amino alkyd resin, epoxy resin, chlorinated rubber resin, polyoxyl Resin, fluororesin, cellulose acetate resin, nitrocellulose resin, hydroxyethyl cellulose, water-soluble salt of stupid ethylene-maleate copolymer, (mercapto) acrylate a water-soluble salt of a (co)polymer, a water-soluble amino alkyd resin, a water-soluble amine-based polyester resin, and a water-soluble polyamine resin, and these may be used singly or in combination of two or more. . The reactive group of the reactive film forming material may, for example, be a hydroxy group, an alkyl hydroxy group, an isocyanate group, a masking isocyanate group or an epoxy group. Further, an oligomer or a monomer may be used depending on the application, and a crosslinking agent such as a hydroxydecyl melamine-based or isocyanate-based or epoxy-based crosslinking agent may be used in combination. Specific examples of the energy ray-curable coating film forming material such as the ultraviolet curable resin-based or the electron beam-hardening resin used in the present invention include a photosensitive cyclized rubber-based resin and photosensitivity. a phenol resin, a photosensitive polyacrylate resin, a photosensitive polyamine resin, a photosensitive polyimide resin, and the like; and an unsaturated polyester resin, a polyester acrylate resin, or a polyepoxy acrylic acid. A binder such as an ester resin, a polyurethane acrylate resin, a polyether acrylate resin, or a polyol acrylate resin, or a binder to which a monomer as a reactive diluent is further added. Examples of the plastic which is colored by the coloring agent for plastics of the coloring composition of the present invention include polyethylene, ethylene copolymer, polyolefin such as propylene, polystyrene, and ABS which are conventionally known thermoplastic plastics. , AS, styrene copolymer, vaporized ethylene resin, methacrylic resin, polycarbonate, polyamine, polyacetal, thermoplastic polymerization 'Cellulose plastic, epoxy phenylene resin, fluororesin, thermoplastic elastomer, etc., or thermosetting plastic unsaturated polyester resin, epoxy resin, polyoxyl resin, polyurethane resin A melamine resin, a phenol resin, etc. The content of the black azo pigment of the benzene invention contained in the black colorant belonging to the coloring composition of the present invention varies depending on the use or purpose of use, and cannot be generalized. Coatings, coating agents, dyes, printing inks, toners for printers, inks for ink jets are equivalent to the use of coloring on the surface. Because the film thickness is thin, the content of the black pigment contained in the coloring agent is It is about 3% to 80%, preferably about 5% to 6% by weight. Especially in the case of being used as a light-shielding black material of CF BM, the film thickness is particularly 100149099 38 201241098, so the pigment is dispersed, _ The pigment concentration suitable for the boundary of the color film is thin, and requires a complete light-shielding property, and the viscosity of the coating is preferably about 30% to 6 〇〇/. Or, in the case where the raw material of the woven fabric is colored internally, it is also about 0.05% to 20%, preferably about 1% to about 1%, depending on the thick product of the colored product. When the coloring composition for image recording containing the black azo pigment of the present invention is used as a coloring composition for forming a CF, the coloring composition is directly or transferred or attached to the CF substrate. Plastic film, and according to the method of photolithography, laser/melting (10) lati〇n), ink printing, printing, transfer, attaching, etc. Formed as a method. As a film thickness of BM '4 〇 5 handsome ~ 3 ah, usually the optical density (OD) value is 2.0 or more, preferably 3 〇 or more. When having a spacer function, 'thickening the ship itself In the case of laminating pixels or laminating a colorless resin film, it is preferably a kiss claw. Further, on the CG substrate on which the BM is formed, a color pixel can be formed by a known pixel formation method using a known (four) color image (four) coloring agent. In the present invention, as an article having an advantage with respect to a CF substrate or an organic EL light-emitting substrate, the following may be used. That is, a CF substrate or an organic EL light-emitting group 100149099 201241098 plate in which a BM that absorbs a wavelength range of a visible light region is formed, and in particular, the BM is substantially more electrically insulating, and the CF substrate formed by the BM and the electrode weight is the most. Or an organic EL light-emitting substrate, and a color display panel comprising the same. Similarly, a CF substrate on which BM and colored pixels are formed, a liquid crystal color display device mounted thereon, or an organic EL color display device equipped with the organic EL light-emitting substrate may be mentioned. Further, as an article relating to a solar power generation system, it is possible to suppress the temperature rise due to sunlight, and to form a coloring composition of the black azo pigment of the present invention on a light-reflective sheet such as a reflective underlayer. a plurality of layers forming a back cover of a black or dark colored infrared penetrating layer or a solar power module using the same. [Examples] Next, examples are given to further illustrate the present invention. In addition, "趵" or "%" is a quality standard without any particular limitation. [Manufacturing Example 1] (Manufacturing of "Black Pigment-1") (1) Synthesis of black disazo pigments Concentrated hydrochloric acid is added in a usual manner i 3,3,_:foxy-4,4,-benzidine 2.44 g (0.Gl mole) was used as a hydrochloride, and an excess aqueous solution of sodium nitrite was added to carry out diazotization. Next, a hydroxyacid is added thereto to prepare a 3,3'-didecyloxy-diphenylene (4,4,-) tetragas salt. The boron compound double salt (heavy gas salt) is prepared. In addition, it will be used as an even-synthesis base of 2 rad·UH•benzo(5)吟. The base-3-carboxy-p-aniline 7.65 g (〇.〇2 mol) was dissolved in 25 Gg of a sterol which had been dissolved with sodium oxynitride, for example. The previously prepared tetra-salt salt 100149099 40 201241098 fluorinated demineralized salt solution was kept below 15 ° C, and the above-prepared couple of the synthase was slowly added thereto. Then, the pH was adjusted to 6.5 to 7.0 with sodium acetate and stirred for 1 hour, and then stirred at 25 ° C for 2 hours, and further heated to 40 ° C for 3 hours to terminate the coupling reaction. After the resulting pigment was filtered, the filtrate was washed with methanol, followed by washing with water, followed by drying to obtain a crude pigment of black azo pigment. The yield of the spot color azo pigment obtained was 9.78 g. (2) Preparation of finely divided black fine particle pigment 100 parts of coarse granule pigment of black azo pigment obtained by the synthesis reaction of the above (1), 500 parts of sodium chloride powder and 5 parts of diethylene glycol The kneading machine was added to a kneading machine having a pressure cap, and the coarse particle pigment and the vaporized sodium powder in the kneader were uniformly wetted until they were uniformly wetted. Next, the pressure cooker was turned off, and the contents were pressed in at a pressure of 6 kg/cm2, and kneaded and ground. Specifically, the temperature was managed so that the contents were 92 to 98 〇c, and the kneading/grinding treatment was performed for 2 hours. The obtained ground material is heated to 8 (3 times of warm water of TC; after hour of sandaling treatment, • after the mashing, the obtained mash is washed by water to remove chlorination The pressed cake of the finely divided black azo pigment was obtained by diluting with diethyl alcohol. The particle diameter of the pigment obtained above was measured by the following method. A transmission electron micrograph of the obtained black pigment was photographed ( 60,000 times), the image analysis size distribution software Mac_View (manufactured by M〇untech Co., Ltd.) was used to measure the particle size of the knife cloth. The result was an average particle size of 50 nm. In addition, other manufacturing 100149099 41 201241098 was the same as above. The method measures the average particle diameter of the pigment. The same is true. Next, after the dried cake obtained above is dried, it is pulverized to obtain a ruthenium, 33, -mp, +, , - methoxy group. (4,4,-) finely divided powder pigment of a black pigment of a structure of bis(azo(-1)-2-hydroxyl 11Hbenzo[a] "carbinyl-p-phenyleneamine". [Production Example 2] (Manufacture of "Black Pigment-2") In the same manner as in Production Example 1 (1), 3, 3, _ Dimethoxy- 4,4,-benzidine 2.44 g (0.01 mol) is diazotized. Then, it is combined with 2-base _uh•benzo[a]-oxazolyl-3··carboxyl group Ν-benzimidazolone-5-decylamine 8.17 g (0,02 mol) was coupled to obtain a crude pigment of black azo pigment. The yield of the obtained black azo pigment was 10.07 g. The finening treatment of the obtained crude pigment is carried out in the same manner as in Production Example 1 (2) except that the amount of sodium chloride used in the (2) of Production Example 1 is used in an amount of 8 times the amount of the pigment. Then, after the salt or the like is dissolved by acidic water, the obtained filtrate is washed with water to obtain a pressed cake of a black azo pigment. The obtained pigment has an average particle diameter of 25 nm. The pressed cake obtained above was dried and pulverized to obtain a fine powder pigment of a black pigment. Hereinafter, this material is referred to as "black pigment-2". [Production Example 3] ("Black Pigment-3" Manufactured in the same manner as in Production Example 1 (1), 2.53 g (0.01 mol) of 3,3'-di-gas-4,4'-benzidine was used. Diazotization. Then, it is combined with 2-hydroxy-11H-benzo[a]-carbazole 100149099 42 201241098 -3-carboxy"(2,··methyl)-p-aniline 7.93 § (0·02 Mo Coupling was carried out to obtain a crude pigment of black azo pigment. The yield of the obtained black azo pigment was 10.26 g. Next, the obtained fine pigment was subjected to miniaturization treatment. (2) The amount of sodium chloride used in the room was 10 times the amount of the pigment, and the finening treatment was carried out in accordance with Production Example 1 (2). Then, after the salt or the like is dissolved by the acid water, the filtration is carried out. The obtained filtrate is washed with water to obtain a pressed cake of a black azo pigment. The pigment obtained had an average particle diameter of 20 nm. The pressed cake obtained above was dried and pulverized to obtain a fine powder pigment of a black pigment. Hereinafter, this material is referred to as "black pigment-3". [Production Example 4] (Production of "Black Pigment-4") In the same manner as in Production Example 1 (1), 2,3'-dimethoxy-4,4'-benzidine 2.44 g (〇.〇l) Mohr) is diazotized. Then, it is coupled with 2_hydroxy_11Η^ and [a]-»carbazolyl_3_mercapto-(2,·indenyl)-p-aniline 7 93g (〇.〇2mole) to obtain A crude pigment of black azo pigment. The yield of the obtained black odor pigment was 9.94 g. Next, the finening treatment of the obtained crude pigment is performed. The finening treatment is carried out in accordance with (2) of the production example i, and the salt or the like is dissolved in acidic water and filtered, and the obtained filtrate is washed with water to obtain a pressed cake of a black azo pigment. The pigment obtained had an average particle diameter of 50 nm. The pressed cake obtained above was dried, and then pulverized, and 100149099 43 201241098, a fine powder pigment of a black pigment was obtained. Hereinafter, this material is referred to as "black pigment-4". [Production Example 5] (Production of "Black Pigment_5") In the same manner as in Production Example 1 (1), 3,3,·dichloro-4,4,-benzidine 2 53 g (〇〇1 mol) was used. Diazotize. Then, it was coupled with 7.56 g of 2 hydroxy_UH_benzo[a]-oxazolyl-3-carboxy-p-aniline to obtain a crude pigment of a black azo pigment. The yield of the obtained black azo pigment was 9 86 g. Next, the finening treatment of the obtained crude pigment is performed. In the same manner as in Production Example 1 (2), the finening treatment was carried out in the same manner as in Production Example 1 (2) except that the amount of the gasified sodium used in the (2) of the production example 1 was used in the same manner as in the production of the pigment. After the dissolution, the filtration was carried out, and the obtained filtrate was washed with water to obtain a pressed cake of a black azo pigment. The pigment obtained had an average particle diameter of 85 nm. The pressed cake obtained above was dried and then pulverized to obtain a fine powder pigment of a black pigment. Hereinafter, this material is referred to as "black pigment_5". [Production Example 6] (Production of "Black Pigment·6") In the same manner as in Production Example 1 (1), 2.34 g (0.01 mol) of 3,3,-dimethoxy_4,4,-phenylideneamine was used. ) to be diazotized. Then, it is combined with 2_hydroxy·u^benzo[a]-saltyl-3·carboxy-(2'-methyl)-p-aniline 3.96g (0.〇i Mo) and 5'-chloro 3-Hydroxy-2',3'-dimethoxy-naphthanilide anilide 3.58 (0.01 mol) was coupled to obtain a crude pigment of black azo pigment. The yield of the obtained black azo pigment was 9.59 g. Next, the crude pigment of the black azo pigment 100149099 44 201241098 obtained as described above was pulverized by a dry pulverizer to carry out pigmentation to obtain a fine powder pigment of a black pigment. The pigment obtained had an average particle diameter of 11 Onm. Hereinafter, this material is referred to as "black pigment j". [Production Example 7] (Production of "Black Pigment_7") (1) Production of Black Pigment Derivative-1 1.73 g (0.01 mol) of sulfamic acid was diazotized. Then, it was coupled with 2-lightyl-11Hq benzo[ap-carazolyl-3-carboxy-p-aniline 3.82 g (〇.〇i Mo). Next, after the obtained product was filtered, it was washed with water to obtain a kneaded cake having a black pigment derivative of a sulfonic acid group. Hereinafter, this product is referred to as "pressed cake of black pigment derivative-1". The yield of the pressed cake obtained was 5.49 g in terms of solid content. Further, the pressed cake is dried and pulverized to obtain a fine powder pigment of a phthalic acid derivative having a sulfonic acid group. Hereinafter, this material is referred to as "black pigment derivative-1". (2) (Manufacture of "black pigment_7") The pressed cake of the black pigment-1 obtained in the position (1) of the manufacturing example 1 and the black pigment derivative-1 obtained by the above (1) The pressed cake is formulated in such a manner that the solid content ratio of the pigment is 10:1, and it is sufficiently mixed to make it uniform and then 'the above mixture is dried to obtain a crude pigment containing a black pigment of the pigment. Next, in the case of the fineness treatment of the pigment in the production example 1, (2), the acid solution is used to carry out the 'gluten solution of the salt or the like, and the filtrate is filtered, and the obtained filtrate is washed with water. A pressed cake of black enamel pigment was obtained. The average particle diameter of the obtained pigment was 100149099 45 201241098 50 nm. The pressed cake is dried and pulverized to obtain a finely divided powder of a black pigment containing an anionic pigment derivative. Hereinafter, this material is referred to as "black pigment-7". [Production Example 8] (Production of "Black Pigment-8") A cationic pigment derivative was synthesized by the method described in Japanese Patent No. 3268748. Specifically, first, a ratio of 丨-amino fluorenone, bis(N,^^dimethylaminopropyl)amine, and cyanuric chloride is 2:·1 : 丨, Conversion to 2,4_bis(decyiamino)-6, bis(indene, dimethylaminopropyl)amino group _s_ 彡 as a cationic pigment derivative. The pressed cake of the obtained cationic pigment derivative and the pressed cake of the black crucible 1 obtained in the production example 1) were blended in a manner of 85:15. Then, after sufficiently mixing these to be uniform, drying was carried out to obtain a crude pigment containing a black pigment of a cationic pigment derivative. Then, the obtained crude pigment was subjected to a fine treatment according to the method of (2) in Production Example 1, and then the salt or the like was dissolved with water, filtered, and the filtrate was washed with water to obtain a black azo pigment. Pie. The pigment obtained had an average particle diameter of 50 nm. After the obtained pressed cake is dried, it is pulverized to obtain a finely divided powder pigment containing a black pigment of a cationic yellow pigment derivative. Hereinafter, this material is referred to as "black pigment_8". [Production Example 9] (Production of "Black Pigment_9") In the same manner as in Production Example 1 (1), '3,3'-dimethoxy-4,4,-phenylidamine 1.95 g (0.008 mol) After the diazotization is carried out, add rotten hydrofluoric acid to prepare 100149099 46 201241098 tetranitride salt • fluorinated butterfly double salt (diazonium salt). In addition, 0.69 g (0.004 mol) of the reductive acid was diazotized. The two kinds of diazo liquids are simultaneously coupled with the base-11H-benzo[a]-carbazolyl-3-carboxyl-p-aniline 7.65 g (0.02 mol), while the above two kinds of diazo liquids are used. The droplets are adjusted in such a manner that they are finished at the same time, and are coupled. Thereafter, filtration and washing with water were carried out to obtain a pressed cake of a black azo pigment. The obtained pressed cake was dried to obtain a black pigment (crude pigment) containing a black pigment derivative having a sulfonic acid group. The yield of the obtained black pigment was 9.97 g, and then, the finening treatment of the obtained crude pigment was carried out. Specifically, after the finening treatment by the method of the manufacturing method, the salt or the like is dissolved with acidic water, and the mixture is filtered, and the obtained mash is washed with water to obtain a black azo pigment. The obtained cake has an average particle diameter of 5 Gnm. After the pressed cake is dried, it is pulverized to obtain a fine pigment pigment of a black pigment. Hereinafter, this material is referred to as "black pigment _9". [Production Example 10] (Production of "Black Pigment_1〇") In the same manner as in Production Example 1 (1), 2-methoxy-phenylamine-armamamine 4. 8琢02 mol was used. Diazotization, so that the phenyl-UH- stupid and attached.格三依_6 27 咖料) into (four) combined 'to get the crude pigment of black azo pigment. The yield was ι〇 3. Then, the powder was pulverized by a dry pulverizer to obtain a fine powder pigment i of black. Hereinafter, this product was referred to as "black pigment_1 ()". The pigment obtained was 80 nm in diameter. And 100149099 47 201241098 [Example 1] (Evaluation of optical properties of coating film containing the black pigment of Production Example i) (1) Modulation of black-coated PET film using black pigment-1 In order to observe the manufacturing example i The optical properties of the obtained black pigment were adjusted to prepare a black coating liquid. As the wax to be used, a solvent-based acrylic resin t 50% diterpene butyol mixed solvent solution (acid value: 1 OmgKOH/g) and butylated hydroxydecyl melamine resin are used as 5% by weight. _ Butanol mixed solvent solution is prepared by blending with 8G: 2G (hereinafter, this is called "躐"). As the diluent solvent, a xylene-butanol mixed solvent (4:1) (hereinafter referred to as "diluted solvent") is used. Three parts of black pigment-1, 24 parts of wax, 6 parts of a diluent solvent, and 48 parts of glass beads as a dispersion medium were added to a dispersion container, and dispersion was carried out for 3 hours using a paint mixer. Thereafter, 36 parts of wax was further added and dispersed for 1 minute, and then taken out to obtain a coating liquid. The ratio of the pigment component to the resin solid content in the coating liquid was 1:10. The black coating liquid obtained as described above was applied onto a polyethylene terephthalate (PET) film using a bar coater, dried, and then cured at 130 C to obtain a black coated PET film. The average dry film thickness of the formed black coating film was 34 nm. (2) Measurement of the transmittance of the visible light region and the near-infrared region. The black-coated PET film obtained by the above (1) is measured by the Hitachi spectrophotometer (U-4100 model manufactured by Hitachi, Ltd.). The penetration rate of the infrared part. In Tables 4 and 5, the measurement results of the respective regions are shown. 100149099 48 201241098 Table 4: Spectral transmittance of visible light region of black coated film using black pigment-1 Wavelength transmittance Wavelength transmittance Wavelength transmittance (nm) (%) (nm) (%) (nm ) (%) 400 0 575 0 725 0 425 0 600 0 750 0 450 0 625 0 775 0 500 0 650 0 800 0 525 0 675 0 — — 550 0 700 0 — — 100149099 49 201241098 Table 5: Using black pigment q Spectral transmittance of the infrared region of the black coated film. Wavelength transmittance Wavelength transmittance Wavelength transmittance (nm) (%) (nm) (%) (nm) (%) 800 0 1050 48 1300 64 850 19 1100 51 1350 67 900 34 1150 55 1400 69 950 40 1200 58 1450 72 1000 44 1250 61 1500 74 As shown in the measurement results of the light transmittance of Table 4 and Table 5, the coating system containing black pigment-1 The spectral transmittance of 全% across the entire wavelength range of 400 to 750 nm across the visible light region was confirmed to be almost impossible to penetrate (see Table 4). On the other hand, in the infrared region, the transmittance at 900 nm is about 34%, and on the longer wavelength side, a phenomenon of slow rise has been confirmed (refer to Table 5). (3) Next, the volume resistivity was measured for the black coating film on the P E T film obtained as described above using a high resistivity meter Hiresta-UP [Mitsubishi Chemical Analysis Co., Ltd.]. The measurement results showed 1 〇 14 Ω · cm, and it was confirmed that the insulation was very high. [Example 2] (Evaluation of light reflection characteristics of the coating film containing the black pigment-1 of Production Example 1) (1) Modulation of black color development paper using black pigment-1 In order to observe the reflection property of black pigment-1 The black coating liquid prepared in the first place (1) of Example 1 was coated on a white color spread paper using a 6 mil applicator, and then dried and hardened to obtain a formed coating. Black coated color paper (hereinafter referred to as black color paper). The measured value of the dry film thickness of the black coating film formed on the black color display paper 100149099 50 201241098 is about 35 to 40 nm on the color development paper. (2) The reflectances of the visible light portion and the near-infrared portion of the black color-developed paper obtained in the above (1) were measured, and the measurement results are shown in Table 6. Table 6: Spectral Reflectance of Black Spread Paper Using Black Pigment-1 Wavelength Reflectance Wavelength Reflectance Wavelength Reflectance (nm) (%) (nm) (%) (nm) (%) 400 6 800 12 1200 80 450 5 850 47 1250 82 500 5 900 70 1300 82 550 5 950 76 1350 80 600 5 1000 79 1400 74 650 5 1050 80 1450 71 700 5 1100 82 1500 69 750 6 1150 81 — — Can be confirmed by the results shown in Table 6 : Regarding the black color paper made of black pigment-1, the reflectance is only 5 to 6% at around 750 nm, and the reflectance is sharply increased at 800 nm to 900 nm, and further near the longer wavelength side. In the infrared region, it is about 70% to 80%, or maintains the reflectance above it. As is apparent from the above description, the reflectance of the light of the black color-developing paper is reflected by the reflection from the surface of the pigment, and the light is transmitted through the white paper of the substrate, and the light is converted into light by the combined calculation, so that it becomes high. Therefore, since the black pigment has high light transmittance, it is shown that the substrate having high reflectivity can effectively reflect near infrared rays. Further, in the above Table 6, the reflectance is not 0% but 5% at about 750 nm, which is due to the relationship of the measuring device. [Example 3] 100149099 51 201241098 (1) In the same manner as in Example 1, black pigments 2 to 6 obtained in Production Examples 2 to 6 were used to form a black coating film, and visible light was measured in the same manner as in Example 1. The spectral transmittance of the area and the infrared area. The results are shown in Table 7 and Table 7: Spectral transmittance (%) of visible light region of black color paper using black pigment-2 to 6 using pigment black pigment-2 black pigment-3 black pigment-4 black pigment- 5 Black pigment-6 Average film thickness (μπι) 30 34 34 36 37 Wavelength (nm) Spectroscopic transmittance (%) 400 0 0 0 0 0 450 0 0 0 0 0 500 0 0 0 0 0 550 0 0 0 0 0 600 0 0 0 0 0 650 0 0 0 0 0 700 0 0 0 0 0 750 2 4 0 0 0 Table 8: Spectral transmittance (%) of the infrared region of black color paper using black pigments -2 to 6 Wavelength (nm) Black Pigment-2 Black Pigment-3 Black Pigment-4 Black Pigment-5 Black Pigment-6 900 72 51 31 48 35 1000 78 59 39 58 43 1100 81 66 43 66 51 1200 82 71 47 71 57 1300 84 75 52 77 62 1400 84 78 56 79 66 1500 85 81 60 81 70 (2) In the same manner as in Example 2, black pigments 2 to 6 obtained in Production Examples 2 to 6 were used, respectively, to form a black coating film, and Make black color paper separately. The dry film thickness of the black coating film is about 35 to 40 nm on the black color development paper. The penetration rate was measured in the same manner as in Example 2, which is the same as Example 2 of 100149099 52 201241098. As a result, as shown in Table 9, the spectral reflectance showed the same tendency as the color development paper.丨〇又竹·<展色

100149099

S 53 201241098 The flat plate absorbs light in the visible light region and can penetrate the near infrared ray fully. It can be used in applications such as infrared penetrating filters. [Example 5] (Acrylic resin molded plate) In the same manner as in Example 4, 20 parts of the black pigment-3 prepared in Production Example 3 and 80 parts of the acrylic resin (polymethyl methacrylate) powder were used. After thoroughly mixing the Scherr-mixer, the mixture was mixed and kneaded by a biaxial extrusion kneading machine to prepare an acrylic resin black main batch containing black pigment - 3 〇%. Two parts of the obtained black main body batch were mixed to one part of the acrylic resin particle which consists of the resin powder similar to the above, and further mixed by the Michelle mixer, and then kneaded by the biaxial extrusion. The machine is mixed and kneaded to make black resin particles. The obtained black resin particles were molded in a line-type spiral injection molding machine to obtain a black acrylic resin flat plate having excellent pigment dispersibility. The black resin plate is a light that absorbs the visible light region. It can also penetrate the near infrared rays sufficiently, and can be used as an infrared penetrating calender. [Example 6] (Polyurethane coating agent) 15 parts of black pigment _4 prepared according to Production Example 4 and 1 part of polycarbonate-free yellowing-resistant polyurethane resin, A method of blending a black pigment with a polycarbonate-based non-yellowing polyamine phthalate resin solution or DMF is carried out in a manner of 75 parts of dimethylformamide (hereinafter referred to as "DMF"). The blending solution was sufficiently dispersed by a horizontal type continuous media disperser to obtain a high concentration dispersion of black pigment 100149099 54 201241098. Next, 10 parts of propyl acetate as a diluent solvent was added to a polycarbonate-based non-yellowing polyamine phthalate resin solution (solid content 30%, DMF solvent) for forming a skin layer. One part of isopropyl alcohol and 20 parts of the previously prepared black pigment high-concentration dispersion were mixed and mixed to prepare a black-polyurethane coating liquid. Then, the black coating liquid prepared above was applied to a release paper DNTP-155T-FLAT (trade name, manufactured by Otsuka Printing Co., Ltd.) to have a film thickness of 5 (^m). Then, it was dried under the conditions of rc/1 〇min to form a skin layer. Further, it was prepared as a polycarbonate-based huangliang-type t-aminoformic acid g-resin solution as an adhesive (solid fraction 7). 〇%, benzene: methyl ketone (hereinafter referred to as "MEK") = 1: oxime solvent), mixed with two light release solvents, 10 parts of benzene, MEK20, DMF2 与 and modified Polyisocyanate-based crosslinking agent (solid content: 75%, ethyl acetate), 1 part by weight, amine-based cross-linking catalyst (solid content 0.5% MEK solvent), 0.15 parts. Then, the second agent is applied to the epidermis. The surface of the layer (the surface on the opposite side to the surface on which the release paper is contacted) is applied to a sheet having a film thickness of 75 μm, and then subjected to (10) (3) minutes; the line is dried. The obtained back layer is obtained. The sheet with the skin layer is laminated on the adhesive layer side to the substrate (fabric) to form a laminate having a total thickness of 1 J 〇 _: the obtained laminate is heated to (10). The laminating roller is separated from the gap of _ handsome, and then repeatedly bonded. Then, after 6 〇t/48 hours of aging, the synthetic fake dermis is obtained by peeling off the release paper. The synthetic pseudo-skin obtained can be reduced (reduced) In addition to heat accumulation, it is excellent in heat deterioration resistance, hydrolysis deterioration resistance, and light resistance. 100149099 55 201241098 It is suitable for durability such as vehicular properties and oleic acid resistance, etc., and the like. The agent contains a white pigment to be colored white, thereby imparting a new property to the adhesive layer, and forming a double structure composed of a skin layer containing a black azo pigment exhibiting both visible light blocking properties and infrared penetrating properties. A polyamino phthalate synthetic leather which can reflect heat rays is obtained. This synthetic leather is particularly suitable for use in automotive interior decoration and the like [Example 7] (raw liquid colored woven fabric) Production Example 5 is carried out by using a Michelle mixer 5% by weight of the prepared black pigment and 5 parts of the ethyl bis-stearate powder as a pigment dispersion meter to obtain a powder coloring agent with a pigment content of 50% (dry color) Secondly, 1.0 part of the dry color obtained is blended into the polypropylene resin particles % 〇彳8, mixed by a Michelle mixer, and then mixed by a zigzag/extruder to modulate the pigment into 〇 .5% of the black tree granules. The obtained black resin granules were woven in a melt spinning machine to obtain a clear black polypropylene original color woven fabric having a fineness of 10 denier and excellent pigment dispersibility. The woven fabric made of cloth can reflect the heat radiation of sunlight, and can be expected to avoid the effect of warming up. Since α 匕 ' is particularly suitable for applications such as sun umbrellas or curtains. [Example 8] (resin molding) Titanium oxide white 75 parts of the pigment were mixed with a black pigment -6 5 parts, 20 parts prepared by the production of Example 6, and a polyethylene resin powder 100149099 56 201241098 as a pigment dispersion meter to obtain a powder coloring agent (dry color). Next, 1.0 part of the obtained powder coloring agent was blended into 100 parts of polybutylene terephthalate (PBT) resin pellets, and after mixing by a Micheler mixer, kneading was performed by an extruder to prepare Black resin pellets. The obtained black particles were molded in a wire spiral injection molding machine to obtain a black resin molded plate excellent in pigment dispersibility. The obtained resin-formed sheet is capable of reflecting heat rays of direct sunlight. Therefore, it is suitable for the use of a resin molded article which avoids heating. [Example 9] (heat-shielding back cover sheet for solar power generation module) (1) 15 parts of black pigment _4 prepared in Production Example 5, acrylic acid polyol (hydroxyl price: 1 〇〇) butyl acetate solution 25 parts (solid content: 5%) and 50 parts of butyl acetate were sufficiently prepared and mixed, and then pigment dispersion was carried out using a horizontal continuous medium disperser using glass beads as a dispersion medium, thereby preparing a black pigment high-concentration dispersion. . ^ In the 9G portion of the black pigment high-altitude dispersion obtained above, the same (10) acid (tetra) acetic acid yg| solution is added, and the benzo-based monomer and the HALS-based monomer are copolymerized with acrylic acid. Alcohol (2). - 50 parts of acetic acid butyl liquid for black ink. Then two or two black inkizers add a trimeric isocyanate as a hardener, and the hexamethylene is a trimeric (solid form: job, gena%: 2 after thorough mixing, adding butyl vinegar approximately (1) In the 8G portion of the titanium oxide white pigment, it is prepared to mix 4 G of the acrylic acid butyl acetate solution used in the above (1), and the acetic acid is used. And the pigment dispersion is carried out in the same horizontal cross-web disperser as used in the above (1) to prepare a white pigment high-concentration dispersion liquid. In the above-mentioned white pigment high-concentration dispersion liquid 140 parts, Add 44 parts of acrylic acid polyol acetate solution to white ink. Then, for this white oil, add the same hexamethylene diisocyanate as the hardener. 18 parts of the trimer, after thorough mixing, add about 40 parts of butyl acetate to adjust the viscosity, and prepare a white coating liquid. (3) Poly(p-diphenyl) ethanediacetate (pET) substrate sheet (film) Thickness: just (four) on the surface (1) The black coating liquid prepared is formed into a black coating film (dry film thickness: _). Then, the self-color coating liquid of the above (2) is applied to the base (four) surface, and the film is dried, and the film thickness is: (4) A white-coated multi-layer PET sheet coated with a black coating film on the surface and a coating film on the back surface. The water-vapor barrier property and gas are improved on the black-white multi-layer PET sheet obtained in the above (3). Barrier, overlap on the surface, laminate the two shame, alumina vapor-deposited polyester film (film thickness: 12μηι), and laminate the PET substrate sheet at 1ΛΛ. t is a PET back cover for a solar power generation module. The above-mentioned adhesive is used as described above. The adhesive is the same as the above (1) j, which is made up of (4) acid poly s solution 7G parts, hexa Base diisocyanate 100149099 58 201241098 Adhesive consisting of 15 parts of vinegar trimer and 15 parts of butyl acetate. The black coating film obtained according to the above and the appearance of the back panel of the PET film are coated on the plurality of layers. It is black and beautiful, and it has the optical characteristics of the material used. The optical property n, the light in the infrared region of the sunlight passes through the black coating layer on the surface, and the light passing through the infrared region is reflected on the self-color layer domain of the substrate and is again transmitted through the inner layer to be radiated to the outside. The back cover plate exhibits excellent heat-shielding property by absorbing less sunlight, so it is suitable as a back cover plate for avoiding warming of the sun grip group. The mold is used as the solar power generation module after obtaining the above-mentioned cover plate. In the case of use, it can be used as follows (4), that is, the solar power generation unit is sealed by sandwiching a sealing material composed of a vinyl acetate-based vinyl resin, and the surface is attached to the surface of the light-receiving surface side. The sealing sheet is a protective sheet on the non-light-receiving surface side of the back surface, and the black surface of the light-shielding back cover is bonded to the light-receiving side, and then the transparent glass substrate is mounted on the light-receiving surface, whereby the solar power generation mold can be fabricated. group. [Example 10] (heat-shielding back cover for solar power generation module) (1) 40 parts of black pigment-6 obtained in Production Example 6 and 60 parts of polyester resin powder black were mixed by a Michelle mixer. A powdery colorant is obtained. Next, 12.5 parts of the obtained powdery coloring agent was blended to 87.5 parts of the PET resin pellets, and after mixing by a Michelle mixer, the mixture was kneaded by a biaxial extruder to prepare black resin pellets by a granulator. Then, by γ 100149099 59 201241098 modulo [out of λ, the silk is used as the black ρΕτ film of the face thickness. (2) A white PET sheet (film thickness: 180 μm) which was kneaded by a titanium oxide pigment was prepared. Then, the black acrylic film obtained in the above (1) was attached to the surface thereof using the same acrylic polyol/hexamethylene diisocyanate-based adhesive as described in (4) of Example 9, whereby a black layer was formed. White PET film of PET film. (3) In order to impart moisture resistance and gas barrier properties to the white PET sheet having the black PET film laminated thereon, first, the acrylic polyol used in the above (2) is used as the surface of the sheet. A methyl diisocyanate-based adhesive was laminated, and a cerium oxide-aluminum oxide vapor-deposited polyester film was laminated. Then, a pET substrate sheet (film thickness: ΙΟΟμιη) was laminated thereon using the same adhesive as above to form a back cover for a solar power generation module. The back cover panel for a solar power generation module formed by laminating the black film and the white PET sheet obtained as described above has a black appearance and is excellent in appearance, and the optical property of the black pigment-6 used is σ. The following optical properties are available. That is, the light in the infrared region of the sunlight penetrates the black film layer on the surface, and is reflected by the white bracts below, and penetrates the black film again to radiate the outside. Therefore, the black-and-white multi-layer enamel film absorbs less sunlight. It shows excellent secrecy, so it is particularly suitable as a post-fire board for solar power modules that avoid temperature rise. When it can be used for a module for power generation, it can be used as follows according to the conventional method. That is, the solar power generation unit 100149099 60 201241098 is sandwiched and sealed with a sealing material composed of a vinyl acetate vinyl resin, and a surface sealing sheet is attached to the surface of the light receiving surface, and The protective sheet on the light-receiving side is formed by bonding the black surface of the light-shielding back cover toward the light-receiving side, and then mounting the transparent glass substrate on the light-receiving surface, whereby a solar power generation module can be produced. [Example 11] (Plastic dyeing agent for woven fabric) 71 parts of a pressed cake containing 25 parts of black pigment _ 获得 obtained by the production example 1 and a nonionic pigment dispersing agent 1 part by mass basis One part of the foaming agent and 18 parts of water were sufficiently prepared and mixed, and then pigment dispersion was carried out in a horizontal continuous medium disperser using glass beads as a dispersion medium to prepare a black pigment local concentration dispersion (black color substrate). Two parts of the obtained black color substrate, 25 parts of a reactive alkyl acrylate emulsion (solid content: 4% by weight), and an antifoaming agent were prepared. 5 parts, 1 part of dispersing agent, 3 parts of dispersion stabilizer for oil droplet type emulsification in water, 38 parts of mineral pine gp, 12.5 parts of water according to average f|| (strong emulsification dispersing machine) Type black emulsion slurry. Then, the prepared black emulsion (4) was mixed with 2 parts of the nitro-imine cross-linking agent (solid powder) and mixed thoroughly, and the black color was _. The obtained black was printed on the n-cotton blended fabric on the whole surface, and subjected to hardening for 15 minutes to obtain a black non-substrate which can shield the heat rays [Example 12] (gravure printing ink) 11 Addition to a 40 〇/〇 methyl ethyl ketone·toluene of a polyurethane resin obtained by subjecting the black pigment_1〇100149099 201241098 isocyanate terminal polyester obtained in Production Example 10 to a chain length extended with a diamine. 1 : 3) Mixing the solvent solution in 3 parts. Next, 2 parts of a cationic polymer dispersant, 2.5 parts of a 40% benzene solution of a polycarboxy quinone imine compound derived from methyl phenyl diisocyanate, and mercapto ethyl ketone-nonyl benzene-isopropanol (5) 〇: 3〇: 2〇) 54.5 parts of a mixed solvent, and thoroughly mixed using a high-speed mixer. Then, the above mixture was subjected to fine dispersion of the pigment in a horizontal continuous medium disperser using glass beads as a dispersion medium to modulate the black gravure ink. The obtained black gravure printing ink was separately printed on a polyimide film, a polyester film, or a polypropylene film using a gravure printing machine to obtain a black polypropylene enamel which exhibited optical characteristics of blocking visible light and penetrating infrared rays. [Example 13] (Formation of BM of CF) (1) (Preparation of pigment dispersion liquid for BM) (Preparation of black pigment dispersion liquid) 25 parts of black pigment obtained in Production Example 9 and benzyl benzyl methacrylate曰-mercaptoacrylic acid-2-transethylethyl methacrylate g-based copolymer (Morby: 60: 20: 20 'weight average molecular weight 3 〇 0 〇〇) 4 〇% solution 2 parts, cationic Two parts of the polymer dispersant and 53 parts of propylene glycol monodecyl ether acetate (PGMA) were sufficiently prepared to be mixed. Next, the pigment was finely dispersed using a continuous horizontal media disperser to obtain a black pigment dispersion (hereinafter referred to as "black pigment dispersion"). (2) (Preparation of photosensitive black photoresist ink) 100149099 62 201241098 6 parts of black pigment dispersion liquid obtained in the above (1), 50 parts PGMA solution of acrylated acrylic polyol photosensitive resin, 3 parts, three 1 part of hydroxydecylpropane triacrylate, 1 part of dipentaerythritol hexaacrylate, ethyl ketone as a photopolymerization initiator, 1-[9-ethyl_6-(2-mercaptobenzylidene)-9H - oxazolyl-3-yl]-, 1-(indolyl) ("IRGUCURE OXE02", manufactured by BASF Corporation) 1 part and PGMA 51 parts. Then, it was sufficiently stirred by a high-speed stirrer to be uniformly filtered, and then filtered with a filter having a pore size of 3 μm to prepare a black resist ink containing black pigment-9 (hereinafter referred to as "photosensitive black resist ink-1"). (3) (Evaluation of black photoresist film) Using the photosensitive black photoresist ink _ 上述 obtained above, it was coated on a glass substrate by a spin coater. Then, after pre-drying at 6 〇〇c, prebaking was performed after exposure to an ultrahigh pressure mercury lamp at a light amount of 4 〇〇mJ/cm, and post-baking at 230 C for 30 minutes to obtain a thickness. 3μπι black coating film (black photoresist ink film). The optical characteristics of this coating film showed high absorbance in the wavelength range of about 400 to 750 nm in the visible light region and high penetration in the infrared region of 900 to 1500 nm as shown in Table 1A. Further, the volume specific resistance of the coating film was 1014 Å · cm or more, and high insulation was confirmed. 100149099 63 201241098 Table 10: Spectral transmittance of black photoresist film Wavelength (nm) Transmittance (%) Wavelength (nm) Transmittance (%) Wavelength (nm) Transmittance (%) 400 1 700 0 1000 60 450 1 750 -0 1100 69 500 0 800 a 1 1200 74 550 0 850 27 1300 79 600 0 900 1 45 1400 81 650 0 950 55 1500 84 (4) (modulation of BM pattern) Using the photosensitivity obtained above The black photoresist ink-1 was applied to a glass substrate by a spin coater in a usual manner, and then prebaked at 8 ° C for 10 minutes to obtain a black coating film having a film thickness of 3 μm. The black coating film was exposed to a negative reticle pattern of the BM pattern and exposed to light of 100 mJ/cm using an ultrahigh pressure mercury lamp, and then developed by an alkaline developing solution, washed with water, and dried to form a BM pattern. The BM film forming the BM pattern obtained as described above exhibits high electrical insulation as described in the above (3), and thus can be used for various CF improvement methods for forming BM on an active device such as a TFT, for example, instead of a spacer. The structure of the BM, IPS mode, COA mode, etc., which maintains the thickness of the liquid crystal layer. Further, the BM film can sufficiently absorb the visible light region until it reaches the long wavelength region, and thus it is also possible to use the BM as an LCD panel using an LED backlight. (5) (Preparation of each of the red, green, blue, yellow, and purple pigment dispersions) PR254 (diketone ratio slightly more than each red pigment), PRl77 (g) as described in the above (1) , _ red pigment), PG36 (峨^: green pigment), PB15. 6 (ε-type ugly blue pigment), PY138 (yellow pigment) and ργ23 (two 100149099 64 201241098 ° and other purple pigments) The pigments and materials are known to have a base, a pigment, and a pigment composition to prepare each component; (The color of each color and the color of the purple color will be the same as described in (7), respectively, and the addition of 9.2 parts of the 50% solution of the pre-sensitive resin, photopolymerizable single. 3 parts of the body, 3 parts of the initial mash, and 54.5 parts of the solvent were used to prepare a red photoresist ink. In the same manner as above, the (4) dispersions containing yttrium and Mm, respectively, were blended in a ratio of 5:5, and The pigment dispersion liquid containing ΡΒ15.6 and pV23, respectively, is prepared in a ratio of 8:2, and the green photoresist ink and the blue photoresist ink are separately prepared. (6) (Formation of RGB pixels of CF) The glass substrate formed with the BM formed in the above (4) is mounted on a spin coater, and after the above-mentioned prepared photosensitive red photoresist ink is spin-coated, it is pre-baked for 8 minutes at 8 GC. Then, A photomask having a town-inlaid pattern is exposed on the coated surface of the glass substrate by using a proximity exposure machine according to the amount of light of the ultrahigh pressure mercury lamp of l〇〇mj/cm2. Then, after developing with a special developer and a special rinsing agent Wash and dry to form a red setting The mosaic pattern is on the glass substrate. Further, in the same manner as described above, the green mosaic pattern is formed using the photosensitive green photoresist ink, and the blue mosaic pattern is formed using the photosensitive blue light 100149099 65 201241098 to form the blue mosaic pattern. In the same manner as described above, the photosensitive black resist ink was used in the same manner as described above except that the black pigment -7 obtained in the production example 7 was used instead of the black pigment -9 used in the above BM& rgb pixel. In addition, the above-described ΒΜ pattern and RGB pixel pattern are formed to suppress the formation of CF of BM and RGB pixels. [Example 14] (Formation of BM of CF) (1) (Modulation of pigment dispersion for BM) (Preparation of Black Pigment Dispersion) In the same manner as in Example 13 (1), black pigment-8 was substituted for black pigment _9, and the same benzyl methacrylate previously used was used. 25 parts of a 4-ethylidene ethyl methacrylate copolymer 40% solution and 53 parts of propylene glycol monodecyl ether acetate (PGMA) are fully prepared and mixed, and then dispersed by continuous horizontal media. Machine to divide the pigment In order to obtain a black pigment dispersion liquid, the material is hereinafter referred to as "black pigment dispersion liquid-2". (2) (Modulation of photosensitive black photoresist ink), except at place (2) described in Example 13. Black pigment dispersion-1 was used, and a black photoresist ink was prepared in the same manner as in Example 13 (2) except that the black pigment dispersion liquid-2 obtained above was used. Hereinafter, this material is referred to as "photosensitive black light. (Resist ink-2) (3) (Modulation of BM pattern) 100149099 66 201241098 In the same manner as described in Example 13 (4), the photosensitive black photoresist ink-2 was coated on a glass substrate by a spin coater. And pre-baked to obtain a black film with a thickness of 3 μm. On the coating film, a mask pattern was cast through the bm diagram, and exposure was carried out using an ultrahigh pressure mercury lamp, and after development with an experimental developer, it was washed with water and dried to form a ruthenium pattern. The ruthenium film forming the ruthenium pattern has a high electrical insulating property, and in the same manner as in the thirteenth embodiment, the cp improvement method of forming a ruthenium on the silk element, for example, the structure of the BM replacing the fixed spacer, or The structure of the mode, COA mode, etc. Further, since the visible light region can be sufficiently absorbed until the long wavelength region, BM » (4) (formation of RGB pixels of CF) which is an LCD panel using an LED backlight can be used, as in the description (6) of the thirteenth embodiment. The glass substrate on which the BM was obtained obtained in the above (3) was mounted on a spin coater, and the photosensitive red photoresist ink obtained by the month (5) of Example 13 and the photosensitive green photoresist ink were used. The blue resist ink forms a color mosaic pattern of each color to obtain CF formed with BM and RGB pixels. [Evaluation Results] The CF obtained by the application of Example 13 and Example 14 was excellent in color, optical density, light transmittance, and hybridity, and excellent in optical properties. 100149099 67

Claims (1)

201241098 VII. Patent Application Range: 1. A black azo pigment which exhibits two optical characteristics of visible light opacity and infrared ray penetration, and is characterized by being a black polyazo pigment having the following structure: The molecule has two or more azo bonds and at least one 2-hydroxyl-11H_benzo[a]-carbazolyl-3-carboxylic acid guanamine residue introduced by the even component, and the average particle diameter thereof is 10nm~200nm. 2. The black azo pigment according to item i of the patent application, wherein the black colored film containing the black odor pigment on the visible light-shielding transparent substrate has a wavelength of about gamma to 75 Å in visible light The spectral transmittance of about 5% or less is shown in the range; the above-mentioned infrared penetrating property shows that the black colored film exhibits a transmittance of about 30% or more in the wavelength range of 9 (9) to 15 QQ nm of the infrared region. 3. The black azo pigment according to the second or second aspect of the invention, wherein the polyazo pigment has at least one of the following structures (1) to (4): a compound of two or more amine groups (formula.HaN-Ar-NH2) is diazotized to form a diazonium salt diaZ〇mUm), and the salt will be used as an even-synthesis group. The structure represented by _CN=N_Ar_N=Nc] formed by the sulfo-aryl arylamine (abbreviated as hbc) and formed by argon/coupling (2) using two or more amines which will belong to the diazonium component The compound of the base (2 Ar-NH2) is diazotized to form a diazonium salt, and the salt will be used as an even component. 2_secret_oil·benzo(5)+sodium aryl aryl 100149099 68 201241098 醯The structure (τ) of the [HBc_N:=N_Ar_N==N_Cpn4] formed by the azo/coupling of the amine (abbreviated as HBC) and other coupling components other than the compound (Cp), in its molecule, An even synthesis of two or more 2_hydroxy_UH 笨(5)_ oxazolylcarboxylic acid decylamine residues (abbreviated as HBC-) (representing &~HBC- HBC) 'Di-N-HBC-HBC-N is formed by diazotization using a compound having an amine group as a diazo component (denoted as Ar-NH2) to cause azo/coupling thereof. =N-Ar] 构造 示 构造 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有An even component (expressed as HBc_Cp) of a residue other than the compound (expressed as Cp-), which is diazotized using a compound having an amine group as a diazo component (denoted as Ar-N%), a structure represented by [Ar-N=N-HBC-Cp-N=N-Ar] formed by azo/coupling thereof. 4. A black azo pigment according to item 3 of the patent application, wherein Any one of the above-mentioned azo component and the above diazo component is selected from the following: (Aa) The above-mentioned coupling component (HBC) is 2-hydroxyl_UH_benzo(5)-oxazolyl-3-aniline, 2 -hydroxy-11H-benzo[a]-carbazolyl-3-ylnaphthylamine and the derivatives (Ab) of the above-mentioned coupling component (HBC-HBC) are phenyl-bis(2-hydroxy-11H) -Benzo[a> carbazolyl-3-carboxylic acid decylamine), phenylene-bis(2-hydroxy-UH-benzo[a]- Mercapto-3-carboxylic acid decylamine), stilbene-bis(2-hydroxyl-11H_benzo[a]_咔100149099 69 201241098 oxazolyl-3 carboxylic acid decylamine) and these street creatures (Ac) the above-mentioned coupling component ((4) is light base dongcaocarboxylic acid aryl aryl amine, ^ & _6_N-carboxylic acid aryl amide, 2 经 蒽 蒽 蒽 蒽 芳 芳 、 、 Aryl decyl amide, 2-hydroxy-1-°-carzolyl aryl decylamine and the derivatives (Ad) of the above-mentioned coupling component (HBC_Cp) are phenyl (_丨) (2) _hydroxy-indole benzo[a]-flavored s--3-carboxylic acid decylamine) (_4) _ (2-hydroxy_3_naphthyl decanoic acid decylamine), extended joint stupid base (-4)- (2-hydroxy-11H-benzo[a]-indolyl_3_redeced decylamine) (-4')-(2-hydroxy-3-naphthoquinone decylamine), (2_mercapto- phenylphenyl-11H-benzo[a]-carbazolyl-3-carboxylic acid decylamine) (-4)-(2-hydroxy-3.naphthoic acid decylamine) and the derivatives thereof (Ba The compound having two amine groups (HzN-Ar-NH2) used as the above diazo component is phenyldiamine, diaminobiphenyl, diaminonaphthalene, diaminofluorenone, diamine -benzophenone, diaminopyridine and the derivatives (Bb) as the above weight Use of a component and the amine compound (Ar-NH2) with an aniline, naphthylamine, anthrone group, phenoxyaniline, aniline and derivatives phenylimino of these. 5. A method for producing a black azo pigment, which comprises a synthetic step of a black polyazo pigment for obtaining a black azo pigment according to any one of claims 1 to 4, and a pigment which is required as needed A manufacturing method of the step of miniaturizing, characterized in that (I) the method for synthesizing the black polyazo pigment is in the group consisting of any one of the following (1) to (4), 100149099 70 201241098; The synthesis is carried out by the synthesis method selected: (1) The diazonium salt formed by diazotizing a compound having two or more amine groups (representative formula: Guanrui 2) is used to make the 2-ruthenyl group Synthetic method for azo/coupling of aryl decylamine (abbreviated as HBc) (7) Synthesis method of polyazo pigment having the following structure: the structure is a compound for a compound having two or more amine groups :Η2Ν·ΑΓ-ΝΗ2) The diazonium salt formed by heavy gasification is made 2-passive,-stupid [(tetra)indolyl-3_ sulphuric acid aryl decylamine (abbreviated as HBC) and other couplings other than the compound The composition of the composition (not shown as CP) for oxygen/coupling; a compound having two or more amine groups (representative formula A) is diazotized to form a diazonium salt, and an even synthesis component such as mol or less ((9) is subjected to azo/coupling, and two or more are required. The coupling component (Cp) is a method for synthesizing and removing the polyazo pigment which has been coupled, and then subjecting the above-mentioned coupling component (brain) to azo/coupling of the uncoupled diazonium salt group (3 1) There are more than two 2_-based sulfhydryl benzo(5)-decyl _3 in the knives. The coupling of the acid amide residue (abbreviated as HBC_) (expressed as HBOHBC) 'make the compound with an amine group (Synthesis method (3-2) in which the nitrogen component formed by diazotization is reduced/coupled by diazotization is carried out for 2-carbyl group, 11H-benzo[a]"kawaki_3_remediation The diazonium salt formed by heavy gasification of a compound having an amine group (denoted as Ar_NH2) is subjected to azo/coupling to condense the azo dyed lining with the green polyamine at 100149099 71 201241098 to form a polycarboxylate amine. Synthetic method (4-1) for a hydrazine residue having 2-hydroxy-11H_benzox]-carbazolyl-3-carboxylate in one molecule ( Abbreviated as HBC-) and other coupling components other than the compound (expressed as CP-), the coupling component (expressed as HBC-Cp), the compound having an amine group (denoted as Ar_NH2) is diazotized to form a diazonium salt for azo/coupling synthesis method (4-2) for 2-hydroxy-11H-benzo[a]-carbazolyl-3-furic acid and other azo compound tareties, respectively, having one Amine-based compound (denoted as Ar-NH2) is azo/coupled by diazotization of a diazonium salt, followed by condensation of the obtained azo dye carboxylic acid with an aryl polyamine to form a poly a method for synthesizing tartary acid and (II) in the case where the polyazo pigment synthesized by the above method is coarse, having a fine particle size of the pigment according to any one of the following methods (1) or (2) Steps to 10 nm to 200 nm: (1) Use of ball mill, sand mill, attritor, crucible continuous media disperser, kneader, continuous single-axis kneading machine, continuous biaxial kneading machine, three Any of the pigment grinders or pigment dispersers selected from the group consisting of rolls and open drum continuous mixers Micronization process (2) in a kneading machine, the water-soluble salts, water-soluble organic solvent to be due to the need for kneading / grinding of the salt milling (salt_miUing) method together. 6.-Coloring composition' characterized in that it contains 100149099 72 201241098 black azo pigment according to any one of the claims of the patent or in the solid dispersion medium, or according to item 5 of the patent application scope. The pigment component of the black azo pigment obtained by the production method. 7. The colored composition of claim 6, wherein the pigment component containing the black odor pigment is used for performing chromatic colored coloring of dark color or dark color or black coloring of achromatic color. The black azo pigment is used alone or in combination with the black azo pigment and a group selected from the group consisting of colored pigments, white pigments, other black pigments, and body pigments for correcting the black azo pigment. Made of pigment. 8. The coloring composition of claim 7, wherein the black azo pigment and the color ratio of the colored pigment, white pigment, other black pigment or body pigment used to modify the black azo pigment are used in a computer. • The color comparison system is determined by the optimization method. 9. The coloring composition of claim 6, wherein the liquid dispersion medium comprises a polymer which may also have a reactive group, a copolymer which may also have a reactive group, and may also have a reactive group. The at least one film-forming material of the monomer is selected and is itself a liquid or further contains a solvent and/or water. 8. The coloring composition of claim 6, wherein the solid dispersion medium contains self-heating At least one solid dispersion medium selected from the group consisting of a plastic resin, a thermosetting resin, a wax, a fatty acid decylamine, and a fatty acid metal soap. 11. The colored composition according to any one of claims 6 to 10, wherein the coloring composition is used for coatings, coating agents, plastics, 100149099 73 201241098 fibers, printing inks, At least for any use. 12. A method for coloring articles, image recording, and image display, characterized in that the article is colored black or dark by the color of the surface of the article or the color of the article itself. The color composition. U. The coloring method of the article of claim 12, wherein the article is composed of a transparent substrate, by self-coating, coating, dyeing, printing, taking notes, drawing, inkjet printing, electronic photographing Printing, electrostatic printing or photolithography printing selects the sister-finished needle (4) through the substrate for surface coloring, or by the kneading square domain impregnation method for the internal coloring of the upper wire itself. d. The coloring method of the article of claim 13, wherein the surface-colored or internally colored-colored portion exhibits a spectroscopic light of about 5% or less in a wavelength range of about 400 to 750 nm in the visible light region. The transmittance is such that the infrared region of 900 to 1500 nm exhibits a transmittance of about 3% or more, and the article composed of the transparent substrate can have both visible light shielding and infrared transmittance. Optical properties. 15. The method of coloring an article of claim 12, wherein the article itself is light reflective or uses an article provided with a preformed light reflective substrate for surface or light reflectivity of the article On the substrate, the above colored composition is used and applied by coating, coating, attaching, dissolving, laminating, coloring, dyeing, dip dyeing, printing, taking notes, drawing, inkjet printing, printing, electronic photo printing Or electrostatic printing, and applied to the infrared reflective color. u does not produce a coloring matter of the species, which is characterized by the coloring method of the article of any one of claims 12 to 4 (4). & - a solar panel after the power generation module, which is attached to the light-reflective sheet and has a plurality of black-cut infrared hiding layers, characterized in that it contains black polyazo pigment on the infrared penetrating layer. The chromophoric polyazo pigment material is ordered to be converted: the molecular towel has two or more azo bonds L and at least one (10) benzyl benzophenyl ruthenium decylamine residue guided by the even component ( It is abbreviated as HBc_); and its average particle diameter is 10 nm to 200 nm. 18. A method of manufacturing a cover sheet for a solar power generation module, characterized in that a material having a silky property is used as a monolithic sheet, or a substrate having a pre-formed light-reflective substrate is used as light. A reflective sheet comprising a colored composition containing a black polyazo pigment on the surface of the substrate or a light-reflective substrate by coating, coating, attaching, dissolving, laminating, printing, and ink-jetting Printing, electrophotographic printing or xerographic printing, which exhibits a reflective color in the outer line region, and a black or dark colored infrared penetrating layer is laminated on the light reflective sheet; the black polyazo pigment system Having the following structure: having two or more azo bonds in the molecule and at least one 2-hydroxyl_iiH-benzo[a]-carbazolyl-3-carboxylate oxime residue introduced by the even component ( It is abbreviated as HBC-); and its average particle diameter is i〇nm~2〇〇nm. 100149099 75 201241098 19. A color display panel characterized in that a black matrix (BM) formed on a color filter (CF) substrate or an organic EL light-emitting substrate contains a black polyazo pigment, the black polyazo The pigment has a structure having two or more azo bonds in the molecule and at least one 2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxylic acid guanamine residue introduced by the even component. Base (abbreviated as HBC-); and its average particle diameter is from 10 nm to 200 nm. 20. The color display panel of claim 19, wherein the CF substrate or the organic EL light-emitting substrate is formed in a state in which a substantially black matrix of electrical insulation is laminated or contacted with an electrode. 100149099 76 201241098 IV. Designation of representative drawings: (1) The representative representative of the case is: None (2) The symbol of the symbol of the representative figure is simple: None. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: No 100149099 2