TWI478983B - Black azo pigments, manufacturing methods, coloring compositions, coloring methods and colored articles - Google Patents

Description

Black azo pigment, manufacturing method, coloring composition, coloring method, and coloring article

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, it is used for the purpose of utilizing a phenomenon in which a visible light region is absorbed and absorbed, and further has transparency in an infrared region, and exhibits a black polycrystal having a specific structure for optical properties useful for use in the use of infrared rays. An azo dye, and a method for producing the same, a coloring composition, a coloring method thereof, and a colored article.

The black pigment used in a coloring agent such as paint, printing ink or plastic is generally a carbon black pigment or an iron oxide black pigment. These black pigments display 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 780 nm is regarded as visible light, and the light in the region of 0.7 μm to 2.5 μm longer than the visible light is near-infrared light. The black system can absorb light in the wavelength range of visible light, and the carbon black pigment can not only absorb visible light but also absorb light in the near-infrared region.

The near-infrared rays in the light are different from short-wavelength light such as ultraviolet rays, and have little adverse effect on the human body, and are safe light. Therefore, in recent years, many electronic devices for irradiation and reception using infrared rays have been developed. For example, infrared remote control conveyors and their body receivers are popular in electrical appliances, lighting fixtures, warm toilet seats, cameras, even car door locks, engine starters, garage switches, infrared protection around streets or buildings. In everyday life such as crime cameras or infrared surveillance cameras.

Further, Patent Document 1 proposes a vehicle equipped with a visible light capable of simultaneously emitting a headlight of a car, an illuminator for confirming near-infrared rays of a front obstacle, and a filter for blocking visible light and penetrating infrared rays. Use a night vision device.

As a dye used in such an infrared ray transmitter, an infrared ray filter of a receiver, and an infrared ray filter of an infrared camera, it is desirable to transmit light in an infrared ray region and to display light that completely shields the visible light region. A dye having excellent optical properties and excellent durability such as heat resistance, light resistance, and solvent resistance.

In addition, in recent years, solar power generation systems have attracted attention as a clean energy. The solar power generation module that constitutes the solar power generation system is installed in a place where it can directly illuminate sunlight, especially in the open space or the roof or eaves of an outdoor building. However, illuminating the sunlight and absorbing the light system causes the solar power module to heat up and lower the output of the power generating unit. In addition, depending on the appearance of the power module or the appearance of the dirt, the color is black, dark color, and rich color, depending on the situation, this will become a cause of significant temperature rise. . Therefore, in the solar power generation system, even if the color is black, a coloring system capable of suppressing only an increase in temperature is expected. A back cover for a solar cell comprising an anthraquinone pigment has been proposed (Patent Document 2).

Moreover, in recent years, from the viewpoints of improvement, optimization, and energy saving of the living environment, it is desirable to have a heat-shielding coating that is reflected by sunlight, and it is desired to have the above-mentioned desired heat ray-reflecting material for various uses. Development. For example, there may be roofs or walls of houses, offices, warehouses, buildings, etc., roofing or wall painting, road paving, exterior or interior decoration, and painting of ships, and even I am looking forward to heat-shielding materials for agriculture, and I also expect heat-releasing materials such as electronic parts.

In addition, in the field of information technology, with the recent rapid development of information technology, liquid crystal displays (hereinafter also referred to as "LCD") are used as information display components in various aspects of televisions, projectors, personal computers, Display screens of mobile information machines, monitors, car navigators, mobile phones, electronic computers or electronic dictionaries, information disclosure boards, navigation boards, display boards, sign boards, etc., digital cameras or camera photographs, etc. Various information shows the associated machine. Along with this phenomenon, improvement in display quality and cost reduction are required, and quality improvement and cost reduction of a color filter (hereinafter also referred to as "CF") are performed. For the CF mounted on the LCD, it is also required to have better superior quality in terms of color characteristics and optical characteristics such as fineness, color density, light transmittance, contrast, and the like, and it is desirable to have a corresponding Development of materials such as required characteristics.

Regarding the CF aspect of the LCD, R (red), G (green), and B (blue) pixels are arranged in a strand shape, a mosaic shape, a triangular shape, and the like, and the back surface is illuminated by a backlight to make R, G, and B. The color-wise mixing of the penetrating light of the pixels is performed to emit a color as an image. Then, a black matrix (hereinafter also referred to simply as "BM") is formed in a lattice shape around each pixel to shield unnecessary light or to prevent color mixture. Regarding the color pixel, a red pigment, a green pigment, a blue pigment, a yellow pigment, or a purple pigment is used, but each of them is improved. In addition, as for the BM, the light-shielding material for completely shielding the light in the visible light region of the backlight is transferred from the metal chromium film to the use of the size of the substrate or the environmental burden of the chromium compound. Black pigment resin BM.

The backlight is also replaced by a cold cathode fluorescent tube to a light emitting diode (LED), which is associated with an increase in color purity and an increase in color reproduction area. The red area is proposed to have a clear light of about 600-620 nm in the backlight of the cold cathode fluorescent tube, and as the light from the red light-emitting part in the backlight of the LED, and at the maximum light-emitting wavelength. In the vicinity of 640 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. Therefore, the improvement of BM and the improvement of the light-shielding black pigment used in BM are also in progress. For example, in order to improve the wide viewing angle as a weakness of the LCD in the prior art, a lateral 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 (COA 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 The work of the fitting step can also be improved and rationalized.

Further, in order to achieve such an improved method (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 of realizing a uniform cell gap due to the spacers fixed thereto, it is proposed to increase the thickness of the BM itself or to superimpose the resin of the spacer member such as the colored layer or the photoresist layer on the BM and thicken it. A method of supporting a cell gap of a substrate. Further, by not using the bead spacers, it is possible to improve the deterioration of display quality due to scattering or penetration of light (Patent Documents 4 and 5).

In the above-described methods such as the IPS method, the BOA method, and the COA method, the BM is formed on an active device such as a TFT. Of course, when the BM is not electrically insulating, there is a fear that the TFT causes an erroneous operation. The carbon black pigment which is generally used as a light-shielding black pigment is a pigment having a low electric resistance value, and is not suitable for a light-shielding black pigment used as such a method, and is preferably a light-shielding material having high electrical insulating properties.

On the other hand, there is a proposal for covering a carbon black pigment which is defined by an amount of oxygen in a high-insulating resin film to improve electrical insulating properties (Patent Document 6), or An insulating carbon black pigment selected from a volume resistance value or a carbon black pigment which is covered with a resin to improve electrical insulation properties, and the formation of the insulating BM is suitable for use in the COA method (Patent Document 7).

However, the carbon black pigment is a material which is originally electrically conductive, and even if it is covered with a resin as in the prior art as described above, it is difficult to complete the insulation.

In addition, in the case of a display using an organic EL element that has been continuously developed, there has been proposed use of a BM for preventing the light from the adjacent light-emitting element and improving the sharpness of the light-emitting picture (Patent Document 8).

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent No. 4120513

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2007-128943

[Patent Document 3] Japanese Patent Laid-Open No. 2006-148051

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2000-66018

[Patent Document 5] Japanese Patent Laid-Open Publication No. 2002-341332

[Patent Document 6] Japanese Patent No. 3543501

[Patent Document 7] Japanese Patent No. 4338479

[Patent Document 8] Japanese Patent Laid-Open Publication No. 2004-221081

In view of the above, it is expected that the development of a black pigment which exhibits excellent physical properties and firmness as a pigment and which is useful for various applications and exhibits both optical characteristics of visible light blocking property and infrared penetrating property is expected. Specifically, for example, it may be used for an infrared filter for an electronic device that shields unnecessary visible light rays from being transmitted and utilized by an infrared signal; or in black or dark colors constituting a solar power generation system. In the light distribution sheet, it is possible to suppress a plurality of layer coloring systems in which an infrared penetrating black layer is provided on a solar reflective substrate due to temperature rise of sunlight; or as a BM of CF, even in a wide wavelength range of light emission In the case of an LED backlight, the light in the visible light region can be completely shielded, and even if the BM is formed on an active device such as a TFT, high electrical insulation can be maintained without any use of the TFT to cause an erroneous operation. The BM of the organic EL display is also suitable for use in high-visible light-shielding properties, and it is also desirable as a black pigment which is superior in physical properties and firmness of the pigment.

In view of the above, it is an object of the present invention to provide a black pigment which exhibits superior physical properties and robustness as a pigment and which can be applied to the above various applications and exhibits both optical properties of visible light blocking property and infrared penetrating property. A method for producing a pigment, a colored composition containing the pigment, a coloring method using the same, and a colored article.

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, and as a result, it has been found that the black polyazo pigment having a specific structure absorbs light at a high level and absorbs light in a wavelength range of visible light. Almost all regions of the region have a wavelength of about 400 to 750 nm, and in addition, on the long wavelength side of the infrared region of about 900 to 1500 nm, they exhibit high permeability, and even fine in such a manner that their average particle diameter becomes 10 nm to 200 nm. The pigmented black pigment is suitable for the various applications previously listed to solve the above problems and to complete the present invention.

That is, the present invention provides a black azo pigment which exhibits two optical characteristics of visible light ray blocking property and infrared ray penetrating property, and is characterized by being a black polyazo pigment having the following structure in a molecule: Having at least one azo bond and at least one 2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxylic acid decylamine residue introduced by the coupling component; and having an average particle diameter of 10 nm~ 200nm.

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 transmittance of about 5% or less in a wavelength range of about 400 to 750 nm in the visible light range. The infrared penetrating property described above exhibits a transmittance of about 30% or more in a wavelength range of 900 to 1500 nm in the infrared region.

A black azo pigment, wherein the polyazo pigment has a structure having at least one of the following structures (1) to (4):

(1) A diazonium formed by diazotizing a compound having two or more amine groups (representative formula: H ₂ N-Ar-NH ₂ ) which is a diazo component, and the salt may be used. The azo/coupling of 2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxylic acid aryl decylamine (abbreviated as HBC) as a coupling component is formed by [HBC-N=N -Ar-N=N-HBC] The configuration shown.

(2) A diazonium salt formed by diazotizing a compound having two or more amine groups (representative formula: H ₂ N-Ar-NH ₂ ) which is a diazo component, and which is used as a coupling The component is 2-azo-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 formation is represented by [HBC-N=N-Ar-N=N-Cp].

(3) in its molecule, for an even synthesis (having HBC) having two or more 2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxylic acid decylamine residues (abbreviated as HBC-) -HBC), using a compound having an amine group as a diazo component (denoted as Ar-NH ₂ ) for diazotization to form an azo/coupling according to [Ar-N=N-HBC-HBC -N=N-Ar] The configuration shown.

(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 HBC-Cp) is diazotized using a compound having an amine group as a diazo component (denoted as Ar-NH ₂ ) to cause azo/coupling. The structure shown is [Ar-N=N-HBC-Cp-N=N-Ar].

In addition, in the above description, "Ar" represents a representative residue of an aromatic compound and a heterocyclic compound, and when it is two or more in the formula, it may be the same or may be different. Further, "Ar-N=N-" or "-N=N-Ar-N=N-" in the formula means an "arylazo residue" after coupling of a diazonium salt of a diazo component. The following all mean the same thing.

According to another embodiment of the present invention, there is provided a method for producing a black azo pigment, which is a method for producing a black azo pigment of the present invention, which is a synthetic step having a black polyazo pigment and which is required as needed A method for producing a step of miniaturizing the pigment, characterized in that (I) the method for synthesizing the black polyazo pigment can be classified into any one of the following four types, and the poly couple synthesized according to the methods In the case where the nitrogen pigment is coarse, the average particle diameter of the pigment is finely adjusted to 10 nm to 200 nm by any of the following methods.

According to another embodiment of the present invention, there is provided a coloring composition comprising the black azo pigment of the present invention described above or obtained by the above production method in a liquid dispersion medium or a solid dispersion medium. Made from the pigment component of black azo pigment.

According to still another embodiment of the present invention, there is provided a method of coloring an article, wherein the colored composition is used when the article is colored black or dark by coloring of the surface of the article or coloring of the article itself.

According to still another embodiment of the present invention, there is provided a colored article characterized by the method of coloring the article.

According to another embodiment of the present invention, there is provided a solar power generation module back cover plate which is characterized in that a plurality of infrared penetrating layers of black or dark color are laminated on a light reflective sheet, wherein The infrared penetrating layer has a structure having two or more azo bonds in the molecule and at least one 2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxyl group introduced by the even component. The structure of a decylamine residue (abbreviated as HBC-); and a black polyazo pigment having an average particle diameter of 10 nm to 200 nm.

According to still another embodiment of the present invention, there is provided a method of manufacturing a solar panel according to the present invention, characterized in that the substrate itself has light reflectivity as a light reflective sheet, or a pre-formed light is used. The substrate of the reflective substrate serves 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 at least one introduced by the even component. a structure of a 2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxylic acid decylamine residue (abbreviated as HBC-); containing 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, which 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-hydroxy-11H-benzo[a]-carbazolyl-3-carboxylic acid decylamine residue (abbreviated as HBC-) introduced by the coupling component; It also contains a black polyazo pigment having an average particle diameter of 10 nm to 200 nm.

According to the above 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 becomes a useful optical characteristic which exhibits both visible light blocking property and infrared penetrating property. 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 in a practical automobile or the like.

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 of the LCD can of course be colored black, and the color can be more vivid than other colored. 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 an opaque black pigment which is an IPS liquid crystal panel using an LED backlight and an organic EL display.

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. It is a material for preventing the rise of direct sunlight in the painting of houses, buildings, etc., road paving, and even the decking and exterior decoration of ships. Further, regarding the solar power generation system, a back cover plate in which a plurality of layers of black or dark colored infrared penetrating layers are formed on the reflective underlayer by suppressing temperature rise due to sunlight can be used. Further, it is also possible to use a coloring material for camouflage for military equipment or camouflage prevention.

Next, the present invention will be described in further detail by way of the best mode for carrying out the invention.

The black azo pigment characterized by the present invention exhibits, as an optical property, an almost complete absorption including and absorbing a visible light region, particularly in a wavelength range on the long wavelength side, or exhibits high wear in a near-infrared region. Transmittance. 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. About 30% or more. Moreover, as electrical characteristics, it exhibits very high electrical insulation.

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. Stable manufacturing was carried out, 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 high penetration property of the infrared region is particularly required, the black polyazo pigment is preferably a pigment having a fine particle diameter, and the average particle diameter of the pigment needs to be about 10 nm to 200 nm. In the case where further high transmittance is further desired, an ultrafine black polyazo pigment having an average particle diameter of about 10 nm to 50 nm or a disperse dye which imparts molecular dispersion in the medium during the coloring processing step is preferred. A black azo pigment of the nature of sex.

In the present invention, the polyazo pigment is as described above, and means a disazo pigment or a trisazo pigment having two or more azo bonds in the molecule.

The polyazo pigment exhibits a chemical structure of black, and the inventors have found that there are two or more azo bonds in the molecule and at least one 2-hydroxy-11H-benzoic group introduced by the azo compound thereof. The chemical structure of a]-carbazolyl-3-carboxylic acid decylamine residue (refer to the following formula).

2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxylic acid decylamine residue

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. A method of performing azo or coupling as a diazo component, or a method of performing azo or coupling using an even component having two or more coupling positions of an even component. This is detailed in this regard.

The black azo pigment of the present invention is preferably one having the following structures (1) to (4).

(1) using a diazolium salt formed by diazotization of a compound having two or more amine groups (representative formula: H ₂ N-Ar-NH ₂ ) as a diazo component, and the salt will be [HBC-N=N-Ar formed by azo/coupling of 2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxylic acid aryl decylamine (abbreviated as HBC) as a coupling component Black polyazo pigment of the structure shown by -N=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.

(2) A diazonium salt formed by diazotizing a compound having two or more amine groups (representative formula: H ₂ N-Ar-NH ₂ ) which is a diazo component, and which is used as a coupling The component is 2-azo-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-naphthoic acid decylamine.

(3) in its molecule, for an even synthesis (having HBC) having two or more 2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxylic acid decylamine residues (abbreviated as HBC-) -HBC), which is diazotized using a compound having an amine group as a diazo component (denoted as Ar-NH ₂ ) to form an azo/coupling [Ar-N=N-HBC-HBC- A black polyazo pigment of the configuration shown by N=N-Ar].

Examples of the black polyazo pigment having the structure (3) represented by [Ar-N=N-HBC-HBC-N=N-Ar], as described below, may be exemplified for the passage of a phenyl group or a biphenyl group. HBC-HBC having two couplings of a 2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxylic acid decylamine residue, and an aniline having an amine group as a diazo component A structural example in which diazotization is formed.

(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 HBC-Cp) is diazotized using a compound having an amine group as a diazo component (denoted as Ar-NH ₂ ) to cause azo/coupling. A black azo pigment having a structure represented by [Ar-N=N-HBC-Cp-N=N-Ar] was formed.

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 2-hydroxy-3-naphthoic acid aryl decylamine which is other than the compound. The HBC-Cp which is an even component of the residue is a structural example in which diazotization is carried out by using aniline having one amine group as a diazo component.

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).

The method (1) is a diazonium salt formed by diazotizing a compound having two or more amine groups (representative formula: H ₂ N-Ar-NH ₂ ) to give 2-hydroxy-11H-benzo[ A]-carbazolyl-3-carboxylic acid aryl decylamine (abbreviated as HBC) is a synthetic method for azo/coupling. The black polyazo pigment obtained by the synthesis method of (1) is a structure having the structure [HBC-N=N-Ar-N=N-HBC] described previously.

(2) The method of synthesizing a polyazo pigment having a structure in which a compound having two or more amine groups (representative formula: H ₂ N-Ar-NH ₂ ) is diazotized The formed diazonium salt is subjected to 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). An azo/coupling structure; a diazonium salt formed by diazotizing a compound having two or more amine groups (representative formula: H ₂ N-Ar-NH ₂ ) to give a molar or less The coupling component (Cp) is subjected to azo/coupling, and if necessary, two or more coupling components (Cp) are used to separate and remove the coupled polyazo pigment, and then the above-mentioned coupling component (HBC) is not coupled. A nitrogen salt group is subjected to an azo/coupling synthesis method. 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 (3-1) or (3-2). The black polyazo pigment obtained by the synthesis methods of (3-1) 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-NH ₂ ).

(3-2) For 2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxylic acid, a compound having an amine group (denoted as Ar-NH ₂ ) is diazotized to form a weight The nitrogen salt is subjected to azo/coupling, followed by condensation of a carboxylic acid of an azo dye with an aryl polyamine to prepare a polycarboxylate.

The method of (4) is the method of the following (4-1) or (4-2). The black polyazo pigment obtained by the synthesis methods of (4-1) and (4-2) has the previously described [Ar-N=N-HBC-Cp-N=N-Ar] The structure of the display.

(4-1) having a 2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxylic acid decylamine residue (abbreviated as HBC-) in one molecule and other coupling residues other than the compound (denoted as Cp-) of the coupling component (represented as HBC-Cp), of a compound having one amine group (represented as Ar-NH ₂₎ is diazotized to form a diazonium salt to be a method of synthesizing an azo / coupling .

(4-2) For 2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxylic acid and other carboxylic acids of the coupling component, a compound having an amine group (expressed as Ar-NH ₂ ) The diazonium salt formed by diazotization is subjected to azo/coupling, and then the obtained carboxylic acid of the two azo dyes is condensed with an arylpolyamine to prepare a polycarboxylate.

The diazo component and the even component which can be used in each of the above-described synthesis methods will be described.

(A) Specific exemplification for the coupling component.

(a) as a coupling component (HBC), for example, 2-hydroxy-11H-benzo[a]-carbazolyl-3-aniline, 2-hydroxy-11H-benzo[a]-carbazolyl-3- Naphthylamine and the like and derivatives thereof. The substituent of the derivative is, for example, an alkane (carbon number: 1 to 10) group, an alkoxy group (carbon number: 1 to 10) group, a trifluoromethyl group, a halogen group, an alkyloxycarbonyl group, or a cyclic imine group. Coupling of one or more of an oxy 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, or the like ingredient.

Specific examples thereof include 2-hydroxy-11H-benzo[a]-carbazolyl-3-aniline, 2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxy-p-fennel Annisidide, 2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxy-(2-methyl)-p-anisidine, 2-hydroxy-11H-benzo[a]-carbazole Ben-3-mid-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-carbocarbamide), extended biphenyl Base-bis(2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxylic acid decylamine), stilbene-bis(2-hydroxy-11H-benzo[a]-carbazolyl- 3-carboxylic acid decylamine) and such derivatives. The substituent of the derivative is, for example, a known substituent introduced into the aryl group, for example, an alkane (carbon number: 1 to 10) group, an alkoxy group (carbon number: 1 to 10) group, a trifluoromethyl group, a halogen group, or the like. Or an even component of the above.

Specifically, for example, phenyl-(1,4-)bis(2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxylic acid decylamine), 2-chloro-phenylene-phenyl- (1,4-) bis(2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxylic acid decylamine), 2,5-dichloro-phenylene-(1,4-) double (2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxylic acid decylamine), 2-methyl-phenylphenyl-(1,4-)bis(2-hydroxy-11H-benzo) [a]-carbazolyl-3-carboxylic acid decylamine), biphenyl-(4,4'-)bis(2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxylic acid Indoleamine, 3,3'-dichloro-extension 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-naphthoic acid aryl decylamine, 2-hydroxy-6-naphthoic acid aryl decylamine, and 2-hydroxy-3-indolecarboxylic acid. Aryl decylamine, 2-hydroxy-3-dibenzofurancarboxylic acid aryl decylamine, 2-hydroxy-1-oxazolylcarboxylic acid aryl decylamine, and the like, and derivatives thereof. For example, CIAzoic Coupling Component 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-naphthoic acid-N-benzimidazolone-5-decylamine, 2-hydroxy-3-naphthoic acid -N-o-phthalimido-4-amine and the like.

(d) as the above-mentioned coupling component (HBC-Cp), a carboxylic acid which is a Cp residue in which an amine group of an HBC residue is bonded to a guanamine, and 2-hydroxy-3-naphthoic acid and 2-hydroxy-6 are mentioned. -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-naphthoic acid decylamine ), phenyl (-1)-(2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxylic acid decylamine) (-4)-(2-hydroxy-3-naphthoic acid decylamine) , (2-methyl-) phenyl (-1)-(2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxylic acid decylamine) (-4)-(2-hydroxyl) Benzyl phthalate, phenyl (-4)-(2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxylic acid decylamine) (-4')-(2 -Hydroxy-3-naphthoic acid decylamine) and the like.

(B) Specific exemplification for diazo components

(a) a compound having two or more amine groups (representative formula: H ₂ N-Ar-NH ₂ ) as the above diazo component, for example, a phenylenediamine, a diaminobiphenyl, a diaminonaphthalene , diamino hydrazine, diamino-benzophenone, diaminopyridine and derivatives thereof. The substituent of the derivative is, for example, a known substituent introduced into the aryl group, for example, an alkane (carbon number: 1 to 10) group, an alkoxy group (carbon number: 1 to 10) group, a trifluoromethyl group, a halogen group, or the like. Or a diazo component of or above.

Specific examples thereof include 1,4-phenylenediamine, 2-chloro-1,4-phenylenediamine, 2,5-dichloro-1,4-phenylenediamine, and 2 -Chloro-5-methyl-1,4-phenylenediamine, 2,5-dimethyl-1,4-phenylenediamine, 2-nitro-1,4-phenylenediamine 1,3-phenylenediamine, 4-chloro-1,3-phenylenediamine, 4-methoxy-1,3-phenylenediamine, 4-nitro-1,3- Phenyldiamine; 4-chloro-1,2-phenylenediamine, 4,5-dimethyl-1,2-phenylenediamine, 4-nitro-1,2-phenylene Diamine; 3,3'-dichloro-4,4'-benzidine, 2,2',5,5'-tetrachloro-4,4'-benzidine, 3,3'-dimethyl-4 , 4'-benzidine, 3,3'-dimethoxy-4,4'-benzidine; 1,5-diaminonaphthalene, 1,2-diaminonaphthalene; 1,2-diamine Anthracene, 1,5-diaminopurine; 3,4-diamino-benzophenone; 2,6-diaminopyridine.

(b) a compound having one amine group (denoted as Ar-NH ₂ ) as the above diazo component, and examples thereof include aniline, naphthylamine, aminoguanidine, phenoxyaniline, phenyliminoaniline, and the like. Such derivatives. The substituent of the derivative is, for example, a known substituent introduced into the aryl group, for example, an alkane (carbon number: 1 to 10) group, an alkoxy group (carbon number: 1 to 10) group, a trifluoromethyl group, a halogen group, and a nitrate One or more diazo components such as a phenyl ether group, a phenylimino group, a benzhydryl fluorenylamino group, an anilinocarbonyl group, or a cyclic ureido group. Specific examples thereof include CIAzoic Diazo Component 5, 8, 9, 10, 32, 33, 34, 35, 36, 37, 41, 42, 43, 47 and the like.

The step of adjusting the particle diameter of the pigment particles which are finely divided by the pigment constituting the method for producing the black azo pigment of the present invention will be described. The black azo pigment of the present invention has a fine particle diameter of the pigment by using any of the following methods (1) or (2) when the polyazo pigment obtained by the above-mentioned synthetic method is coarse in particle diameter. Obtained to about 10 nm to 200 nm. That is, in order to increase the transmittance of infrared rays of a coating film or the like of the polyazo pigment obtained by the above-described synthesis method, it is necessary that the particle diameter of the dispersed pigment is smaller than the wavelength of light, specifically, The average particle size needs to be about 10 nm to 200 nm. Therefore, when the black azo pigment of the present invention is coarsened in the pigment synthesized by the above method, in order to adjust the average particle diameter of the pigment to the desired particle diameter, it is necessary to carry out the following known pigment miniaturization step. To make fine pigments.

Specifically, the pigment miniaturization step selected by the following method is carried out: (1) using a ball mill, a sand mill, an attritor, a horizontal continuous medium disperser, a kneader, a continuous single-axis kneading machine , a continuous biaxial kneading machine, a three-roller and an open drum continuous kneading machine, etc., among the groups consisting of selecting a finer method of the pigment grinder or the pigment disperser or (2) in the kneading machine, and water-soluble Solvent salt-milling method for salting and mixing/grinding together with water-soluble organic solvents required

The average particle diameter is adjusted to be about 10 nm to 200 nm. Further, in the case where it is further desired to have a high transmittance of infrared rays, it is preferred to prepare an ultrafine pigment having an average particle diameter of about 10 nm to 50 nm.

The particle size of the pigment can be adjusted to suit the application used. The adjustment of the particle size is mainly controlled according to the salt amount ratio of the pigment and the kneading time. In the case of applications requiring high transmittance infrared color filters, the pigment particles are preferably smaller, for example, preferably fine pigment particles of 10 nm to 50 nm, or even ultrafine pigment particles of 10 nm to 30 nm. In the dispersed state, in other words, it is desirable to carry out the molecularly dispersed dissolution state in a dispersion carrier such as a plastic medium.

On the other hand, in the case of a BM-like use of CF which requires a light-shielding property of visible light, it is preferably about 50 nm to 100 nm which is slightly larger than the penetrating use. Further, in terms of applications requiring infrared reflectivity, it is preferred that the substrate be reflective, and that the pigment particles are large (100 nm to 200 nm).

In the above-mentioned solvent salt milling method, water-soluble inorganic salts are added to the pigment in comparison with the desired pigment particle size by several times (specifically, 3 to 20 times) of the ground pigment. Further, a water-soluble organic solvent having a viscosity such as ethylene glycol, diethylene glycol or polyethylene glycol is further added, followed by kneading and grinding. As the water-soluble inorganic salt used in the grinding aid, sodium chloride, sodium sulfate or the like can be used. After the grinding, it is added to dilute sulfuric acid, water, or the like, and the grinding aid is dissolved, and filtered and washed with water to obtain a filter slurry (pressed cake) of the pigment. The pressed cake is subjected to dispersion processing in a wet disperser as it is, or processed to an oily colorant by flash distillation, or after being dried by hot air, pulverized by a dry pulverizer to be a powder pigment, or even The various coloring agents can be processed depending on the application by dispersion or the like by various wet dispersers, kneaders, and the like. Further, it may be subjected to a resin treatment in water to obtain a dispersible treatment pigment or a processing pigment.

When the black azo pigment of the present invention is used as a coloring agent, an anionic or cationic pigment derivative may be added to the black azo pigment, particularly in the liquid pigment dispersion. The method for adding the pigment derivatives may be a method in which a diazo component or an even component having an ionic group is used in the synthesis of the above pigment, and the method is introduced by an additional method; or an ion synthesized separately is used. The pigment derivative of the base is carried out by a known method such as a method of adding a fine particle formation step or a method of preparing a pigment dispersion. As the pigment derivative at this time, a coloring pigment derivative such as yellow, blue, or red may be appropriately used in addition to black to perform color tone adjustment or the like.

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 Tables 1 and 2, the black disazo pigment ("black pigment-1") obtained in Production Example 1 of the present invention described below was used, and the black pigment prepared in accordance with Example 1 below was contained - 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 0% in the entire wavelength range of 400 to 750 nm across the visible light, and it was confirmed that the transmittance was not exhibited in the visible light region. . On the other hand, as shown in Table 2, in the infrared region of 900 nm, there is a penetration of 34%, while on the longer wavelength side, the transmittance is gradually increased, and in addition, it is expected to be at a higher wavelength. It will also show high penetration.

Table 1: Spectral transmittance of visible light region of black pigment-1

Table 2: Spectral transmittance of the infrared region of black pigment-1

Further, the electrical insulating properties of the coating film containing the black azo pigment of the present invention are similarly as shown in the following Example 1, and the volume specific resistance value of the coating film containing the black pigment-1 is 10 ¹⁴ Ω·cm. It was confirmed that it showed good electrical insulation.

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 as described above. 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. The pigment component of the black azo pigment is used in various forms including a liquid coloring composition in a liquid dispersion medium or a solid coloring composition contained in a solid dispersion medium.

The black azo pigment of the present invention may be used alone as a black azo pigment as a pigment component, or may be selected from a colored pigment, a white pigment, other black pigments and an extender pigment as one of a plurality of pigment components in combination with a target color. Or two or more types may be used in combination with the above. In order to correct the color of the black azo pigment, the blending ratio of the colored pigment, the white pigment, the other black pigment or the extender pigment used in combination with the black azo pigment of the present invention is not particularly limited, and is determined by using a computer-color ratio system. The method of optimization is also the 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 anthraquinone pigment, a quinolinone pigment, a diketopyrrole pigment, a ruthenium/thioxanoid pigment, an anthrone pigment, an anthraquinone pigment, a phthalocyanine pigment, or a porphyrin pigment can be used. , isoporphyrin pigment, isoindolinone pigment, two a pigment, a quinolinone pigment, a nickel azo pigment, a metal complex pigment, an insoluble azo pigment, a soluble azo pigment, a high molecular weight azo pigment, an azomethine black pigment, An organic pigment such as an aniline black pigment; and a mixture of at least one pigment selected from inorganic pigments such as a carbon black pigment and a composite oxide pigment, an iron oxide pigment, and a titanium oxide pigment, or a mixture of two or more pigments, and a mixed crystal pigment.

As the organic pigment, for example, CI Pigment Yellow (abbreviated as PY) of a yellow pigment - 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 (abbreviated as PO) - 61, 64 of an orange pigment, 71, 73, etc., red pigment CI pigment red (abbreviated as PR) - 4, 5, 23, 48: 2, 48: 4, 57: 1, 112, 122, 144, 146, 147, 150, 166, 170, 177, 184, 185, 202, 207, 214, 220, 221, 242, 254, 255, 264, 272, and the like.

Also, CI Pigment Blue (abbreviated as PB) for blue pigments -15:1, 15:2, 15:3, 15:4, 15:5, 15:6, 16, 17:1, 60, 80, Aluminum phthalocyanine blue, green pigment pigment green (abbreviated as PG)-7,36,58, poly(13-16) bromophthalocyanine, etc., purple pigment CI pigment purple (abbreviated as PV)-19, PV-23, PV-37, etc., black pigment aniline black pigment, carbon black pigment, titanium oxide black pigment, etc., especially for CF BM, as a user of the black azo pigment of the present invention, preferably It is a carbon black pigment and a titanium oxide black pigment which are surface-treated and have been improved in insulation.

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. 2005-330466 can also be used. In other words, it is preferable to apply a method in which the infrared ray-absorbing 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 liquid coloring composition containing the black azo pigment of the present invention is mainly used as a coloring agent for coating, impregnating, drawing, printing, etc. on the surface of the article, and can be used for coloring paints, coating agents, and plastics. , fiber coloring, printing ink, stationery, video recording, video display and other uses. The dispersion medium in which the black azo pigment of the present invention is dispersed may further contain a reactive polymer or a non-reactive polymer having a reactive group as a film forming material (or a coating film forming material), and has a reactive group. At least one selected from the group consisting of an oligomer or a non-reactive oligomer and a monomer having a reactive group or a non-reactive monomer having no reactive group, and the liquid itself may or may be further contained Solvent and / or water.

Further, when the liquid coloring composition is prepared, if a high-concentration pigment processed product in which the pigment to be used is finely dispersed in a dispersion medium at a high concentration is prepared in advance, the processed product can be used to easily produce the coloring agent. The liquid high-concentration 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 belonging to a high concentration pigment dispersion, and a bulk material. 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 soap 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 the coloring of absorbing the visible light region and penetrating the infrared ray region, the substrate of the article is made transparent, and the coloring composition is used, by painting, coating, dyeing, printing, taking notes, drawing, inkjet printing. The surface of the transparent substrate is colored by electrophotographic printing, electrostatic printing or photolithography, or internally by coloring the transparent substrate or impregnating the coloring composition. 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, when the black azo pigment of the present invention is used, it exhibits high absorbency and visible light opacity in a wavelength range of about 400 to 750 nm particularly in the visible light region, and is about 900 nm to 1500 nm or more. The infrared region of the wavelength shows a highly penetrating color.

When performing coloring to absorb the visible light region and reflect the infrared ray region, a light-reflective or light-reflective substrate which is light-reflective or formed in advance may be used depending on the material constituting the article itself, and the colored composition of the present invention may be applied thereon. Achieved. The details of this section will be described later. The coloring method at this time can be applied by using a known method such as painting, coating, stocking, dyeing, dip dyeing, printing, taking notes, drawing, inkjet printing, electrophotographic printing or xerographic printing. It exhibits high absorbency in the visible light region and a highly reflective color in the near-infrared region.

The spectral reflectance of the above black pigment-1 was measured, and the results are shown in Table 3. The sample to be measured was coated on a white color paper using a spreader and coated coated paper (hereinafter referred to as black color paper).

Table 3: Spectral reflectance of black color paper of black pigment-1

As shown in Table 3, the coating film containing the black pigment-1 was absorbed from the visible light region to about 750 nm, and showed only a reflectance of about 5%. From about 800 nm to 900 nm, the reflectance sharply increased. The near-infrared region on the longer wavelength side maintains a reflectance of 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. Resin binder used, etc. In addition, examples of the photosensitive resin binder include photosensitive resin adhesives used in various coating materials, coating agents, printing inks, inkjet inks, and photolithography technologies which are ultraviolet curable or electron beam hardened. .

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. Vinyl resin such as resin; polyester resin, amine resin modified polyester resin, polyurethane resin, acrylic polyol ethyl urethane resin, soluble polyamine resin, soluble Polyimide resin, soluble polyamidoximine resin, soluble polyester quinone resin, alkyd resin, amino alkyd resin, epoxy resin, chlorinated rubber resin, polyoxyn resin , fluororesin, cellulose acetate resin, nitrocellulose resin, hydroxyethyl cellulose, water-soluble salt of styrene-maleate copolymer, (meth) acrylate The (co)polymer water-soluble salt, the water-soluble amino alkyd resin, the water-soluble amine-based polyester resin, and the water-soluble polyamine resin may be used singly or in combination of two or more.

Examples of the reactive group of the reactive film forming material include a methylol group, an alkylhydroxymethyl group, an isocyanate group, a masking isocyanate group, and an epoxy group. Further, an oligomer or a monomer may be used depending on the application, and a crosslinking agent such as a methylol 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 an ultraviolet curable resin or an electron beam curable resin used in the present invention include a photosensitive cyclized rubber resin and a photosensitive phenol resin. Photosensitive polyacrylate resin, photosensitive polyamido resin, photosensitive polyimide resin, and the like; and unsaturated polyester resin, polyester acrylate resin, poly epoxy acrylate resin, A binder such as 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, vinyl chloride resin, methacrylic resin, polycarbonate, polyamide, polyacetal, thermoplastic polyester, cellulose-based plastic, epoxy benzene resin, fluororesin, Thermoplastic elastomers, etc., or unsaturated polyester resins of thermosetting plastics, epoxy resins, polyoxyxylene resins, polyurethane resins, melamine resins, phenol resins, and the like.

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 the purpose of use, and cannot be generalized. For example, in coatings, coating agents, dyeing agents, printing inks, toners for printers, and inks for ink jetting, which are equivalent to coloring on the surface, since the film thickness is thin, the coloring agent contains black pigment. The content is about 3% to 80%, preferably about 5% to 60%. In particular, when it is used as a light-shielding black material of BM of CF, the film thickness is extremely thin, and complete light-shielding property is required, so that the pigment is stably dispersed and maintained at a viscosity suitable for coating, and a uniform colored film is formed. The pigment concentration of the boundary is preferably about 30% to 60%.

Further, in the case where the material which is colored by the coloring of the plastic or the coloring of the woven fabric is internally colored, it is also about 0.05% to 20%, preferably about 0.1% to 10%, depending on the thickness of the colored product. %about.

In the case where the coloring composition for image recording containing the black azo pigment of the present invention is used as a coloring composition for forming BM of CF, the colored composition is directly or transferred or attached to the CF substrate. A plastic film and a method of forming one or more selected by photolithography, laser/ablation method, inkjet printing method, printing method, transfer method, and attaching method And formed.

The film thickness of BM is 0.5 μm to 3 μm, and usually 1 μm to 2 μm. The optical density (OD) value is 2.0 or more, preferably 3.0 or more. In the case where the BM itself is thickened, it is preferable to laminate the pixels or laminate the colorless resin film, and it is preferably 5 μm to 10 μm.

Further, on the CG substrate on which the BM is formed, a known color pixel forming coloring agent can be further used to form a color pixel by a known pixel forming method.

In the present invention, as an article having advantages with respect to a CF substrate or an organic EL light-emitting substrate, the following may be mentioned. That is, a CF substrate or an organic EL light-emitting substrate in which a BM that absorbs a wavelength range of a visible light region is formed, in particular, a BM is substantially more electrically insulating, and a CF substrate or an organic EL light-emitting formed by overlapping the BM and the electrode is exemplified. a substrate, and a color display panel comprising the same. Similarly, a CF substrate on which BM and colored pixels are formed or a liquid crystal color display device mounted thereon, or an organic EL color display device equipped with the above 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, the examples are given to further illustrate the invention. In addition, "g" or "%" is a quality standard without any particular limitation.

[Manufacturing Example 1] (Manufacture of "Black Pigment-1") (1) Synthesis of black disazo pigment

After adding concentrated hydrochloric acid to 2.44 g (0.01 mol) of 3,3'-dimethoxy-4,4'-benzidine as a hydrochloride, the excess sodium nitrite aqueous solution was added to carry out heavy weight. Nitriding. Next, boron oxyhydrogen acid is added thereto to prepare a 3,3'-dimethoxy-diphenyl (4,4'-tetrakis) borate double salt (diazonium salt). In addition, 7.65 g (0.02 mol) of 2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxy-p-aniline as a coupling component was dissolved in 250 g of methanol having dissolved sodium hydroxide 0.8 g. Modulation in the middle. The previously prepared tetranitride ‧ boron fluoride double salt solution was kept at 15 ° C or lower, and the solution of the above-mentioned prepared coupling component was slowly added thereto. Then, the pH was adjusted to 6.5 to 7.0 with sodium acetate, and the mixture was stirred for 1 hour, and then stirred at 25 ° C for 2 hours, and further heated to 40 ° C and stirred for 3 hours to terminate the coupling reaction. After the produced pigment was filtered, the filtrate was washed with methanol, followed by washing with water, followed by drying to obtain a crude pigment of a black azo pigment. The yield of the obtained black azo pigment was 9.78 g.

(2) Modulation of finely divided black particle pigments

100 parts of the coarse particle pigment of the black azo pigment obtained by the synthesis reaction of the above (1), together with 500 parts of sodium chloride powder and 50 parts of diethylene glycol, are added to a kneading machine equipped with a pressure cap, The coarse particle pigment and the sodium chloride powder in the kneader are uniformly wetted until they are uniformly wetted. Next, the pressure cooker was closed, and the contents were pressed in at a pressure of 6 kg/cm ² , and kneaded and ground. Specifically, while the temperature is managed at 92 to 98 ° C depending on the contents, the kneading/grinding treatment is performed for 2 hours. The obtained ground product was stirred for 1 hour in 3000 parts of warm water heated to 80 ° C, and then filtered, and the obtained filtrate was washed with water to remove sodium chloride and diethylene glycol. A pressed cake of finely divided black azo pigment is obtained.

The particle diameter of the pigment obtained above was measured by the following method. A transmission electron microscope photograph (60,000 times) of the black pigment obtained was photographed, and a particle size distribution was measured using "Image Resolution Particle Size Distribution Software Mac-View" (manufactured by Mountech). This result was an average particle diameter of 50 nm. Further, in the other production examples, the average particle diameter of the pigment was measured in the same manner as described above.

Next, after drying the pressed cake obtained above, it is pulverized to obtain 3,3'-dimethoxy-extended biphenyl (4,4'-) bis(azo(-1)- A finely divided powder pigment of a black pigment of 2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxy-p-benzidine.

[Production Example 2] (Manufacture of "Black Pigment-2")

In the same manner as in Production Example 1 (1), 2.44 g (0.01 mol) of 3,3'-dimethoxy-4,4'-benzidine was diazotized. Then, it was coupled with 8.17 g (0.02 mol) of 2-hydroxy-11H-benzo[a]-oxazolyl-3-carboxy-N-benzimidazolone-5-decylamine to obtain a black couple. A crude pigment of nitrogen pigment. The yield of the obtained black azo pigment was 10.07 g.

Next, the finening treatment of the obtained crude pigment is performed. In the method, the amount of sodium chloride used in the (2) of Production Example 1 was used in an amount equal to 8 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 acidic water, the mixture is 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 25 nm. Further, 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-2".

[Production Example 3] (Manufacture of "Black Pigment-3")

In the same manner as in Production Example 1 (1), 2.53 g (0.01 mol) of 3,3'-dichloro-4,4'-benzidine was diazotized. Then, it was coupled with 7.93 g (0.02 mol) of 2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxy-(2'-methyl)-p-aniline to obtain black azo. A crude pigment of pigment. The yield of the obtained black azo pigment was 10.26 g.

Next, the finening treatment of the obtained crude pigment is performed. The finening treatment was carried out in the same manner as in Production Example 1 (2) except that the amount of sodium chloride used in the place (2) contained in Production Example 1 was 10 times the amount of the pigment. Then, after the salt or the like is dissolved by acidic water, the mixture is 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 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".

[Manufacturing Example 4] (Manufacture of "Black Pigment-4")

In the same manner as in Production Example 1 (1), 2.44 g (0.01 mol) of 3,3'-dimethoxy-4,4'-benzidine was diazotized. Then, it was coupled with 7.93 g (0.02 mol) of 2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxy-(2'-methyl)-p-aniline to obtain black azo. A crude pigment of pigment. The yield of the obtained black azo pigment was 9.94 g.

Next, the finening treatment of the obtained crude pigment is performed. The fineness treatment was carried out in accordance with (2) described in Production Example 1, and the salt or the like was dissolved in acidic water and filtered, and then 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 50 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-4".

[Manufacturing Example 5] (Manufacture of "Black Pigment-5")

In the same manner as in Production Example 1 (1), 2.53 g (0.01 mol) of 3,3'-dichloro-4,4'-benzidine was diazotized. Then, it was coupled with 7.56 g (0.02 mol) of 2-hydroxy-11H-benzo[a]-carbazolyl-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. The finening treatment was carried out in the same manner as in Production Example 1 (2), except that the amount of sodium chloride used in the place (2) contained in Production Example 1 was used in an amount of four times the amount of the pigment. Then, after the salt or the like is dissolved by acidic water, the mixture is 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 85 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-5".

[Manufacturing Example 6] (Manufacture of "Black Pigment-6")

In the same manner as in Production Example 1 (1), 2.44 g (0.01 mol) of 3,3'-dimethoxy-4,4'-benzidine was diazotized. Then, it was combined with 2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxy-(2'-methyl)-p-aniline 3.96 g (0.01 mol) 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 obtained above was pulverized by a dry pulverizer to be pigmented to obtain a fine powder pigment of a black pigment. The pigment obtained had an average particle diameter of 110 nm. Hereinafter, this material is referred to as "black pigment-6".

[Production Example 7] (Manufacture of "Black Pigment-7") (1) Manufacture of black pigment derivative-1

1.73 g (0.01 mol) of sulfamic acid was diazotized. Then, it was coupled with 3.82 g (0.01 mol) of 2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxy-p-aniline. Next, after the obtained product was filtered, it was washed with water to obtain a pressed cake having a black pigment derivative of a sulfonic acid group. Hereinafter, this material 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 having a sulfonic acid group-containing pigment derivative. 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 production example 1 and the pressed cake of the black pigment derivative-1 obtained according to the above (1) were 10:1 by the solid content ratio of the pigment. The method is formulated and thoroughly mixed to make it uniform. Then, the above mixture is dried to obtain a crude pigment containing a black pigment of a pigment derivative. Next, in the case of (2) in the production example 1, after the finening treatment of the pigment, the salt or the like is dissolved by acidic water, and the obtained filtrate is washed with water to obtain a black even. Pressed cake of nitrogen pigment. The pigment obtained had an average particle diameter of 50 nm. The pressed cake is dried and pulverized to obtain a fine powder pigment of a black pigment containing an anionic pigment derivative. Hereinafter, this material is referred to as "black pigment-7".

[Production Example 8] (Manufacture of "Black Pigment-8")

A cationic pigment derivative was synthesized by the method described in Japanese Patent No. 3268748. Specifically, first, a reaction ratio of 1-aminoindole, bis(N,N-dimethylaminopropyl)amine, and cyanuric chloride is 2:1:1, thereby Synthesis of 2,4-bis(decylamino)-6-bis(N,N-dimethylaminopropyl)amino-s-three as a cationic pigment derivative . The pressed cake of the obtained cationic pigment derivative and the pressed cake of the black pigment-1 obtained in Production Example 1 (1) were blended in such a manner that the solid content ratio was 85:15. Then, after the mixture is sufficiently mixed to be uniform, it is dried to obtain a crude pigment containing a black pigment of a cationic pigment derivative. Next, 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 fine 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] (Manufacture of "Black Pigment-9")

In the same manner as in Production Example 1 (1), after diazotization of 1.95 g (0.008 mol) of 3,3'-dimethoxy-4,4'-benzidine, borofluoric acid was added thereto to prepare four. Nitrogen salt ‧ boron fluoride double salt (diazonium salt). In addition, 0.69 g (0.004 mol) of sulfamic acid was diazotized. The two kinds of diazonium-containing liquids are simultaneously coupled with 2-hydroxy-11H-benzo[a]-oxazolyl-3-carboxy-p-aniline 7.65 g (0.02 mol), and the above two types of diazonium The droplets of the liquid are adjusted in such a manner that they are finished at the same time, and are coupled. Thereafter, filtration and water washing 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 fine treatment of the obtained crude pigment was carried out. Specifically, after the fine treatment was carried out in the method of (2) in Production Example 1, the salt or the like was dissolved with acidic water, filtered, and the obtained 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 pressed cake was dried, it was pulverized to obtain a fine powder pigment of a black pigment. Hereinafter, this material is referred to as "black pigment-9".

[Production Example 10] (Manufacture of "Black Pigment-10")

In the same manner as in Production Example 1 (1), 4.85 g (0.02 mol) of 2-methoxy-5-N-phenylamine-mercaptoaniline was diazotized to give a 1,4-phenylene group. Bis(2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxydecylamine) 6.27 g (0.01 mol) was coupled to obtain a crude pigment of a black azo pigment. The yield was 10.35 g. Next, pulverization was carried out by a dry pulverizer to obtain a fine powder pigment of a black pigment. Hereinafter, this material is referred to as "black pigment-10". The pigment obtained had an average particle diameter of 80 nm.

[Example 1] (Evaluation of optical characteristics of coating film containing black pigment-1 of Production Example 1) (1) Modulation of black coated PET film using black pigment-1

In order to observe the optical characteristics of the black pigment-1 obtained in Production Example 1, a black coating liquid was prepared. As the wax to be used, a 50% xylene-butanol mixed solvent solution (acid value: 10 mgKOH/g) of a carboxyl group-containing acrylic resin and 50% xylene-butanol of a butylated methylol melamine resin. The mixed solvent solution was prepared at a ratio of 80:20 to prepare a wax (hereinafter, this product is referred to as "wax"). 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 dilution 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 10 minutes, and then taken out to be 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 resulting black coating film had an average dry film thickness of 34 nm.

(2) Measurement of transmittance in visible light region and near infrared region

The black-coated PET film obtained in the above (1) was measured for the transmittance of the visible light portion and the near-infrared portion by a Hitachi spectrophotometer (U-4100 model, manufactured by Hitachi Manufacturing Co., Ltd.). In Tables 4 and 5, the measurement results of the respective regions are shown.

Table 4: Spectral transmittance of visible light region of black coated film using black pigment-1

Table 5: Spectral transmittance of the infrared region of a black coated film using black pigment-1

As shown by the measurement results of the light transmittance of Table 4 and Table 5, the coating film containing black pigment-1 spans the entire wavelength range of 400 to 750 nm in the visible light region, and the spectral transmittance is 0%, which is almost impossible to confirm. Penetration (refer to 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 specific resistance was measured for the black coating film on the PET film obtained as described above using a high resistivity meter Hiresta-UP [manufactured by Mitsubishi Chemical Co., Ltd.]. The measurement results showed 10 ¹⁴ Ω ‧ cm, and it was confirmed that the insulation was very high.

[Example 2] (Evaluation of light reflection characteristics of a coating film containing the black pigment-1 of Production Example 1) (1) Modulation of black color paper using black pigment-1

In order to observe the reflection characteristics of the black pigment-1, the black coating liquid prepared in the first place (1) of Example 1 was coated on a white color development paper, and dried using a 6 mil applicator. And hardening, and the black-coated color-developing paper which formed the coating film (it is hereafter called a black-color display paper) is obtained. The measured value of the dry film thickness of the black coating film formed on the black color development paper was 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 development paper obtained in the above (1) were measured, and the measurement results are shown in Table 6.

Table 6: Spectral reflectance of black color paper using black pigment-1

From the results shown in Table 6, it was confirmed that the black color paper made of black pigment-1 showed only a reflectance of 5 to 6% at around 750 nm, and the reflectance increased sharply at 800 nm to 900 nm. Further, in the near-infrared region on the longer wavelength side, it is about 70% to 80%, or the reflectance thereof is maintained. As can be seen 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, the black pigment has high light transmittance, and it is shown that the substrate having high reflectivity can effectively reflect near infrared rays. Further, in the above Table 6, at about 750 nm, the reflectance is not 0% but a value of 5%, which is due to the relationship of the measuring device.

[Example 3]

(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 in the same manner as in Example 1, the light-transmitting of the visible light region and the infrared region was measured. rate. The results are shown in Tables 7 and 8.

Table 7: Spectral transmittance (%) of the visible light region of black color paper using black pigment-2~6

Table 8: Spectral transmittance (%) of the infrared region of black color paper using black pigment-2~6

(2) In the same manner as in Example 2, black pigments 2 to 6 obtained in each of Production Examples 2 to 6 were used to form a black coating film, and black-colored paper was separately produced. The dry film thickness of the black coating film is about 35 to 40 nm on the black color development paper. The spectral transmittance was measured in the same manner as in Example 2. As a result, as shown in Table 9, the spectral reflectance showed the same tendency as the black stretch paper obtained by using the black pigment-1.

Table 9: Spectral reflectance of visible light and infrared regions of black pigments 2 to 6 (%)

[Example 4] (Polycarbonate resin molded plate)

20 parts of the black pigment-2 prepared in the production example 2 and 80 parts of the polycarbonate resin powder were sufficiently mixed by a Michelle mixer (powder high-speed mixer), and then mixed by a twin-screw extruder. After mixing, a black resin batch containing a black pigment-2 20% polycarbonate resin was prepared. Two parts of the obtained black main batch were prepared to 100 parts of polycarbonate pellets composed of the same resin powder as described above, and mixed by a Michelle mixer, followed by mixing and kneading by a twin-axis extruder. And made into black resin particles. The obtained black resin pellets were molded by an in-line spiral injection molding machine to obtain a black polycarbonate resin flat plate excellent in pigment dispersibility. The black resin plate absorbs light in the visible light region and can penetrate the near infrared rays sufficiently, and 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 sufficiently mixed by a Michelle mixer, followed by a double The shaft press-out mixer was mixed and kneaded to prepare a black body batch containing an acrylic resin containing 20% of black pigment-3.

Two parts of the obtained black main batch were prepared to 100 parts of the acrylic resin pellets composed of the same resin powder as described above, and then further mixed by a Michelle mixer, followed by a biaxial extrusion kneader. Mix and knead to make black resin particles. The obtained black resin pellets were molded by a linear spiral injection molding machine to obtain a black acrylic resin flat plate excellent in pigment dispersibility. The black resin plate absorbs light in the visible light region and can penetrate the near infrared rays sufficiently, and can be used as an infrared penetrating filter.

[Example 6] (polyurethane coating agent)

15 parts of black pigment-4 prepared according to Production Example 4, 10 parts of polycarbonate-free yellowing-resistant polyurethane resin, and 75 parts of dimethylformamide (hereinafter referred to as "DMF"). In a manner, a black pigment and a polycarbonate-free yellowing-type polyurethane resin solution, DMF were blended. This blending liquid was sufficiently dispersed by a horizontal continuous medium disperser to obtain a black pigment high-concentration dispersion. Next, 10 parts of propyl acetate as a diluent solvent was added to 100 parts of a polycarbonate-based non-yellowing type polyurethane resin solution (solid content 30%, DMF solvent) for forming a skin layer. 10 parts of propanol and 20 parts of the high-concentration dispersion of the black pigment prepared previously were mixed and mixed to prepare a black polyurethane coating liquid.

Next, the black coating liquid prepared above was applied to a release paper DNTP-155T-FLAT (trade name, manufactured by Dainippon Printing Co., Ltd.) to have a sheet thickness of 50 μm, and then applied to 100 sheets. Drying was carried out under conditions of ° C/10 minutes to form a skin layer. In addition, a polycarbonate-based yellow-denatured polyurethane resin solution (solid content: 70%, toluene: methyl ethyl ketone (hereinafter referred to as "MEK") = 1:1 solvent) was prepared as an adhesive. In 100 parts, 10 parts of toluene as a diluent solvent, 20 parts of MEK, 20 parts of DMF, and 10 parts of a modified polyisocyanate-based crosslinking agent (solid content: 75%, ethyl acetate solvent) and an amine-based crosslinking catalyst ( The solid content is 0.5% MEK solvent) 0.15 parts. Then, the adhesive was applied onto the surface of the skin layer (the surface opposite to the surface contacting the release paper) to a sheet having a thickness of 75 μm, and then dried at 80 ° C for 5 minutes. The sheet having the obtained back layer and the skin layer was laminated on the back layer side to the substrate (fabric) to form a laminate having a total thickness of 1,100 μm, and the obtained laminate was separated by a laminate drum heated to 100 ° C. The gap of 500 μm was opened and pressure-bonded. Next, after aging at 60 ° C / 48 hours, it was peeled off from the release paper to obtain a synthetic hide. The synthetic pseudo-skin system obtained is excellent in durability such as heat deterioration resistance, hydrolysis deterioration resistance, photodegradation resistance, and oleic acid resistance, and is suitable for vehicle use and the like, in addition to reducing (reducing) heat buildup.

Further, the above-mentioned adhesive used contains a white pigment to be colored white, thereby imparting light reflectivity to the adhesive layer, and forming a black azo pigment containing optical properties exhibiting both visible light blocking properties and infrared penetrating properties. In the double structure of the skin layer, a polyurethane-synthesized leather which can reflect heat rays is obtained. This synthetic leather is especially suitable for automotive interiors and other purposes.

[Example 7] (raw liquid colored woven fabric)

50 parts of the black pigment prepared in Production Example 5 and 50 parts of the ethyl bis-stearate powder as a pigment dispersion meter were mixed by a Michelle mixer to obtain a powder coloring agent having a pigment content of 50%. (dry color). Next, 1.0 part of the obtained dry color was blended to 99.0 parts of polypropylene resin pellets, and then mixed by a Michelle mixer, followed by kneading using a zigzag type 40 m/m extruder, whereby the pigment was divided into 0.5%. Black resin particles. The obtained black resin pellets were woven in a melt spinning machine to obtain a vivid black polypropylene stock-colored woven fabric excellent in pigment dispersibility of 10 denier. The woven fabric made of the colored woven fabric can be expected to avoid the effect of warming because it can reflect the heat rays of direct sunlight. Therefore, it is especially suitable for sun umbrellas or curtains.

[Example 8] (resin molding)

5 parts of black pigment prepared in Preparation Example 6, 20 parts of titanium oxide white pigment, and 75 parts of polyethylene resin powder as a pigment dispersion meter were mixed by a Micheler mixer 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 PBT resin molded plate excellent in pigment dispersibility. The obtained resin-formed sheet is because it can reflect heat rays of direct sunlight. Therefore, it is suitable for use of a resin molded article which avoids heating.

[Embodiment 9] (heat shield back cover for solar power generation module)

(1) After 15 parts of black pigment-4 prepared in Production Example 5, 25 parts of an acrylic acid polyol (hydroxyl: 100) butyl acetate solution (solid content: 50%), and 50 parts of butyl acetate were sufficiently prepared and mixed. A pigment dispersion was carried out using a horizontal continuous medium disperser using glass beads as a dispersion medium to prepare a black pigment high-concentration dispersion.

To 90 parts of the black pigment high-concentration dispersion obtained above, 22 parts of the same butyl acrylate acetate solution as described above was added, and the benzotriazole-based monomer and the HALS-based monomer were copolymerized with acrylic acid. 50 parts of an alcohol (hydroxyl price: 100) butyl acetate solution was used for black ink formation. Next, 24 parts of a trimeric isocyanate type hexamethylene diisocyanate trimer (solid content: 100%, isocyanate %: 21.7%) as a hardener was added to the black inkizer, and after sufficiently mixing, acetic acid was added. Approximately 20 parts of butyl ester, adjust the viscosity, and prepare a black coating solution.

(2) 40 parts of the titanium oxide white pigment, and 40 parts of the butyl acrylate acetate solution used in the above (1), and 20 parts of butyl acetate, and then used in the same manner as in the above (1) The horizontal continuous media disperser performs pigment dispersion to prepare a white pigment high concentration dispersion.

To 140 parts of the white pigment high-concentration dispersion obtained above, 44 parts of an acrylic acid butyl acetate solution was added to white ink. Then, 18 parts of the same hexamethylene diisocyanate trimer as the hardener was added to the white inkizer, and after thorough mixing, about 40 parts of butyl acetate was added to adjust the viscosity, and the preparation was adjusted. White coating solution.

(3) On the surface of a polyethylene terephthalate (PET) substrate sheet (film thickness: 100 μm), the black coating liquid prepared in the above (1) was applied and dried to form a black coating film (dry). Film thickness: 5 μm). Then, the white coating liquid prepared in the above (2) was applied to the back surface of the substrate, and dried to form a white coating film (dried film thickness: 5 μm), and a black coating film was applied on the surface and a white coating was formed on the back surface. A black-white multi-layer PET film coated with a film.

(4) In order to further impart water vapor barrier properties and gas barrier properties to the black-and-white multi-layer PET sheet obtained in the above (3), the white coating film surface on the back surface overlaps, and the cerium oxide ‧ alumina is vapor-deposited An ester film (film thickness: 12 μm) was laminated, and a PET substrate sheet (film thickness: 100 μm) was further laminated thereon to prepare a PET back cover sheet for a solar power generation module. In the above lamination, the following adhesives were used. As the adhesive, an adhesive composed of 70 parts of an acrylic polyester solution, 15 parts of a hexamethylene diisocyanate trimer and 15 parts of butyl acetate was used in the same manner as in the above (1).

The PET back cover sheet coated with the black coating film and the white coating film obtained as described above in a plurality of layers has a black appearance and is excellent in appearance, and the optical properties of the black pigment-4 used have the above optical properties. By. That is, the light in the infrared region of the sunlight penetrates the black coating layer on the surface, and the light that has penetrated the infrared region is reflected on the white layer of the substrate and penetrates the black layer again to be radiated to the outside. Therefore, since the back cover sheet exhibits excellent heat shielding properties by absorbing less sunlight, it is particularly suitable as a back cover sheet for a solar power generation module that avoids temperature rise.

When the cover sheet obtained as described above is used as a solar power generation module, it can be used as follows according to a conventional method. In other words, the solar power generation unit is sandwiched and sealed by a sealing material made of vinyl acetate-based vinyl resin, and a surface sealing sheet is attached to the surface of the light-receiving surface side to protect the non-light-receiving side of the back surface. In the sheet, the black surface of the light-shielding back cover is bonded to the light-receiving side, and the transparent glass substrate is attached to the light-receiving surface, whereby a solar power generation module can be produced.

[Embodiment 10] (heat shielding back cover for solar power generation module)

(1) 40 parts of the black pigment-6 obtained in Production Example 6 and 60 parts of the polyester resin powder were mixed by a Micheler mixer to obtain a powdery coloring agent. Next, 12.5 parts of the obtained powdery coloring agent was blended to 87.5 parts of PET resin pellets, and the mixture was mixed by a Michelle mixer, and then kneaded by a twin-screw extruder to prepare black resin pellets by a granulator. Next, molding was carried out by a T-die extruder to prepare a black PET film having a film thickness of 50 μm.

(2) A white PET sheet (film thickness: 180 μm) which was kneaded by a titanium oxide pigment was prepared. Then, the same acrylic polyol ‧ hexamethylene diisocyanate-based adhesive as described in (4) of Example 9 was applied to the surface thereof, and the black PET film obtained in the above (1) was attached thereto to form a laminated black. 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 on the back surface of the sheet. A diisocyanate-based adhesive, and a cerium oxide-alumina-deposited polyester film is laminated. Then, a PET substrate sheet (film thickness: 100 μm) was laminated thereon using the same adhesive as above to form a back cover for a solar power generation module.

The back cover sheet 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 is based on the optical characteristics of the black pigment-6 used. Those having the following optical properties. 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 PET sheet below, and penetrates the black film again to be radiated to the outside. Therefore, the black-and-white multi-layer PET sheet exhibits excellent heat shielding properties by absorbing less sunlight, and is therefore particularly suitable as a back cover for solar power generation modules that avoid temperature rise.

When the cover sheet obtained as described above is used as a solar power generation module, it can be used as follows according to a conventional method. In other words, the solar power generation unit is sandwiched and sealed by a sealing material made of vinyl acetate-based vinyl resin, and a surface sealing sheet is attached to the surface of the light-receiving surface side to protect the non-light-receiving side of the back surface. In the sheet, the black surface of the light-shielding back cover is bonded to the light-receiving side, and the transparent glass substrate is attached to the light-receiving surface, whereby a solar power generation module can be produced.

[Example 11] (dyeing agent for woven fabric)

After the black pigment-1 obtained in the production example 1 and the 25 parts of the pressed cake, the nonionic pigment dispersant 10 parts, the antifoaming agent 1 part, and the water 18 parts were sufficiently prepared and mixed, The pigment dispersion was carried out in a horizontal continuous medium disperser using glass beads as a dispersion medium to prepare a black pigment high-concentration dispersion (black color substrate). 20 parts of the obtained black color substrate, 25 parts of reactive alkyl acrylate latex (solid content 40%), 0.5 part of antifoaming agent, 1 part of dispersing agent, 3 parts of dispersion stabilizer for oil droplet type emulsification in water, ore 38 parts of material slugs and 12.5 parts of water were emulsified and dispersed according to a homogenizer (strong emulsification disperser) to prepare an oil droplet type black emulsion slurry in water. Then, 2 parts of a carboxydiamine-imine crosslinking agent (solid content 40%) was added to the prepared black emulsion slurry, and the mixture was sufficiently mixed to prepare a black paste. The obtained black was dyed on a polyester-cotton blend fabric and printed on the entire surface, and hardened at 120 ° C for 15 minutes to obtain a black baseless dye cloth which can shield the heat rays.

[Example 12] (gravure printing ink)

The black pigment -10 11 parts obtained in Production Example 10 was added to a 40% methyl ethyl ketone-toluene (1:3) of a polyurethane resin having a chain length extended by an isocyanate terminal polyester. The solvent solution was mixed in 30 parts. Next, 2 parts of a cationic polymer dispersant, 2.5 parts of a 40% toluene solution of a polycarboxy quinone imine compound derived from methylphenyl diisocyanate, and methyl ethyl ketone-toluene-isopropanol (50:30) were added. : 20) 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 prepare a 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 film which exhibited optical characteristics of shielding visible light and penetrating infrared rays.

[Example 13] (Formation of BM of CF) (!) (modulation of pigment dispersion for BM) (modulation of black pigment dispersion)

The black pigment obtained in Preparation Example 9 was 25 parts, benzyl methacrylate-methacrylic acid-2-hydroxyethyl methacrylate copolymer (Morby: 60:20:20, weight average 20 parts of a molecular weight of 30,000) 40% solution, 2 parts of a cationic polymer-based dispersing agent, and 53 parts of propylene glycol monomethyl ether acetate (PGMA) were sufficiently prepared and 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-1").

(2) (modulation of photosensitive black photoresist ink)

40 parts of the black pigment dispersion obtained in the above (1), 6 parts of a 50% PGMA solution of an acrylated acrylic polyol photosensitive resin, 1 part of trimethylolpropane triacrylate, and dipentaerythritol hexaacrylate 1 Ethyl ketone as a photopolymerization initiator, 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-carbazolyl-3-yl]-, 1-(O- Ethyl acetate ("IRGUCURE OXE02", manufactured by BASF) 1 part and PGMA 51 parts. Thereafter, the mixture was sufficiently stirred and homogenized by a high-speed stirrer, and then filtered using 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)

The photosensitive black photoresist ink-1 obtained above was applied onto a glass substrate by a spin coater. Then, after preliminary drying at 60 ° C, prebaking was performed, and after exposure with an ultrahigh pressure mercury lamp at a light amount of 400 mJ/cm, post-baking was performed at 230 ° C for 30 minutes to obtain a black coating film having a thickness of 3 μm. (black photoresist ink film).

The optical characteristics of this coating film were as shown in Table 10, showing high absorption 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. Moreover, the volume specific resistance of the coating film was 10 ¹⁴ Ω ‧ cm or more, and high insulation was confirmed.

(4) (modulation of BM pattern)

Using the photosensitive black photoresist ink-1 obtained above, it was applied onto a glass substrate by a spin coater in accordance with a usual method, and then prebaked at 80 ° 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 with an alkali 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 insulating properties as described in the above (3). Therefore, various CF improving methods for forming BM on an active device such as a TFT can be used, for example, instead of the spacer. The structure of the BM, IPS mode, COA mode, etc., which maintains the thickness of the liquid crystal layer. Further, since the BM film can sufficiently absorb the visible light region up to the long wavelength region, it is also possible to use a BM which is an LCD panel using an LED backlight.

(5) (modulation of each pigment dispersion of red, green, blue, yellow, and purple)

In the same manner as described in the above (1), PR254 (diketopyrrolepyrrole pigment), PR177 (lanthanide red pigment), PG36 (copper phthalocyanine green pigment), PB15:6 (ε-type phthalocyanine) were used. Blue pigment), PY138 (yellow pigment) and PV23 (two For each of the pigments of the violet pigment, 1 part of a pigment derivative having a known sulfonic acid group corresponding to each pigment was added to 19 parts of the pigment to obtain a pigment composition of each color. Using the obtained pigment composition, various pigment dispersion liquids each having a pigment content of 20%, a resin dispersant of 6%, red, green, blue, yellow, and purple were prepared.

Next, 33 parts of the pigment dispersion liquid which was prepared by containing the above-prepared PR254 and PR177 in a ratio of 8:2 was used, and a photosensitive resin 50% solution was added in the same manner as described in the above (2). Red resist ink was prepared by preparing 9.2 parts, 3 parts of photopolymerizable monomer, 0.3 part of photopolymerization initiator, and 54.5 parts of solvent. Similarly to the above, the pigment dispersion liquid containing PG36 and PY138, respectively, is blended at a ratio of 5:5, and the pigment dispersion liquid containing PB15:6 and PV23, respectively, is blended at a ratio of 8:2. The green photoresist ink and the blue photoresist ink are separately modulated.

(6) (formation of CF RGB pixels)

The glass substrate on which the BM was formed in accordance with the above (4) was attached to a spin coater, and the prepared photosensitive red photoresist ink was spin-coated, and then prebaked at 80 ° C for 10 minutes. Then, a mask having a mosaic pattern was exposed on the coated surface of the glass substrate using a proximity exposure machine in an amount of light of 100 mJ/cm ² of the ultrahigh pressure mercury lamp. Next, development is carried out using a dedicated developer and a special rinsing agent, followed by washing and drying to form a red mosaic pattern on the glass substrate. Further, in the same manner as described above, a green mosaic pattern was formed using a photosensitive green photoresist ink, and a blue mosaic pattern was formed using a photosensitive blue photoresist ink to obtain CF in which BM and RGB pixels were formed.

Further, in the same manner as described above, the photosensitive black resist ink was prepared in the same manner as described above except that the black pigment-9 used in the above-described manner was used instead of the black pigment-9 used in the above, and the BM pattern and the BM pattern were formed. RGB pixel pattern to obtain CF formed with BM and RGB pixels.

[Example 14] (Formation of BM of CF) (1) (Modulation of pigment dispersion for BM) (modulation of black pigment dispersion)

In the same manner as in Example 13 (1), the black pigment-8 was substituted for the black pigment-9, and the same benzyl methacrylate-methacrylic acid-2-hydroxyethyl group was used previously. After 25 parts of the methacrylate copolymer 40% solution and 53 parts of propylene glycol monomethyl ether acetate (PGMA) were thoroughly prepared and mixed, the pigment was dispersed by a continuous horizontal media disperser to obtain black pigment dispersion. liquid. Hereinafter, this material is referred to as "black pigment dispersion-2".

(2) (modulation of photosensitive black photoresist ink)

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 instead of the black pigment dispersion liquid-1 at (2) described in Example 13. . Hereinafter, this material is referred to as "photosensitive black photoresist ink-2".

(3) (modulation of BM pattern)

In the same manner as described in (13) of Example 13, the photosensitive black resist ink-2 was applied onto a glass substrate by a spin coater, and prebaked to obtain a black coating film having a thickness of 3 μm. The coating film was exposed to a negative mask pattern of a BM pattern, and exposed using an ultrahigh pressure mercury lamp. After development with an alkaline developing solution, it was washed with water and dried to form a BM pattern.

The BM film forming the BM pattern can be used for various CF improvement methods for forming BM on the active device, for example, in place of the BM of the fixed spacer, or IPS, because of its high electrical insulating properties. The structure of the mode, COA mode, etc. Further, since the visible light region can be sufficiently absorbed until the long wavelength region, the BM which is an LCD panel using the LED backlight can be used.

(4) (formation of CF RGB pixels)

The glass substrate on which the BM obtained in the above (3) was formed was attached to a spin coater in the same manner as described in Example 13 (6), and the photosensitive red color obtained in (5) described in Example 13 was used. The photoresist ink, the photosensitive green photoresist ink, and the photosensitive blue photoresist ink form a mosaic pixel pattern of each color to obtain CF in which BM and RGB pixels are formed.

[evaluation result]

The CFs obtained in Examples 13 and 14 have CFs having excellent color properties and optical properties such as fineness, color density, light transmittance, and contrast properties.

Claims (17)

A black azo pigment which exhibits two optical characteristics of visible light blocking property and infrared light transmittance; the optical property is a black colored film containing the black azo pigment on a transparent substrate in the visible light range of 400 to 750 nm In the wavelength range, the spectral transmittance of 5% or less is exhibited. Further, the black colored film exhibits a transmittance of 30% or more in the wavelength range of 900 to 1500 nm in the infrared region; the black azo pigment is attached to the molecule. There are two or more azo bonds and at least one 2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxylic acid carboamide residue introduced by the even component, and at least The black polyazo pigment of any one of (1) to (4), which has an average particle diameter of 10 nm to 200 nm; (1) as a diazo component, which is selected from a 1,4-phenylene group Diamine, 2-chloro-1,4-phenylenediamine, 2,5-dichloro-1,4-phenylenediamine, 2-chloro-5-methyl-1,4-phenylene Diamine, 2,5-dimethyl-1,4-phenylenediamine, 2-nitro-1,4-phenylenediamine; 1,3-phenylenediamine, 4-chloro- 1,3-phenylenediamine, 4-methoxy-1,3-phenylenediamine, 4-nitro-1,3- Phenyldiamine; 4-chloro-1,2-phenylenediamine, 4,5-dimethyl-1,2-phenylenediamine, 4-nitro-1,2-phenylene Amine; 3,3'-dichloro-4,4'-benzidine, 2,2',5,5'-tetrachloro-4,4'-benzidine, 3,3'-dimethyl-4, 4'-benzidine, 3,3'-dimethoxy-4,4'-benzidine; 1,5-diaminonaphthalene, 1,2-diaminonaphthalene; 1,2-diaminopurine Any compound having two or more amine groups, which is a group of 2,6-diaminopyridinium; 3,4-diamino-benzophenone; 2,6-diaminopyridine (representative formula: H ₂ N-Ar-NH ₂ ) a diazonium formed by diazotization, and the salt is selected as a coupling component selected from 2-hydroxy-11H-benzo[a]-carbazolyl-3 -aniline, 2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxy-p-anisidine, 2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxy- (2-Methyl)-p-anisidine aniline, 2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxy-N-benzimidazolone (benzimidazolone-5-nonylamine, 2-hydroxy- Any one of the group of 11H-benzo[a]-carbazolyl-3-carboxy-naphthyldecylamine 2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxylic acid aryl decylamine ( Abbreviated as HBC) formed by azo/coupling [HBC-N=NA a structure shown by rN=N-HBC]; (2) as a diazo component, which is selected from 1,4-phenylenediamine, 2-chloro-1,4-phenylenediamine, 2,5 -dichloro-1,4-phenylenediamine, 2-chloro-5-methyl-1,4-phenylenediamine, 2,5-dimethyl-1,4-phenylenediamine , 2-nitro-1,4-phenylenediamine; 1,3-phenylenediamine, 4-chloro-1,3-phenylenediamine, 4-methoxy-1,3- Phenyldiamine, 4-nitro-1,3-phenylenediamine; 4-chloro-1,2-phenylenediamine, 4,5-dimethyl-1,2-phenylene Diamine, 4-nitro-1,2-phenylenediamine; 3,3'-dichloro-4,4'-benzidine, 2,2',5,5'-tetrachloro-4,4 '-Biphenylamine, 3,3'-dimethyl-4,4'-benzidine, 3,3'-dimethoxy-4,4'-benzidine; 1,5-diaminonaphthalene, 1 ,2-diaminonaphthalene; 1,2-diaminopurine, 1,5-diaminoguanidine; 3,4-diamino-benzophenone; group of 2,6-diaminopyridine Any one of two or more amine groups (representative formula: H ₂ N-Ar-NH ₂ ) is diazotized to form a diazonium salt, and the salt is selected as a coupling component selected from 2-hydroxy- 11H-benzo[a]-carbazolyl-3-aniline, 2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxy-p-anisidine, 2-hydroxy-11H -Benzo[a]-carbazolyl-3-carboxy-(2-methyl)-p-anisidine, 2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxy-N-benzo Any one of the group of imidazolidin-5-nonylamine, 2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxy-naphthyldecylamine 2-hydroxy-11H-benzo[a]-indole Azolyl-3-carboxylic acid aryl decylamine (abbreviated as HBC) and other than the compound selected from the group consisting of CIAzoic Coupling Component 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-naphthoic acid- N-benzimidazolone-5-decylamine, 2-hydroxy-3-naphthoic acid-N-phthalimido-4-amine, 5'-chloro-3-hydroxy-2', 3' a structure represented by [HBC-N=N-Ar-N=N-Cp] formed by azo/coupling of any other diene component (denoted as Cp) of a group of dimethoxy-naphthylaniline aniline (3) in its molecule, for a phenyl group having two or more 2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxylic acid decylamine residues (abbreviated as HBC-) -(1,4-)bis(2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxylic acid carboamide), 2-chloro-phenylene-(1,4-) Bis(2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxylic acid decylamine) 2,5-Dichloro-phenyl-(1,4-)bis(2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxylic acid decylamine), 2-methyl-phenylene Benzyl-(1,4-)bis(2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxylic acid decylamine), phenyl-(4,4'-) bis(2- hydroxy-11H-benzo[a]-carbazolyl-3-carboxylic acid decylamine), 3,3'-dichloro-exobiphenyl-(4,4'-) bis(2-hydroxy-11H- Benzo[a]-carbazolyl-3-carboxylic acid decylamine), stilbene-(1,5-)bis(2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxylic acid Any one of the groups of the indoleamines (denoted as HBC-HBC), which is selected from the CIAzoic Diazo Component as a diazo component, 5, 8, 9, 10, 32, 33, 34 Any of a group of 35, 36, 37, 41, 42, 43, 47 having an amine group (denoted as Ar-NH ₂ ) is subjected to diazotization to form its azo/coupling. Ar-N=N-HBC-HBC-N=N-Ar]; (4) in its molecule, for 2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxylate The acid amide residue (abbreviated as HBC-) and other azo residue residues (expressed as Cp-) other than the compound are selected from the group consisting of phenyl (-1)-(2-hydroxy-11H-benzo[a] - oxazolyl-3-carboxylic acid decylamine) (-4)-(2-hydroxy-3-naphthoic acid decylamine), benzene Base (-1)-(2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxylic acid decylamine) (-4)-(2-hydroxy-3-naphthoic acid decylamine), (2 -Methyl-)phenyl (-1)-(2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxylic acid decylamine) (-4)-(2-hydroxy-3-naphthalene) Benzyl formate), phenyl (-4)-(2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxylic acid decylamine) (-4')-(2-hydroxy-3) Any one of the coupling components (denoted as HBC-Cp) of naphthoic acid decylamine, which is selected from the group consisting of CI azodiagen components 5, 8, 9, 10, 32, 33, 34, 35, 36 as a diazo component Any one of the groups of 37, 41, 42, 43, 47 having an amine group (denoted as Ar-NH ₂ ) is subjected to diazotization to form its azo/coupling [Ar-N= The structure shown by N-HBC-Cp-N=N-Ar]. A method for producing a black azo pigment, which comprises a step of synthesizing a black polyazo pigment of a black azo pigment according to claim 1 of the patent application scope, and a step of preparing the pigment to be fined as needed. It is characterized in that (I) the above-mentioned black polyazo pigment is synthesized by any one of the following (1) to (4): (1) for a group selected from 1,4-phenylenediamine, 2- Chloro-1,4-phenylenediamine, 2,5-dichloro-1,4-phenylenediamine, 2-chloro-5-methyl-1,4-phenylenediamine, 2, 5-dimethyl-1,4-phenylenediamine, 2-nitro-1,4-phenylenediamine; 1,3-phenylenediamine, 4-chloro-1,3-extension Phenyldiamine, 4-methoxy-1,3-phenylenediamine, 4-nitro-1,3-phenylenediamine; 4-chloro-1,2-phenylenediamine, 4,5-Dimethyl-1,2-phenylenediamine, 4-nitro-1,2-phenylenediamine; 3,3'-dichloro-4,4'-benzidine, 2 , 2',5,5'-tetrachloro-4,4'-benzidine, 3,3'-dimethyl-4,4'-benzidine, 3,3'-dimethoxy-4,4 '-benzidine; 1,5-diaminonaphthalene, 1,2-diaminonaphthalene; 1,2-diaminopurine, 1,5-diaminopurine; 3,4-diamine - benzophenone; a group of 2,6-diaminopyridine Any of the diazonium salts formed by diazotization of a compound having two or more amine groups (representative formula: H ₂ N-Ar-NH ₂ ) is selected from 2-hydroxy-11H-benzo[a]-fluorene Azyl-3-aniline, 2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxy-p-anisidine, 2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxyl -(2-methyl)-p-anisidine, 2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxy-N-benzimidazolone-5-decylamine, 2-hydroxy-11H- Any one of the group of benzo[a]-carbazolyl-3-carboxy-naphthyldecylamine 2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxylic acid aryl decylamine (abbreviated as HBC) synthesis method for azo/coupling; (2) synthesis method of polyazo pigment having the following structure: the configuration is selected for 1,4-phenylenediamine, 2-chloro-1 , 4-phenylene diamine, 2,5-dichloro-1,4-phenylenediamine, 2-chloro-5-methyl-1,4-phenylenediamine, 2,5-di Methyl-1,4-phenylenediamine, 2-nitro-1,4-phenylenediamine; 1,3-phenylenediamine, 4-chloro-1,3-phenylene Amine, 4-methoxy-1,3-phenylenediamine, 4-nitro-1,3-phenylenediamine; 4-chloro-1,2-phenylenediamine, 4,5 -Dimethyl-1,2-phenylene diamine, 4- Base-1,2-phenylenediamine; 3,3'-dichloro-4,4'-benzidine, 2,2',5,5'-tetrachloro-4,4'-benzidine, 3 , 3'-dimethyl-4,4'-benzidine, 3,3'-dimethoxy-4,4'-benzidine; 1,5-diaminonaphthalene, 1,2-diamine Naphthalene; 1,2-diaminopurine, 1,5-diaminopurine; 3,4-diamino-benzophenone; any of the 2,6-diaminopyridine groups having two The above amine group compound (representative formula: H ₂ N-Ar-NH ₂ ) is diazotized to form a diazonium salt selected from 2-hydroxy-11H-benzo[a]-carbazolyl-3- Aniline, 2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxy-p-anisidine, 2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxy-(2-A Base)-p-anisidine, 2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxy-N-benzimidazolone-5-decylamine, 2-hydroxy-11H-benzo[a] - 2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxylic acid aryl decylamine (abbreviated as HBC) and the compound of the group of carbazolyl-3-carboxy-naphthyl decylamine Other than the selected from the group consisting of CI azo couples 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-naphthoic acid-N-benzimidazolone-5-decylamine, 2- Any one of a group of 3-naphthoic acid-N-phthalimido-4-meramine, 5'-chloro-3-hydroxy-2',3'-dimethoxy-naphthylaniline aniline Other coupling components (denoted as Cp) are azo/coupled structures; diazonium salts formed by diazotizing a compound having two or more amine groups (representative formula: H ₂ N-Ar-NH ₂ ) The azo/coupling of the coupling component (Cp) of the molar or less is carried out, and two or more coupling components (Cp) are required to separate and remove the polyazo pigment which has been coupled, and then the above-mentioned coupling component is obtained. (HBC) a synthesis method for azo/coupling of an uncoupled diazonium salt group; (3) having two or more 2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxylates in the molecule The acid amide residue (abbreviated as HBC-) is selected from the group consisting of phenyl-(1,4-)bis(2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxylic acid decylamine), 2-chloro-phenyl-(1,4-)bis(2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxylic acid decylamine), 2,5-dichloro-phenylene -(1,4-)bis(2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxylic acid decylamine), 2-methyl-phenylene-(1,4-)bis ( 2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxylic acid decylamine), debiphenyl (4,4'-) bis(2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxylic acid decylamine), 3,3'-dichloro-extended biphenyl-(4,4 '-) bis(2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxylic acid decylamine), stilbene-(1,5-) bis(2-hydroxy-11H-benzo[ Any one of the groups of a]-carbazolyl-3-carboxylic acid decylamine (expressed as HBC-HBC) is selected from the group consisting of CI azodiagen components 5, 8, 9, 10, 32, 33, A method for synthesizing azo/coupling of a diazo component formed by diazotization of a compound having an amine group (Ar-NH ₂ ) in any group of 34, 35, 36, 37, 41, 42, 43, 47 (4) having a 2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxylic acid decylamine residue (abbreviated as HBC-) in one molecule and other coupling residues other than the compound ( Represented as Cp-) selected from the group consisting of phenyl (-1)-(2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxylic acid decylamine) (-4)-(2-hydroxy- (naphthalene 3-naphthoate), phenyl (-1)-(2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxylic acid decylamine) (-4)-(2-hydroxy- (naphthyl 3-naphthoate), (2-methyl-) phenyl (-1)-(2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxylic acid decylamine) (-4 )-(2-hydroxy-3-naphthoic acid decylamine), extended biphenyl (-4)-(2-hydroxy-11H-benzo[a]-carbazolyl-3-carboxylate Any one of the coupling components of (-4')-(2-hydroxy-3-naphthoic acid decylamine) (expressed as HBC-Cp), which is selected from the group consisting of CI azo and diazonium components 5, 8, 9, 10 a diazonium salt formed by diazotization of a compound having an amine group (denoted as Ar-NH ₂ ) of any of the groups 32, 33, 34, 35, 36, 37, 41, 42, 43, 47 An azo/coupling synthesis method; and (II) in the case where the polyazo pigment synthesized by the above method is coarse, having an average particle diameter of the pigment according to any one of the following (1) or (2) Steps of miniaturization to 10 nm to 200 nm: (1) use of ball milling, sanding, attritor, horizontal continuous media disperser, kneader, continuous single-axis kneading machine, continuous two-axis kneading machine, A method for miniaturizing any of the pigment grinders or pigment dispersers selected from the group consisting of a three-roller and an open-roller continuous kneading machine; (2) in a kneading machine, with a water-soluble salt, water-soluble organic as needed The solvent is subjected to a salt-milling method of kneading/grinding together. A colored composition comprising a black azo pigment containing the black azo pigment of claim 1 or a black azo pigment obtained according to the manufacturing method of claim 2 in the liquid dispersion medium or the solid dispersion medium Made of pigment ingredients. The coloring composition of claim 3, wherein the pigment component containing the black azo pigment is used for performing colored chromatic coloring, or achromatic dark or black coloring, which is the black color nitrogen The pigment is used alone or in combination with the black azo pigment and one or more selected from the group consisting of colored pigments, white pigments, other black pigments, and body pigments for correcting the black azo pigment. to make. The colored composition of claim 4, wherein the ratio of the above black azo pigment to the colored pigment, white pigment, other black pigment or body pigment used to modify the black azo pigment is computer-color The comparison system is determined by the optimization method. The coloring composition of claim 3, wherein the liquid dispersion medium comprises a polymer which may also have a reactive group, an oligomer which may also have a reactive group, and a monomer which may also have a reactive group. The at least one film forming material is selected from the body and is either liquid or further contains a solvent and/or water. The colored composition according to claim 3, wherein the solid dispersion medium contains at least one solid dispersion medium selected from the group consisting of a thermoplastic resin, a thermosetting resin, a wax, a fatty acid decylamine, and a fatty acid metal soap. The coloring composition according to any one of claims 3 to 7, wherein the coloring composition is used for coatings, coating agents, plastics, fibers, printing inks, stationery, and image recording. At least one of the uses for use and image display. A method of coloring an article, characterized in that the coloring composition of claim 4 is used when the article is colored black or dark by coloring of the surface of the article or coloring of the article itself. The coloring method of the article of claim 9, wherein the article is composed of a transparent substrate, by self-coating, coating, dyeing, printing, taking notes, drawing, inkjet printing, electronic photo printing Any one of electrostatic printing or photolithographic printing is performed by surface-coloring the transparent substrate, or internally coloring the substrate itself by a kneading method or an impregnation method. The coloring method of the article of claim 10, wherein the surface coloring or the internal coloring is a coloring portion exhibiting a spectral transmittance of about 5% or less in a wavelength range of about 400 to 750 nm in the visible light region. On the other hand, in the infrared region of 900 to 1500 nm, the transmittance is about 30% or more, and the article made of the transparent substrate can have both optical characteristics of visible light blocking and infrared light transmittance. The method of coloring an article according to claim 9 wherein the article itself has light reflectivity or an article provided with a preformed light reflective substrate for the surface of the article or the light reflective substrate Using the above colored composition and applying, coating, attaching, dissolving, laminating, coloring, dyeing, dip dyeing, printing, taking notes, drawing, inkjet printing, electronic photo printing or xerographic printing It shows the color of reflection in the infrared region. A colored article characterized by the method of coloring the article of any one of claims 9 to 12. Solar photovoltaic module rear cover plate, which is attached to light reflective sheet The upper plurality of infrared penetrating layers having a black or dark color layer is characterized in that the infrared penetrating layer contains the black polyazo pigment of the first application of the patent scope. A method for manufacturing a solar panel of a solar power generation module, characterized in that a substrate having a light reflectivity as a light reflective sheet or a substrate provided with a light reflective substrate formed in advance is used as light reflectivity a colored composition comprising the black polyazo pigment of the first aspect of the patent application by coating, coating, attaching, dissolving, laminating, on the surface of the substrate or the light-reflective substrate Printing, inkjet printing, electrophotographic printing, or xerographic printing, which exhibits a reflective color in the infrared region, and a black or dark color infrared penetrating layer is laminated on the light-reflective sheet. 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 the black polyazo pigment of claim 1 of the patent application. The color display panel of claim 16, 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.